WO2011163250A1

WO2011163250A1 - Aqueous polyurethane dispersions

Info

Publication number: WO2011163250A1
Application number: PCT/US2011/041276
Authority: WO
Inventors: Dean C. Webster; Mohammed J. Nasrullah; Richard R. Roesler; Scott D. Allen
Original assignee: Ndsu Research Foundation; Novomer, Inc.
Priority date: 2010-06-21
Filing date: 2011-06-21
Publication date: 2011-12-29

Abstract

In one aspect, the present invention encompasses aqueous polyurethane dispersions (PUDs) comprising aliphatic polycarbonate polyols derived from epoxides and CO₂. In another aspect, the present invention encompasses coating and adhesive compositions derived from the inventive aqueous polyurethane dispersions. In other aspects, the present invention encompasses isocyanate-terminated prepolymers having a plurality of epoxide-CO₂-derived polyol segments linked via urethane bonds formed from reaction with polyisocyanate compounds. Such prepolymers are useful for the manufacture of higher polymers and/or for the formulation of aqueous polyurethane dispersions.

Description

AQUEOUS POLYURETHA E DISPERSIONS

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit of United States provisional application serial number 61/356,939, filed June 21, 2010 the entirety of which is hereby incorporated herein by reference.

FIELD OF THE INVENTION

This invention pertains to novel aqueous polyurethane dispersions incorporating aliphatic polycarbonate polyols, as well as methods of making, formulating and using the novel materials in the fields of coatings and adhesives. Also provided are films and coatings made from the novel PUD, as well as surfaces and articles coated with said films and coatings.

SUMMARY OF THE INVENTION

Aqueous polyurethane dispersions (PUDs) have recently emerged to replace their solvent-based counterparts for a number of applications due to increasing health and environmental awareness. Waterborne PUDs are an important class of polymer dispersion that can be used in many industrial applications such as coatings for wood fimshing; glass fiber sizing; adhesives; automotive topcoats and other applications. Research in the area of polyurethane technology has already spanned many decades and the uses of polyurethanes for coatings applications and efforts to enhance knowledge pertaining to their structure- property relationships continue to expand due to the high performance characteristics of polyurethanes.

The recognition that carbon dioxide is a potential atmospheric pollutant and that rising levels of atmospheric carbon dioxide can cause global climate change has prompted a search for materials whose production, use, and disposal release less carbon dioxide than current processes. Recently, Novomer has developed a novel process for the synthesis of low molecular weight aliphatic polycarbonate polyols from the metal-catalyzed copolymerization of carbon dioxide with epoxides. These polyols have an improved carbon footprint relative to existing materials and can be used as a polyol component in polyurethanes.

In one aspect, the present invention encompasses aqueous polyurethane dispersions (PUDs) comprising aliphatic polycarbonate polyols. In certain embodiments, the inventive PUDs are derived from prepolymers which are constructed from an aliphatic polycarbonate polyol.

In another aspect, the present invention encompasses coating compositions and adhesive compositions derived from the inventive aqueous polyurethane dispersions.

In another aspect, the present invention encompasses isocyanate-terminated prepolymers having a plurality of epoxide-C0₂-derived polyol segments linked via urethane bonds formed from reaction with polyisocyanate compounds. Such prepolymers are useful for the manufacture of higher polymers and/or for the formulation of aqueous polyurethane dispersions.

In certain embodiments, inventive compositions of the invention include isocyanate- functionalized prepolymers of formula:

wherein,

R¹, R², R³, and R⁴ are, at each occurrence in the polymer chain, independently selected from the group consisting of -H, fluorine, an optionally substituted C_1-30 aliphatic group, and an optionally substituted C_1-2o heteroaliphatic group, and an optionally substituted C_6-10 aryl group, where any two or more of R¹, R², R³, and R⁴ may optionally be taken together with mtervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms;

n and n' are each independently an integer from about 3 to about 1,000, and may be the same or different;

y" is, at each occurrence, independently 0 or 1;

-X- is independently at each occurrence -0-, -S-, or -NR-, where R is an optionally

substistuted Q.n aliphatic group; is a multivalent moiety; Β^βΗ represents the carbon skeleton of a diisocyanate;

C ZZI> represents a segment comprising the carbon skeleton of an optionally present coreactant having any combination of hydroxyl-, amino-, carboxyl-, or thio-groups; m is an integer greater than zero; and

p is zero or greater.

In certain embodiments, prepolymers of the present invention incorporate hydropbilic functional groups that aid in forming stable aqueous dispersions from the prepolymers or higher polymers derived from them.

In another aspect, the present invention provides methods of preparing isocyanate- terminated prepolymers, higher polymers, and aqueous polyurethane dispersions

incorporating epoxide-C0₂-derived polycarbonate polyols.

In certain embodiments, methods of the present invention comprise the steps of: a) providing one or more aliphatic polycarbonate polyols of formula PI,

contacting the aliphatic polycarbonate polyol with one or more reagents having a plurality of isocyanate groups, optionally in the presence of one or more coreactants capable of reacting with isocyanate groups, where the coreactants are selected from any of those disclosed herein; and

allowing the polyol to react with the reagent having a plurality of isocyanate groups to form a prepolymer,

wherein, each of R 1 , R 2 , R 3 , R 4 , n, and fa_/ is as defined and described in the classes and subclasses herein;

Y is, at each occurrence, independently -H or the site of attachment to any of the chain-extending moieties described in the classes and subclasses herein; and x and y are each independently an integer from 0 to 6, where the sum of x and y is between 2 and 6.

Definitions

Definitions of specific functional groups and chemical terms are described in more detail below. For purposes of this invention, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75^th Ed., inside cover, and specific functional groups are generally defined as described therein. Additionally, general principles of organic chemistry, as well as specific functional moieties and reactivity, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March March 's Advanced Organic Chemistry, 5^th Edition, John Wiley & Sons, Inc., New York, 2001; Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989; Carruthers, Some Modern Methods of Organic Synthesis, 3^rd Edition, Cambridge University Press, Cambridge, 1987; the entire contents of each of which are incorporated herein by reference.

Certain compounds of the present invention can comprise one or more asymmetric centers, and thus can exist in various stereoisomeric forms, e.g., enantiomers and/or diastereomers. Thus, inventive compounds and compositions thereof may be in the form of an individual enantiomer, diastereomer or geometric isomer, or may be in the form of a mixture of stereoisomers. In certain embodiments, the compounds of the invention are enantiopure compounds. In certain embodiments, mixtures of enantiomers or diastereomers are provided.

Furthermore, certain compounds, as described herein may have one or more double bonds that can exist as either the Z or E isomer, unless otherwise indicated. The invention additionally encompasses the compounds as individual isomers substantially free of other isomers and alternatively, as mixtures of various isomers, e.g., racemic mixtures of enantiomers. In addition to the above-mentioned compounds per se, this invention also encompasses compositions comprising one or more compounds.

As used herein, the term "isomers" includes any and all geometric isomers and stereoisomers. For example, "isomers" include cis- and tr ra-isomers, E- and Z- isomers, R— and S-enantiomers, diastereomers, (D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixtures thereof, as falling within the scope of the invention. For instance, a stereoisomer may, in some embodiments, be provided substantially free of one or more corresponding stereoisomers, and may also be referred to as "stereochemically enriched."

Where a particular enantiomer is preferred, it may, in some embodiments be provided substantially free of the opposite enantiomer, and may also be referred to as "optically enriched." "Optically enriched," as used herein, means that the compound or polymer is made up of a significantly greater proportion of one enantiomer. In certain embodiments the compound is made up of at least about 90% by weight of a preferred enantiomer. In other embodiments the compound is made up of at least about 95%, 98%, or 99% by weight of a preferred enantiomer. Preferred enantiomers may be isolated from racemic mixtures by any method known to those skilled in the art, including chiral high pressure liquid

chromatography (HPLC) and the formation and crystallization of chiral salts or prepared by asymmetric syntheses. See, for example, Jacques, et al., Enantiomers, Racemates and Resolutions (Wiley Interscience, New York, 1981); Wilen, S.H., et al, Tetrahedron 33:2725 (1977); Eliel, E.L. Stereochemistry of Carbon Compounds (McGraw-Hill, NY, 1962);

Wilen, S.H. Tables of Resolving Agents and Optical Resolutions p. 268 (E.L. Eliel, Ed., Univ. of Notre Dame Press, Notre Dame, IN 1972).

The term "epoxide", as used herein, refers to a substituted or unsubstituted oxirane. Such substituted oxiranes include monosubstituted oxiranes, disubstituted oxiranes, trisubstituted oxiranes, and tetrasubstituted oxiranes. Such epoxides may be further optionally substituted as defined herein. In certain embodiments, epoxides comprise a single oxirane moiety. In certain embodiments, epoxides comprise two or more oxirane moieties.

The term "polymer", as used herein, refers to a molecule of high relative molecular mass, the structure of which comprises the multiple repetition of units derived, actually or conceptually, from molecules of low relative molecular mass. In certain embodiments, a polymer is comprised of substantially alternating units derived from C0₂ and an epoxide (e.g., poly(ethylene carbonate). In certain embodiments, a polymer of the present invention is a copolymer, terpolymer, heteropolymer, block copolymer, or tapered heteropolymer incorporating two or more different epoxide monomers. With respect to the structural depiction of such higher polymers, the convention of showing enchainment of different monomer units or polymer blocks separated by a slash may be used herein:

These structures are to be interpreted to encompass copolymers incorporating any ratio of the different monomer units depicted unless otherwise specified. This depiction is also meant to represent random, tapered, block co-polymers, and combinations of any two or more of these and all of these are implied unless otherwise specified.

The terms "halo" and "halogen" as used herein refer to an atom selected from fluorine (fluoro, -F), chlorine (chloro, -CI), bromine (bromo, -Br), and iodine (iodo, -I).

The term "aliphatic" or "aliphatic group", as used herein, denotes a hydrocarbon moiety that may be straight-chain (i.e., unbranched), branched, or cyclic (including fused, bridging, and spiro-fused polycyclic) and may be completely saturated or may contain one or more units of unsaturation, but which is not aromatic. Unless otherwise specified, aliphatic groups contain 1-40 carbon atoms. In certain embodiments, aliphatic groups contain 1-20 carbon atoms. In certain embodiments, aliphatic groups contain 3-20 carbon atoms. In certain embodiments, aliphatic groups contain 1-12 carbon atoms. In certain embodiments, aliphatic groups contain 1-8 carbon atoms. In certain embodiments, aliphatic groups contain 1-6 carbon atoms. In some embodiments, aliphatic groups contain 1-5 carbon atoms, in some embodiments, aliphatic groups contain 1-4 carbon atoms, in some embodiments aliphatic groups contain 1-3 carbon atoms, and in some embodiments aliphatic groups contain 1 or 2 carbon atoms. Suitable aliphatic groups include, but are not limited to, linear or branched, alkyl, alkenyl, and alkynyl groups, and hybrids thereof such as

(cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.

The term "heteroaliphatic," as used herein, refers to aliphatic groups wherein one or more carbon atoms are independently replaced by one or more atoms selected from the group consisting of oxygen, sulfur, nitrogen, or phosphorus. In certain embodiments, one to six carbon atoms are independently replaced by one or more of oxygen, sulfur, nitrogen, or phosphorus. Heteroaliphatic groups may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and include saturated, unsaturated or partially unsaturated groups. As used herein, the term "bivalent C_1-8 (or Ci_-3) saturated or unsaturated, straight or branched, hydrocarbon chain", refers to bivalent alkyl, alkenyl, and alkynyl, chains that are straight or branched as defined herein.

The term "unsaturated", as used herein, means that a moiety has one or more double or triple bonds.

The terms "cycloaliphatic", "carbocycle", or "carbocyclic", used alone or as part of a larger moiety, refer to a saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic ring systems, as described herein, having from 3 to 12 members, wherein the aliphatic ring system is optionally substituted as defined above and described herein.

Cycloaliphatic groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, norbornyl, adamantyl, and cyclooctadienyl. In some embodiments, the cycloalkyl has 3-6 carbons. The terms "cycloaliphatic", "carbocycle" or "carbocyclic" also include aliphatic rings that are fused to one or more aromatic or nonaromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, where the radical or point of attachment is on the aliphatic ring. In certain embodiments, the term "3- to 7-membered carbocycle" refers to a 3- to 7-membered saturated or partially unsaturated monocyclic carbocyclic ring. In certain embodiments, the term "3- to 8-membered carbocycle" refers to a 3- to 8-membered saturated or partially unsaturated monocyclic carbocyclic ring. In certain embodiments, the terms "3- to 14-membered carbocycle" and "C_3-14 carbocycle" refer to a 3- to 8-membered saturated or partially unsaturated monocyclic carbocyclic ring, or a 7- to 14-membered saturated or partially unsaturated polycyclic carbocyclic ring.

The term "alkyl," as used herein, refers to saturated, straight- or branched-chain hydrocarbon radicals derived from an aliphatic moiety containing between one and six carbon atoms by removal of a single hydrogen atom. Unless otherwise specified, alkyl groups contain 1-12 carbon atoms. In certain embodiments, alkyl groups contain 1-8 carbon atoms. In certain embodiments, alkyl groups contain 1-6 carbon atoms. In some embodiments, alkyl groups contain 1-5 carbon atoms, in some embodiments, alkyl groups contain 1-4 carbon atoms, in some embodiments alkyl groups contain 1-3 carbon atoms, and in some embodiments alkyl groups contain 1-2 carbon atoms. Examples of alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec- butyl, sec-pentyl, iso-pentyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-decyl, n-undecyl, dodecyl, and the like.

The term "alkenyl," as used herein, denotes a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon double bond by the removal of a single hydrogen atom. Unless otherwise specified, alkenyl groups contain 2-12 carbon atoms. In certain embodiments, alkenyl groups contain 2-8 carbon atoms. In certain embodiments, alkenyl groups contain 2-6 carbon atoms. In some embodiments, alkenyl groups contain 2-5 carbon atoms, in some embodiments, alkenyl groups contain 2-4 carbon atoms, in some embodiments alkenyl groups contain 2-3 carbon atoms, and in some embodiments alkenyl groups contain 2 carbon atoms. Alkenyl groups include, for example, ethenyl, propenyl, butenyl, l-methyl-2-buten-l-yl, and the like.

The term "alkynyl," as used herein, refers to a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon triple bond by the removal of a single hydrogen atom. Unless otherwise specified, alkynyl groups contain 2-12 carbon atoms. In certain embodiments, alkynyl groups contain 2-8 carbon atoms. In certain embodiments, alkynyl groups contain 2-6 carbon atoms. In some embodiments, alkynyl groups contain 2-5 carbon atoms, in some embodiments, alkynyl groups contain 2-4 carbon atoms, in some embodiments alkynyl groups contain 2-3 carbon atoms, and in some embodiments alkynyl groups contain 2 carbon atoms. Representative alkynyl groups include, but are not limited to, ethynyl, 2-propynyl (propargyl), 1-propynyl, and the like.

The term "alkoxy", as used herein refers to an alkyl group, as previously defined, attached to the parent molecule through an oxygen atom. Examples of alkoxy, include but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy, and n-hexoxy.

The term "acyl", as used herein, refers to a carbonyl-containing functionality, e.g., - C(=0)R , wherein R is hydrogen or an optionally substituted aliphatic, heteroaliphatic, heterocyclic, aryl, heteroaryl group, or is a substituted (e.g., with hydrogen or aliphatic, heteroaliphatic, aryl, or heteroaryl moieties) oxygen or nitrogen containing functionality (e.g. , forming a carboxylic acid, ester, or amide functionality). The term "acyloxy", as used here, refers to an acyl group attached to the parent molecule through an oxygen atom. The term "aryl" used alone or as part of a larger moiety as in "aralkyl", "aralkoxy", or "aryloxyalkyl", refers to monocyclic and polycyclic ring systems having a total of five to 20 ring members, wherein at least one ring in the system is aromatic and wherein each ring in the system contains three to twelve ring members. The term "aryl" may be used

interchangeably with the term "aryl ring". In certain embodiments of the present invention, "aryl" refers to an aromatic ring system which includes, but is not limited to, phenyl, biphenyl, naphthyl, anthracyl and the like, which may bear one or more substituents. Also included within the scope of the term aryl", as it is used herein, is a group in which an aromatic ring is fused to one or more additional rings, such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl, phenantriidinyl, or tetrahydronaphthyl, and the like. In certain embodiments, the terms "6- to 10-membered aryl" and "C_6-io aryl" refer to a phenyl or an 8- to 10-membered polycyclic aryl ring.

The terms "heteroaryl" and "heteroar-", used alone or as part of a larger moiety, e.g., "heteroaralkyl", or "heteroaralkoxy", refer to groups having 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms; having 6, 10, or 14 π electrons shared in a cyclic array; and having, in addition to carbon atoms, from one to five heteroatoms. The term "heteroatom" refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen. Heteroaryl groups include, without limitation, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, benzofuranyl and pteridinyl. The terms "heteroaryl" and "heteroar-", as used herein, also include groups in which a heteroaromatic ring is fused to one or more aryl, cycloaliphatic, or heterocyclyl rings, where the radical or point of attachment is on the heteroaromatic ring. Nonlimiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-l,4-oxazin-3(4H)-one. A heteroaryl group may be mono- or bicyclic. The term "heteroaryl" may be used interchangeably with the terms "heteroaryl ring", "heteroaryl group", or "heteroaromatic", any of which terms include rings that are optionally substituted. The term "heteroaralkyl" refers to an alkyl group substituted by a heteroaryl, wherein the alkyl and heteroaryl portions independently are optionally substituted. In certain embodiments, the term "5- to 10-membered heteroaryl" refers to a 5- to 6-membered heteroaryl ring having 1 to 3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8- to 10-membered bicyclic heteroaryl ring having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur. In certain

embodiments, the term "5- to 12-membered heteroaryl" refers to a 5- to 6-membered heteroaryl ring having 1 to 3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8- to 12-membered bicyclic heteroaryl ring having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

As used herein, the terms "heterocycle", "heterocyclyl", "heterocyclic radical", and

"heterocyclic ring" are used interchangeably and refer to a stable 5- to 7-membered monocyclic or 7-14-membered polycyclic heterocyclic moiety that is either saturated or partially unsaturated, and having, in addition to carbon atoms, one or more, preferably one to four, heteroatoms, as defined above. When used in reference to a ring atom of a heterocycle, the term "nitrogen" includes a substituted nitrogen. As an example, in a saturated or partially unsaturated ring having 0-3 heteroatoms selected from oxygen, sulfur or nitrogen, the nitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl), or ^"* JR (as in TV-substituted pyrrolidinyl). In some embodiments, the term "3- to 7-membered

heterocyclic" refers to a 3- to 7-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 heteroatoms independently selected from nitrogen, oxygen, or sulfur. In some embodiments, the term "3- to 12-membered heterocyclic" refers to a 3- to 8- membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or a 7- to 12-membered saturated or partially unsaturated polycyclic heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

A heterocyclic ring can be attached to its pendant group at any heteroatom or carbon atom that results in a stable structure and any of the ring atoms can be optionally substituted. Examples of such saturated or partially unsaturated heterocyclic radicals include, without limitation, tetrahy&ofuranyl, tetrahydrothienyl, pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl, and quinuclidinyl. The terms "heterocycle", "heterocyclyl", "heterocyclyl ring", "heterocyclic group", "heterocyclic moiety", and "heterocyclic radical", are used interchangeably herein, and also include groups in which a heterocyclyl ring is fused to one or more aryl, heteroaryl, or cycloaliphatic rings, such as indolinyl, 3H-indolyl, chromanyl, phenanthridinyl, or tetrahydroquinolinyl, where the radical or point of attachment is on the heterocyclyl ring. A heterocyclyl group may be mono- or bicyclic. The term "heterocyclylalkyl" refers to an alkyl group substituted by a heterocyclyl, wherein the alkyl and heterocyclyl portions

independently are optionally substituted.

As used herein, the term "partially unsaturated" refers to a ring moiety that includes at least one double or triple bond. The term "partially unsaturated" is intended to encompass rings having multiple sites of unsaturation, but is not intended to include aryl or heteroaryl moieties, as herein defined.

As described herein, compounds of the invention may contain "optionally

substituted" moieties. In general, the term "substituted", whether preceded by the term "optionally" or not, means that one or more hydrogens of the designated moiety are replaced with a suitable substituent. Unless otherwise indicated, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position. Combinations of substituents envisioned by this invention are preferably those that result in the formation of stable or chemically feasible compounds. The term "stable", as used herein, refers to compounds that are not substantially altered when subjected to conditions to allow for their production, detection, and, in certain embodiments, their recovery, purification, and use for one or more of the purposes disclosed herein.

Suitable monovalent substituents on a substitutable carbon atom of an "optionally substituted" group are independently halogen; -(CH₂)₀_₄R°; -(CH₂)₀_₄OR°; -O-(CH₂)₀_ ₄C(0)OR°; -(CH₂)(MCH(0R^O)₂;

-(CH₂)(_MPh, which may be substituted with R°; -(CH₂)_(M0(CH₂)o-₁Ph which may be substituted with R°; -CH=CHPh, which may be substituted with R°; -N0₂; -CN; -N₃; -{CH₂)_(MN(R⁰)₂; -(CH₂){MN(R°)C(0)R°; - N(R°)C(S)R°; -<CH₂)(MN(R^O)C(0)NR°₂; -N(R°)C(S)NR°₂; -(CH₂)( N(R^O)C(0)0R^O; - N(R°)N(R°)C(0)R°; -N(R°)N(R°)C(0)NR°₂; -N(R°)N(R°)C(0)OR°; -(CH₂)_(MC(0)R⁰; - C(S)R°; -(CH₂)( C(0)0R^o; -(CH₂)₀-₄C(O)N(R°)₂; -(CH₂)(MC(0)SR⁰; -(CH₂)O_

4C(0)OSiR°₃; -(CH₂)(MOC(0)R⁰; -OC(0)(CH₂)(MSR- SC(S)SR°; -(CH₂)(MSC(0)R°; - (CH₂)( C(0)NR°₂; -C(S)NR°₂; -C(S)SR°; -SC(S)SR°, -(CH₂)( OC(0)NR°₂; - C(0)N(OR°)R°; -C(0)C(0)R°; -C(0)CH₂C(0)R°; -C(NOR°)R°; -(CH₂)( SSR⁰; -(CH₂)O- ₄S(0)₂R°; -(CH₂)(MS(0)₂OR⁰; -(CH₂)(MOS(0)₂R°; -S(0)₂NR°₂; -(CH₂)₍ S(0)R⁰; - N(R°)S(0)₂ R°₂; -N(R°)S(0)₂R°; -N(OR°)R°; -C(NH)NR°₂; -P(0)₂R°; -P(0)R°₂; - OP(0)R°₂; -OP(0)(OR°)₂; SiR°₃; -(C_M straight or branched alkylene)0-N(R°)₂; or -(C_M straight or branched alkylene)C(0)0-N(R°)₂, wherein each R° may be substituted as defined below and is independently hydrogen, C_\-_& aliphatic, -CH₂Ph, -0(CH₂)o_iPh, or a 5-6- membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms

independently selected from nitrogen, oxygen, or sulfur, or, notwithstanding the definition above, two independent occurrences of R°, taken together with their intervening atom(s), form a 3-12-membered saturated, partially unsaturated, or aryl mono- or polycyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, which may be substituted as defined below.

Suitable monovalent substituents on R° (or the ring formed by taking two

independent occurrences of R° together with their intervening atoms), are independently halogen, -(CH₂)o_₂R^e, -(haloR^e), -(CH₂)o_₂OH, -(CH^OR*, -<CH₂)₀_₂CH(OR^e)₂; - 0(haloR^e), -CN, -N₃, -CCH₂)o-₂C(0)R^e, -(CH₂)o-₂C(0)OH, -(CH₂)o-₂C(0)OR°, -(CH₂)o_ ₄C(0)N(R°)₂; -(CH₂)o_₂SR^e, - CH₂)o_₂SH, -(CH₂)o_₂NH₂, -(CH₂)₀_₂NHR*, -CCH₂)o-2NR*2, -N0₂, -SiR*₃, -OSiR'₃, -C(0)SR^e -(C_1-4 straight or branched alkylene)C(0)OR^e, or - SSR^e wherein each R* is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently selected from C^ aliphatic, -CH₂Ph, -0(CH₂)o_ tPh, or a 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur. Suitable divalent substituents on a saturated carbon atom of R° include =0 and =S.

Suitable divalent substituents on a saturated carbon atom of an "optionally substituted" group include the following: =0, =S, =NNR^* ₂, =NNHC(0)R^*, =NNHC(0)OR^*, =NNHS(0)₂R^*, =NR^*, =NOR^*, -0(C(R^* ₂))₂_₃0- or -S(C(R^* ₂))₂_₃S- wherein each independent occurrence of R* is selected from hydrogen, C^ aliphatic which may be substituted as defined below, or an unsubstituted 5-6-mernbered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur. Suitable divalent substituents that are bound to vicinal substitutable carbons of an "optionally substituted" group include: -0(CR*₂)2-30- wherein each independent occurrence of R^* is selected from hydrogen, d-6 aliphatic which may be substituted as defined below, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

Suitable substituents on the aliphatic group of R^* include halogen, -R^e, -(haloR*), - OH, -OR^e, -0(haloR^e), -CN, -C(0)OH, -C(0)OR^e, -NH₂, -NHR", -NR^e ₂, or -N0₂, wherein each R⁹ is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently Ci~4 aliphatic, -CH₂Ph, -0(CH₂)o_iPh, or a 5-6- membered saturated, partially unsaturated, or aryl ring having 0^ heteroatoms

independently selected from nitrogen, oxygen, or sulfur.

Suitable substituents on a substitutable nitrogen of an "optionally substituted" group include -R^†, -NR^† ₂, -C(0)R^†, -C(0)OR^†, -C(0)C(0)R^†, -C(0)CH₂C(0)R^†, -S(0)₂R^†, - S(0)₂NR^† ₂, -C(S)NR^† ₂, -C(NH)NR^† ₂, or -N(R^†)S(0)₂R^†; wherein each R^† is independently hydrogen, Ci_6 aliphatic which may be substituted as defined below, unsubstituted -OPh, or an unsubstituted 5-6-membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or, notwithstanding the definition above, two independent occurrences of R^, taken together with their intervening atom(s) form an unsubstituted 3-12-membered saturated, partially unsaturated, or aryl mono- or bicyclic ring having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur.

Suitable substituents on the aliphatic group of R^† are independently halogen, -R*, -

(haloR*), -OH, -OR', -0(haloR^e), -CN, -C(0)OH, -C(0)OR^e, -NH₂, -NHR", -NR^e ₂, or - N0₂, wherein each R^e is unsubstituted or where preceded by "halo" is substituted only with one or more halogens, and is independently d- aliphatic, -CH₂Ph, -O(CH₂)₀-₁Ph, or a 5-6- membered saturated, partially unsaturated, or aryl ring having 0-4 heteroatoms

independently selected from nitrogen, oxygen, or sulfur. When substituents are described herein, the term "radical" or "optionally substituted radical" is sometimes used. In this context, "radical" means a moiety or functional group having an available position for attachment to the structure on which the substituent is bound. In general the point of attachment would bear a hydrogen atom if the substituent were an independent neutral molecule rather than a substituent. The terms "radical" or "optionally- substituted radical" in this context are thus interchangeable with "group" or "optionally- substituted group".

As used herein, the "term head-to-tail" or "HT", refers to the regiochemistry of adjacent repeating units in a polymer chain. For example, in the context of poly(propylene carbonate) (PPC), the term head-to-tail based on the three regiochemical possibilities depicted below:

The term head-to-tail ratio (H:T) refers to the proportion of head-to-tail linkages to the sum of all other regiochemical possibilities. With respect to the depiction of polymer structures, while a specific regiochemical orientation of monomer units may be shown in the

representations of polymer structures herein, this is not intended to limit the polymer structures to the regiochemical arrangement shown but is to be interpreted to encompass all regiochemical arrangements including that depicted, the opposite regiochemistry, random mixtures, isotactic materials, syndiotactic materials, racemic materials, and/or

enantioenriched materials and combinations of any of these unless otherwise specified.

As used herein the term "alkoxylated" means that one or more functional groups on a molecule (usually the functional group is an alcohol, amine, or carboxylic acid, but is not strictly limited to these) has appended to it a hydroxy-terminated alkyl chain. Alkoxylated compounds may comprise a single alkyl group or they may be oligomeric moieties such as hydroxyl-terminated polyethers. Alkoxylated materials can be derived from the parent compounds by treatment of the functional groups with epoxides.

Unless otherwise specified, "a," "an," "the," and "at least one" are used

interchangeably and mean one or more than one.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 shows the reduced modulus of PUD films on microscope slide cured at room- temperature followed by an overnight heat treatment at 70 °C.

Figure 2 shows the hardness of PUD films on microscope slide cured at room-temperature followed by an overnight heat treatment at 70 °C.

Figure 3 shows the Tg from dynamic mechanical analysis (DMA) for the room-temperature cured PUD films.

Figure 4 shows the storage modulus from DMA for the room-temperature cured PUD films. Figure 5 shows the MALDI-TOF mass spectrum of PE170HNA.

Figure 6 shows the MALDI-TOF mass spectrum of Des C2100.

Figure 7 shows the MALDI-TOF mass spectrum of Des C2200.

Figure 8 shows the MALDI-TOF mass spectrum of NOV 7E21.

Figure 9 shows the MALDI-TOF mass spectrum of NOV 94B0.

Figure 10 shows the MALDI-TOF mass spectrum of NOV 7DF1.

Figure 11 shows the Tg of the PUD films cured at RT and 70 °C.

Figure 12 shows the water and MI contact angles and surface energies for PUD coatings cured at room temperature.

Figure 13 shows the water and methylene iodide (MI) contact angles and surface energies for PUD coatings cured at room temperature followed by 70 °C overnight.

Figure 14 shows the nanoindentation of PUD films on microscope slide cured at room

temperature and at 70 °C.

Figure 15 shows the storage modulus at 25 °C from DMA for the room temperature cured PUD films

Figure 16 shows the Tg from DMA for the room temperature cured PUD films

Figure 17 shows the Konig Pendulum Hardness for the RT and 70 °C cured PUD films on aluminum panel. DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS

I. Polyurethane dispersions

In one aspect, the present invention provides novel polyurethane dispersions created from aliphatic polycarbonate polyols. In certain embodiments, the polyurethane dispersions comprise chain-extended compositions formed by reaction of the aliphatic polycarbonate polyols with one or more isocyanate reagents selected from the group consisting of diisocyanates, triisocyanates, higher polyisocyanates, mixtures of any two or more of these, and derivatives or oligomers of any of these including, but not limited to acylurea- isocyanates, biurets, and allophanates. In certain embodiments, the chain-extended compositions incorporate additional segments derived from coreactants such as other polyols, polyhydric alcohols, amines, thiols, and carboxylic acids or functionalized analogs of any of these.

In certain embodiments, compositions of the present invention encompass

prepolymers formed by reaction of aliphatic polycarbonate polyols with reagents comprising di- or poly-isocyanates and, optionally, one or more coreactants. Before fully describing the prepolymer compositions, each of the components (the aliphatic polycarbonate polyols, the isocyanate reagents, and the optionally-present coreactants) will be described.

A. Aliphatic Polycarbonate Polyols

This section describes some of the aliphatic polycarbonate polyols that have utility in making compositions of the present invention. In certain embodiments, compositions of the present invention comprise aliphatic polycarbonate polyols derived from the

copolymerization of one or more epoxides and carbon dioxide. Examples of suitable polyols, as well as methods of making them are disclosed in WO2010/028362 A 1 the entirety of which is incorporated herein by reference.

It is advantageous for many of the embodiments described herein that the aliphatic polycarbonate polyol used have a high percentage of reactive end groups. Such reactive end- groups are typically hydroxyl groups, but other reactive functional groups may be present if the polyols are treated post-polymerization to modify the chemistry of the end groups. In certain embodiments, at least 90% of the end groups of the polycarbonate polyol used are -OH groups. In certain embdodiments, at least 95%, at least 96%, at least 97% or at least 98% of the end groups of the polycarbonate polyol used are -OH groups. In certain embodiments, more than 99%, more than 99.5%, more than 99.7%, or more than 99.8% of the end groups of the polycarbonate polyol used are -OH groups. In certain embodiments, more than 99.9% of the end groups of the polycarbonate polyol used are -OH groups.

In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and one epoxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and propylene oxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and ethylene oxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and cyclohexene oxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and cyclopentene oxide. In certain embodiments, aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and 3 -vinyl cyclohexane oxide.

In embodiments, the aliphatic polycarbonate chains comprise a copolymer of carbon dioxide and propylene oxide along with one or more additional epoxides selected from the group consisting of ethylene oxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3 -vinyl cyclohexene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers, styrene oxides, and epoxides of higher alpha olefins. In certain embodiments, such terpolymers contain a majority of repeat units derived from propylene oxide with lesser amounts of repeat units derived from one or more additional epoxides. In certain embodiments, terpolymers contain about 50% to about 99.5% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 60% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 75% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 80% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 85% propylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 90% propylene oxide- derived repeat units. In certain embodiments, terpolymers contain greater than 95% propylene oxide-derived repeat units. In certain embodiments, aliphatic polycarbonate chains comprise a terpolymer of carbon dioxide and ethylene oxide along with one or more additional epoxides selected from the group consisting of propylene oxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3 -vinyl cyclohexene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers, styrene oxides, and epoxides of higher alpha olefins. In certain embodiments, such terpolymers contain a majority of repeat units derived from ethylene oxide with lesser amounts of repeat units derived from one or more additional epoxides. In certain embodiments, terpolymers contain about 50% to about 99.5% ethylene oxide-derived repeat units. In certain

embodiments, terpolymers contain greater than about 60% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 75% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 80% ethylene oxide- derived repeat units. In certain embodiments, terpolymers contain greater than 85% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 90% ethylene oxide-derived repeat units. In certain embodiments, terpolymers contain greater than 95% ethylen oxide-derived repeat units.

In certain embodiments, in the polymer compositions described hereinabove, aliphatic polycarbonate chains have a number average molecular weight (M„) in the range of 500 g/mol to about 250,000 g/mol.

In certain embodiments, aliphatic polycarbonate chains have an M„ less than about 100,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ less than about 70,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ less than about 50,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ between about 500 g/mol and about 40,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ less than about 25,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ between about 500 g/mol and about 20,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ between about 500 g/mol and about 10,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ between about 500 g/mol and about 5,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ between about 1,000 g/mol and about 5,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ between about 5,000 g/mol and about 10,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ between about 500 g/mol and about 1 ,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ between about 1,000 g/mol and about 3,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ of about 5,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ of about 4,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ of about 3,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ of about 2,500 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ of about 2,000 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ of about 1,500 g/mol. In certain embodiments, aliphatic polycarbonate chains have an M„ of about 1,000 g/mol.

In certain embodiments, the aliphatic polycarbonate polyols used are characterized in that they have a narrow molecular weight distribution. This can be indicated by the polydispersity indices (POT) of the aliphatic polycarbonate polymers. In certain

embodiments, aliphatic polycarbonate compositions have a PDI less than 2. In certain embodiments, aliphatic polycarbonate compositions have a PDI less than 1.8. In certain embodiments, aliphatic polycarbonate compositions have a PDI less than 1.5. In certain embodiments, aliphatic polycarbonate compositions have a PDI less than 1.4. In certain embodiments, aliphatic polycarbonate compositions have a PDI between about 1.0 and 1.2. In certain embodiments, aliphatic polycarbonate compositions have a PDI between about 1.0 and 1.1.

In certain embodiments aliphatic polycarbonate compositions of the present invention comprise substantially alternating polymers containing a high percentage of carbonate linkages and a low content of ether linkages. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the

composition, the percentage of carbonate linkages is 85% or greater. In certain

embodiments, aliphatic polycarbonate compositions of the present invention are

characterized in that, on average in the composition, the percentage of carbonate linkages is 90% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 91 % or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the

composition, the percentage of carbonate linkages is 92% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are

characterized in that, on average in the composition, the percentage of carbonate linkages is 93% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 94% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the

composition, the percentage of carbonate linkages is 95% or greater. In certain

embodiments, aliphatic polycarbonate compositions of the present invention are

characterized in that, on average in the composition, the percentage of carbonate linkages is 96% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 97% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the

composition, the percentage of carbonate linkages is 98% or greater. In certain

embodiments, aliphatic polycarbonate compositions of the present invention are

characterized in that, on average in the composition, the percentage of carbonate linkages is 99% or greater. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that, on average in the composition, the percentage of carbonate linkages is 99.5% or greater. In certain embodiments, the percentages above exclude ether linkages present in polymerization initiators or chain transfer agents and refer only to the linkages formed during epoxide C0₂ copolymerization. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that they contain essentially no ether linkages either within the polymer chains derived from epoxide C0₂ copolymerization or within any polymerization intiators, chain transfer agents or end groups that may be present in the polymer. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that they contain, on average, less than one ether linkage per polymer chain within the composition. In certain embodiments, aliphatic polycarbonate compositions of the present invention are characterized in that they contain essentially no ether linkages.

In certain embodiments where an aliphatic polycarbonate is derived from mono- substituted epoxides (e.g. such as propylene oxide, 1,2-butylene oxide, epichlorohydrin, epoxidized alpha olefins, or a glycidol derivative), the aliphatic polycarbonate is

characterized in that it is regioregular. Regioregularity may be expressed as the percentage of adjacent monomer units that are oriented in a head-to-tail arrangement within the polymer chain. In certain embodiments, aliphatic polycarbonate chains in the inventive polymer compositions have a head-to-tail content higher than about 80%. In certain embodiments, the head-to-tail content is higher than about 85%. In certain embodiments, the head-to-tail content is higher than about 90%. In certain embodiments, the head-to-tail content is greater than about 91%, greater than about 92%, greater than about 93%, greater than about 94%, or greater than about 95%. In certain embodiments, the head-to-tail content of the polymer is as determined by proton or carbon- 13 NMR spectroscopy.

In certain embodiments, compositions of the present invention comprise aliphatic polycarbonate polyols having a structure PI:

wherein,

R¹, R², R³, and R⁴ are, at each occurrence in the polymer chain, independently selected from the group consisting of -H, fluorine, an optionally substituted C_1-30 aliphatic group, and an optionally substituted C_1-20 heteroaliphatic group, and an optionally substituted C₆-₁₀ aryl group, where any two or more of R¹, R², R³, and R⁴ may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms;

Y is, at each occurrence, independently -H or the site of attachment to any of the chain- extending moieties described in the classes and subclasses herein;

n is at each occurrence, independently an integer from about 3 to about 1,000; is a multivalent moiety; and

x and y are each independently an integer from 0 to 6, where the sum of x and > is

between 2 and 6. In certain embodiments, the multivalent moiety _/ embedded within the aliphatic polycarbonate chain is derived from a polyfunctional chain transfer agent having two or more sites from which epoxide/C0₂ copolymerization can occur. In certain embodiments, such copolymerizations are performed in the presence of polyfunctional chain transfer agents as exemplified in published PCT application WO 2010/028362.

In certain embodiments, a polyfunctional chain transfer agent has a formula:

wherein each of

_, x, mdy is as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains in the inventive polymer compositions are derived from the copolymerization of one or more epoxides with carbon dioxide in the presence of such polyfunctional chain transfer agents as shown in Scheme 2:

Scheme 2

In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with a structure P2:

P2 wherein each of R 1 , R 2 , R 3 , R 4 , Y, and « is as defined above and described in the classes and subclasses herein.

In certain embodiments where aliphatic polycarbonate chains have a structure P2, » is derived from a dihydric alcohol. In such instances represents the carbon- containing backbone of the dihydric alcohol, while the two oxygen atoms adjacent to G ^—) are derived from the -OH groups of the diol. For example, if the polyfunctional chain transfer agent were ethylene glycol, then G_/) would be -CH₂CH₂- and P2 would have the following

In c

ertain embodiments where is derived from a dihydric alcohol, the dihydric alcohol comprises a C_2-40 diol. In certain embodiments, the dihydric alcohol is selected from the group consisting of: 1 ,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-l,3-diol, 2-butyl-2- ethylpropane-l,3-diol, 2-methyl-2,4-pentane diol, 2-ethyl-l,3-hexane diol, 2-methyl-l,3- propane diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12- dodecanediol, 2,2,4,4-tetramethylcyclobutane-l,3-diol, 1,3-cyclopentanediol, 1,2- cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3- cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, isosorbide, glycerol monoesters, glycerol monoethers, trimethylolpropane monoesters, trimethylolpropane monoethers, pentaerythritol diesters, pentaerythritol diethers, and alkoxylated derivatives of any of these.

In certain embodiments where

is derived from a dihydric alcohol, the dihydric alcohol is selected from the group consisting of: diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly(ethylene glycol), such as those having number average molecular weights of from 220 to about 2000 g/mol, dipropylene glycol, tripropylene glycol, and higher poly(propylene glycols) such as those having number average molecular weights of from 234 to about 2000 g/mol.

In certain embodiments where

derived from a dihydric alcohol, the dihydric alcohol comprises an alkoxylated derivative of a compound selected from the group consisting of: a diacid, a diol, or a hydroxy acid. In certain embodiments, the alkoxylated derivatives comprise ethoxylated or pro oxylated compounds.

In certain embodiments, where

is derived from a dihydric alcohol, the dihydric alcohol comprises a polymeric diol. In certain embodiments, a polymeric diol is selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether polycarbonates, polycarbonate-copolyesters, and alkoxylated analogs of any of these. In certain embodiments, the polymeric diol has an average molecular weight less than about 2000 g/mol.

In certain embodiments, -/ is derived from a polyhydric alcohol with more than two hydroxy groups. In certain embodiments, the aliphatic polycarbonate chains in polymer com ositions of the present invention comprise aliphatic polycarbonate chains where the

moiety -/ is derived from a triol. In certain embodiments, such aliphatic polycarbonate chains have the structure P3:

wherein each of R , R , R^J, R\ Y, and n is as defined above and described in classes and subclasses herein.

In certain embodiments, where

is derived from a triol, the triol is selected from the group consisting of: glycerol, 1,2,4-butanetriol, 2-(hydroxymethyl)- 1,3 -propanediol; hexane triols, trimethylol propane, trimethylol ethane, trimethylolhexane, 1,4- cyclohexanetrimethanol, pentaerythritol mono esters, pentaerythritol mono ethers, and alkoxylated analogs of any of these. In certain embodiments, alkoxylated derivatives comprise ethoxylated or ropoxylated compounds.

In certain em o ments, is derived from an alkoxylated derivative of a trifunctional carboxylic acid or trifunctional hydroxy acid. In certain embodiments, alkoxylated polymeric derivatives com rise ethoxylated or propoxylated compounds.

In certain embodiments, where

is derived from a polymeric triol, the polymeric triol is selected from the group consisting of polyethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether polycarbonates, polycarbonate-copolyesters, and alkoxylated analogs of any of these. In certain embodiments, the alkoxylated polymeric triols comprise ethoxylated or pro oxylated compounds.

In certain embodiments,

derived from a polyhydric alcohol with four hydroxy groups. In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise aliphatic polycarbonate chains where the moiety is derived from a tetraol. In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure

and subclasses herein.

In certain embodiments, (?) is derived from a polyhydric alcohol with more than four hydroxy groups. In certain embodiments, ( ^v—? /) is derived from a polyhydric alcohol with six hydroxy groups. In certain embodiments, a polyhydric alcohol is dipentaerithrotol or an alkoxylated analog thereof. In certain embodiments, a polyhydric alcohol is sorbitol or an alkoxylated analog thereof. In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the resent invention comprise chains with the structure P5:

wherein each of R , R , R , R , Y, fa__// a anndd nn iiss as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonates of the present invention comprise a combination of bifunctional chains (e.g. polycarbonates of formula P2) in combination with higher functional chains (e.g. one or more polycarbonates of formulae P3 to P5).

In certain embodiments,

is derived from a hydroxy acid. In certain

embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P6:

wherein each of R¹, R², R³, R⁴, Y, v5Jand n is as defined above and described in classes and subclasses herein. In such instances, Cf) represents the carbon-containing backbone of the hydroxy acid, while ester and carbonate linkages adjacent to ( are derived from the -

C0₂H group and the hydroxy group of the hydroxy acid. For example, if © were derived from 3 -hydroxy propanoic acid, then O would be -CH₂CH₂- and P6 would have the following structure:

In certain embodiments, Θ is derived from an optionally substituted C_2-4o hydroxy acid. In certain embodiments, _D is derived from a polyester. In certain embodiments, such polyesters have a molecular weight less than about 2000 g/mol. In certain embodiments, a hydroxy acid is an alpha-hydroxy acid. In certain embodiments, a hydroxy acid is selected from the group consisting of: glycolic acid, DL- lactic acid, D-lactic acid, L-lactic, citric acid, and mandelic acid.

In certain embodiments, a hydroxy acid is a beta-hydroxy acid. In certain embodiments, a hydroxy acid is selected from the group consisting of: 3-hydroxypropionic acid, DL 3-hydroxybutryic acid, D-3 hydroxybutryic acid, L-3-hydroxybutyric acid, DL-3- hydroxy valeric acid, D-3-hydroxy valeric acid, L-3-hydroxy valeric acid, salicylic acid, and derivatives of salicylic acid.

In certain embodiments, a hydroxy acid is a α-ω hydroxy acid. In certain

embodiments, a hydroxy acid is selected from the group consisting of: of optionally substituted C_3-2o aliphatic α-ω hydroxy acids and oligomeric esters.

In certain embodiments, a hydroxy acid is selected from the group consisting of:

In certain embodiments, is derived from a polycarboxylic acid. In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P7:

wherein each of R¹, R², R³, R⁴, Y

is as defined above and described in classes and subclasses herein, and y' is an integer from 1 to 5 inclusive.

In embodiments where the aliphatic polycarbonate chains have a structure P7,

represents the carbon-containing backbone (or a bond in the case of oxalic acid) of a polycarboxylic acid, while ester groups adjacent to

are derived from -C0₂H groups of a polycarboxylic acid. For exam le, if (-?/) were derived from succinic acid

(H0₂CCH₂CH₂C0₂H), then

would be -CH₂C¾- and P7 would have the following

wherein each of R¹, R², R³, R⁴, Y, and n is as defined above and described in classes and subclasses herein.

In certain embodiments,

is derived from a dicarboxylic acid. In certain embodiments, aliphatic polycarbonate chains in polymer compositions of the present invention comprise chains with the structure P8:

In certain embodiments, _^/ is selected from the group consisting of: phthalic acid, isophthalic acid, terephthalic acid, maleic acid, succinic acid, malonic acid, glutaric acid, adi ic acid, pimelic acid, suberic acid, and azelaic acid.

In certain embodiments, each in the structures hereinabove is

independently selected from the group consisting of:

wherein each R^x is independently an optionally substituted group selected from the group consisting of C_2-20 aliphatic, C_2-20 heteroaliphatic, 3- to 14-membered carbocyclic, 6- to 10-membered aryl, 5- to 10-membered heteroaryl, and 3- to 12-membered heterocyclic.

In certain embodiments, each

in the structures herein is independently selected from

wherein R^x is as defined above and described in classes and subclasses In certain embodiments, aliphatic polycarbonate chains comprise:

wherein each of C ^ _> - Y, and n is as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of -Y and n is as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of f⁾ _, - Y, and n is as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of -Y and n is as defined above and described in classes and subclasses herein. In certain embodiments aliphatic polycarbonate chains comprise

wherein each of ) _, - Y, and n is as defined above and described in classes and subclasses herein.

In certain embodiments aliphatic polycarbonate chains comprise

wherein each of -Y and n are is as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of l) _; - Y, and n is as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of -Y and n is as defined above and described in classes and subclasses herein. In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of 0, -Y, and n is as defined above and described in classes and subclasses herein.

wherein each of 0, -Y, R^x, and n is as defined above and described in classes and subclasses herein.

wherein each of -Y, R^x, and n is as defined above and described in classes and subclasses herein.

In certain embodiments aliphatic polycarbonate chains comprise

In certain embodiments aliphatic polycarbonate chains comprise

wherein each of 0, -Y, and n are is as defined above and described in classes and subclasses herein; and each = independently represents a single or double bond.

In certain embodiments aliphatic polycarbonate chains comprise

In certain embodiments aliphatic polycarbonate chains comprise

wherein each of -Y, , and n is as defined above and described in classes and subclasses herein.

wherein each of 0_; R^x, -Y and n is as defined above and described in classes and subclasses herein. In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of-Y, R^x, and n is as defined above and described in classes and subclasses herein.

In certain embodiments aliphatic polycarbonate chains comprise

wherein each of ©_, -Y, and n is as defined above and described in classes and subclasses herein.

In certain embodiments aliphatic polycarbonate chains comprise

certain embodiments, aliphatic polycarbonate chains comprise

wherein each of-Y and n is as defined above and described in classes and subclasses herein.

In certain embodiments aliphatic polycarbonate chains comprise

wherein each of -Y, ^{: =r=} , and n is as defined above and described in classes and subclasses herein.

In certain embodiments, aliphatic polycarbonate chains comprise

wherein each of 0, -Y, and n is as defined above and described in classes and

herein.

In certain embodiments, aliphatic polycarbonate chains comprise

In certain embodiments, in polycarbonates of structures P2a, P2c, P2d, P2f, P2h,

(z)

P2j, P2I, P2I-a, P2n, P2p, and P2r, ^ is selected from the group consisting of: ethylene glycol; diethylene glycol, triethylene glycol, 1,3 propane diol; 1,4 butane diol, hexylene glycol, 1,6 hexane diol, propylene glycol, dipropylene glycol, tripopylene glycol, and alkoxylated derivatives of any of these.

For polycarbonates comprising repeat units derived from two or more epoxides, such as those represented by structures P2f through P2r, depicted above, it is to be understood that the structures drawn may represent mixtures of positional isomers or regioisomers that are not explicitly depicted. For example, the polymer repeat unit adjacent to either end groups of the polycarbonate chains can be derived from either one of the two epoxides comprising the copolymers. Thus, while the polymers may be drawn with a particular repeat unit attached to an end group, the terminal repeat units might be derived from either of the two epoxides and a given polymer composition might comprise a mixture of all of the possibilities in varying ratios. The ratio of these end-groups can be influenced by several factors including the ratio of the differ rent epoxides used in the polymerization, the structure of the catalyst used, the reaction conditions used (i.e temperature pressure, etc.) as well as by the timing of addition of reaction components. Similarly, while the drawings above may show a defined regiochemistry for repeat units derived from substituted epoxides, the polymer compositions will, in some cases, contain mixtures of regioisomers. The regioselectivity of a given polymerization can be influenced by numerous factors including the structure of the catalyst used and the reaction conditions employed. To clarify, this means that the composition represented by structure P2r above, may contain a mixture of several compounds as shown in the diagram below. This diagram shows the isomers graphically for polymer P2r, where the structures below the depiction of the chain show each regio- and positional isomer possible for the monomer unit adjacent to the chain transfer agent and the end groups on each side of the main polymer chain. Each end group on the polymer may be independently selected from the groups shown on the left or right while the central portion of the polymer including the chain transfer agent and its two adjacent monomer units may be independently selected from the groups shown. In certain embodiments, the polymer composition comprises a mixture of all possible combinations of these. In other embodiments, the polymer

Likewise, certain small molecules depicted herein may comprise mixtures of regio- and/or stereoisomers, but be depicted in only one form. For example, dipropylene glycol (DPG) as provided commercially comprises a mixture of regioisomeric and stereoisomeric compounds. Thus while such molecules may be depicted as one regioisomer for convenience— as in structure Ql, for example— it will be understood by one skilled in the art that the compound may actually contain a mixture of isomeric dipropylene glycol moieties.

In certain embodiments, the aliphatic polycarbonate polyol is selected from the group consisting of l, Q2, Q3, Q4, and mixtures of any of these.

In certain embodiments, the aliphatic polycarbonate polyol is selected from the group consisting of:

Poly (propylene carbonate) of formula Ql having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 3 and about 15), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98%) -OH end groups;

Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 3.5 and about 4.5), a

polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 3.5 and about 4.5), a polydisperisty index less than about 1.25, at least 95%> carbonate linkages, and at least 98% -OH end groups; Poly (propylene carbonate) of formula Ql having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 8 and about 9.5), a

Poly (propylene carbonate) of formula Ql having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 13 and about 15), a

Poly(propylene carbonate) of formula Q2 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 3 and about 15), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 3.5 and about 4.5), a

polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least

98% -OH end groups;

Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 3.5 and about 4.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 8 and about 9.5), a

Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 13 and about 15), a

Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 4 and about 16), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 4 and about 5), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 4 and about 5), a

polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 10 and about 11), a

Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 15 and about 17), a

polydisperisty . index less than about 1.25, at least 85% carbonate linkages,, and at least 98% -OH end groups;

Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 4 and about 16), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 4 and about 5), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 4 and about 5), a

Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 10 and about 11), a

polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; and

Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 15 and about 17), a

polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups.

B. Isocyanate Reagents

As described above, the polyurethane dispersions of the present invention comprise isocyanate reagents. The purpose of these isocyanate reagents is to react with the reactive end groups on the aliphatic polycarbonate polyols to form higher molecular weight structures through chain extension and/or cross-linking.

The technology of polyurethane formulation is well advanced and a very large number of isocyanates and related polyurethane precursors are known in the art. While this section of the specification describes isocyanates suitable for use in certain embodiments of the present invention, it is to be understood that it is within the capabilities of one skilled in the art of polyurethane formulation to use alternative isocyanates along with the teachings of this disclosure to formulate additional compositions of matter within the scope of the present invention. Descriptions of suitable isocyanate compounds and related methods can be found in Polvurethanes: Coatings Adhesives and Sealants Meier- Westhues, Ulrich 2007 (ISBN 978-3-87870-334-1), Chemistry and Technology of Polyols for Polvurethanes Ionescu, Mihail 2005 (ISBN 978-1-84735-035-0), and H. Ulrich, "Urethane Polymers," Kirk-Othmer Encyclopedia of Chemical Technology, 1997 the entirety of each of which is incorporated herein by reference. In certain embodiments, the isocyanate reagents comprise two or more isocyanate groups per molecule. In certain embodiments the isocyanate reagents are diisocyanates. In other embodiments, the isocyanate reagents are higher polyisocyanates such as

triisocyanates, tetraisocyanates, isocyanate polymers or oligomers, and the like. In certain embodiments, the isocyanate reagents are aliphatic polyisocyanates or derivatives or oligomers of aliphatic polyisocyanates. In other embodiments, the isocyanates are aromatic polyisocyanates or derivatives or oligomers of aromatic polyisocyanates. In certain embodiments, the compositions may comprise mixtures of any two or more of the above types of isocyanates.

In certain embodiments, an isocyanate reagent is selected from the group consisting of: 1,6- hexamethylenediisocyanate (HDI), isophorone diisocyanate (IPDI), 4,4' methylene- bis(cyclohexyl isocyanate) (Hi₂MDI), 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI), diphenyhnethane-4,4'-diisocyanate (MDI), diphenylmethane-2,4'- diisocyanate (MDI), xylylene diisocyanate (XDI), l,3-bis(isocyanatomethyl)cyclohexane (H6-XDI), 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate (TMDI), m-tetramethylxylylene diisocyanate (TMXDI), p-tetramethylxylylene diisocyanate (TMXDI), isocyanatomethyl-l,8-octane diisocyanate (TIN), triphenylmethane- 4,4',4" triisocyanate, tris(p-isocyanatomethyl)thiosulfate, l,3-bis(isocyanatomethyl)benzene, 1 ,4-tetramethylene diisocyanate, trimethylhexane diisocyanate, 1 ,6-hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, lysine diisocyanate, and mixtures of any two or more of these.

Isocyanates suitable for certain embodiments of the present invention are available commercially under various trade names. Examples of suitable commercially available isocyanates include materials sold under trade names: Desmodur® (Bayer Material Science), Tolonate® (Perstorp), Takenate® (Takeda), Vestanat® (Evonik), Desmotherm® (Bayer Material Science), Bayhydur® (Bayer Material Science), Lupranate® (BASF), Trixene (Baxenden), Hartben® (Benasedo), Ucopol® (Sapici), and Basonat® (BASF). Each of these trade names encompasses a variety of isocyanate materials available in various grades and formulations. The selection of suitable commercially-available isocyanate materials as reagents to produce PUDs for a particular application is within the capability of one skilled in the art of polyurethane coating technology using the teachings and disclosure of this patent application along with the information provided in the product data sheets supplied by the above-mentioned suppliers.

Additional isocyanates suitable for certain embodiments of the present invention are sold under the trade name Lupranate® (BASF). In certain embodiments, the isocyanates are selected from the group consisting of the materials shown in Table 1 :

Lupranate MS 4,4' MDI 33.5 2

Lupranate Ml 2,4' and 4,4' MDI Blend 33.5 2

Lupranate LP30 Liquid Pure 4,4' MDI 33.1 2

Lupranate 227 Monomeric/Modified MDI Blend 32.1 2

Lupranate 5143 Carbodiimide Modified 4,4' MDI 2.2

Lupranate MM103 Carbodiimide Modified 4,4' MDI 2.2

Lupranate 219 Carbodiimide Modified 4,4' MDI 2.2

Lupranate 81 Carbodiimide Modified MDI 2.2

Lupranate 218 Carbodiimide Modified MDI 2.2

Lupranate M10 Low Funct. Polymeric 2.2

Lupranate R2500U Polymeric MDI Variant 2.7

Lupranate M20S Mid-Functionality Polymeric 2.7

Lupranate M20FB Mid- Functionality Polymeric 2.7

Lupranate 245 Low Viscosity Polymeric 2.3

Lupranate TF2115 Mid Functionality Polymeric 2.4

Lupranate 78 Mid Functionality Polymeric 2.3

Lupranate 234 Low Functionality Polymeric 2.4

Lupranate 273 Low Viscosity Polymeric 2.5

Lupranate 266 Low Viscosity Polymeric 2.5

Lupranate 261 Low Viscosity Polymeric 2.5

Lupranate 255 Low Viscosity Polymeric 2.5

Lupranate 268 Low Viscosity Polymeric 2.4

Higher Functional Prepolymer 2.3

Lupranate 223 Low Vise. Derivative of Pure MDI 2.2

Lupranate 5040 Mid Functional, Low Viscosity 2.1

Lupranate 5110 Polymeric MDI Prepolymer 2.3

Lupranate MP102 4,4' MDI Prepolymer 2

Lu ranate 5090 Special 4,4' MDI Prepolymer 2.1

Lupranate 5050 Mid Functional, Mid NCO Prepol 2.1

Lupranate 5030 Special MDI Prepolymer IMA

Lupranate 5080 2,4'-MDI Enhanced Prepolymer 2

Lupranate 5060 Low Funct, Higher MW Prepol 2

Lupranate 279 Low Funct, Special Prepolymer 2

Lupranate 5070 Special MDI Prepolymer 2

Lupranate 5020 Low Functionality, Low NCO 2

|¾lugn¾¾is6cyanate (TDI)

Lu ranate T80- 80/20 :2,4/2,6 TDI 2

Lupranate T80- High Acidity TDI 2

Lupranate 8020 80/20:TDI/Polymeric MDI 2.1

TABLE 1 Other isocyanates suitable for certain embodiments of the present invention are sold under the trade name Desmodur® available from Bayer Material Science. In certain embodiments, the isocyanates are selected from the group consisting of the materials shown in Table 2:

Desmodur® E 3370 Aliphatic polyisocyanate prepolymer based on hexamethylene diisocyanate

Desmodur® E XP 2605 Polyisocyanate prepolymer based on toluene diisocyanate and diphenylmethan diisocyanate

Desmodur® E XP 2715 Aromatic polyisocyanate prepolymer based on 2,4'-diphenylmethane diisocyanate

(2,4'-MDI) and a hexanediol adipate

Desmodur® E XP 2723 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI).

Desmodur® E XP 2726 Aromatic polyisocyanate prepolymer based on 2,4'-diphenylmethane diisocyanate

(2,4'-MDI)

Desmodur® E XP 2727 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate.

Desmodur® E XP 2762 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI).

Desmodur® H Monomeric aliphatic diisocyanate

Desmodur® HL Aromatic/aliphatic polyisocyanate based on toluylene diisocyanate/ hexamethylene diisocyanate

Desmodur® I Monomeric cycloaliphatic diisocyanate.

Desmodur® IL 1351 Aromatic polyisocyanate based on toluene diisocyanate

Desmodur® IL 1451 Aromatic polyisocyanate based on toluene diisocyanate

Desmodur® IL BA Aromatic polyisocyanate based on toluene diisocyanate

Desmodur® IL EA Aromatic polyisocyante resin based on toluylene diisocyanate

Desmodur® L 1470 Aromatic polyisocyanate based on toluene diisocyanate

Desmodur® L 67 BA Aromatic polyisocyanate based on tolulene diisocyanate

Desmodur® L 67 MPAX Aromatic polyisocyanate based on tolulene diisocyanate

Desmodur® L 75 Aromatic polyisocyanate based on tolulene diisocyanate

Desmodur® LD Low-functionality isocyanate based on hexamethylene diisocyanate (HDI)

Desmodur® LS 2424 Monomeric diphenylmethane diisocyanate with high 2,4'-isomer content

Desmodur® MT Polyisocyanate prepolymer based on diphenylmethane diisocyanate

Desmodur® N 100 Aliphatic polyisocyanate (HDI biuret)

Desmodur® N 3200 Aliphatic polyisocyanate (low-viscosity HDI biuret)

Desmodur® N 3300 Aliphatic polyisocyanate (HDI trimer)

Desmodur® N 3368 BA/SN Aliphatic polyisocyanate (HDI trimer)

Desmodur® N 3368 SN Aliphatic polyisocyanate (HDI trimer)

Desmodur® N 3386 BA/SN Aliphatic polyisocyanate (HDI trimer)

Desmodur® N 3390 BA Aliphatic polyisocyanate (HDI trimer)

Desmodur® N 3390 BA/SN Aliphatic polyisocyanate (HDI trimer)

Desmodur® N 3400 Aliphatic polyisocyanate (HDI uretdione)

Desmodur® N 3600 Aliphatic polyisocyanate (low-viscosity HDI trimer)

Desmodur® N 3790 BA Aliphatic polyisocyanate (high functional HDI trimer)

Desmodur® N 3800 Aliphatic polyisocyanate (flexibilizing HDI trimer)

Desmodur® N 3900 Low-viscosity, aliphatic polyisocyanate resin based on hexamethylene diisocyanate

Desmodur® N 50 BA/MPA Aliphatic polyisocyanate (HDI biuret)

Desmodur® N 75 BA Aliphatic polyisocyanate (HDI biuret)

Desmodur® N 75 MPA Aliphatic polyisocyanate (HDI biuret) Desmodur® N 75 MPA/X Aliphatic polyisocyanate (HDI biuret)

Desmodur® NZ 1 Aliphatic polyisocyanate

Desmodur® PC-N Desmodur PC-N is a modified diphenyl-methane-4,4'-diisocyanate (MDI).

Desmodur® PF Desmodur PF is a modified diphenyl-methane-4,4'-diisocyanate (MDI).

Desmodur® PL 340, 60 % Blocked aliphatic polyisocyanate based on IPDI

BA/SN

Desmodur® PL 350 Blocked aliphatic polyisocyanate based on HDI

Desmodur® RC Solution of a polyisocyanurate of toluene diisocyanate (TDI) in ethyl acetate.

Desmodur® RE Solution of triphenylmethane-4,4',4"-triisocyanate in ethyl acetate

Desmodur® RFE Solution of tris(p-isocyanatophenyl) thiophosphate in ethyl acetate

Desmodur® RN Solution of a polyisocyanurate with aliphatic and aromatic NCO groups in ethyl acetate.

Desmodur® T 100 Pure 2,4 '-toluene diisocyanate (TDI)

Desmodur® T 65 N 2,4- and 2,6-toluene diisocyanate (TDI) in the ratio 67 : 33

Desmodur® T 80 2,4- and 2,6-toluene diisocyanate (TDI) in the ratio 80 : 20

Desmodur® T 80 P 2,4- and 2,6-toluene diisocyanate (TDI) in the ratio 80 : 20 with an increased content of hydrolysable chlorine

Desmodur® VH 20 N Polyisocyanate based on diphenylmethane diisocyanate

Desmodur® VK Desmodur VK products re mixtures of diphenylmethane-4,4'-diisocyanate (MDI) with isomers and higher functional homologues (PMDI).

Desmodur® VKP 79 Desmodur VKP 79 is a modified diphenylmethane-4,4'-diisocyanate (MDI) with isomers and homologues.

Desmodur® VKS 10 Desmodur VKS 10 is a mixture of diphenylmethane-4,4'-diisocyanate (MDI) with isomers and higher functional homologues (PMDI).

Desmodur® VKS 20 Desmodur VKS 20 is a mixture of diphenylmethane-4,4'-diisocyanate (MDI) with isomers and higher functional homologues (PMDI).

Desmodur® VKS 20 F Desmodur VKS 20 F is a mixture of diphenylmethane-4,4'-diisocyanate (MDI) with isomers and higher functional homologues (PMDI).

Desmodur® VKS 70 Desmodur VKS 70 is a mixture of diphenylmethane-4,4'-diisocyanate (MDI) with isomers and homologues.

Desmodur® VL Aromatic polyisocyanate based on diphenylmethane diisocyanate

Desmodur® VP LS 2078/2 Blocked aliphatic polyisocyanate based on IPDI

Desmodur® VP LS 2086 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate

Desmodur® VP LS 2257 Blocked aliphatic polyisocyanate based on HDI

Desmodur® VP LS 2371 Aliphatic polyisocyanate prepolymer based on isophorone diisocyanate.

Desmodur® VP LS 2397 Desmodur VP LS 2397 is a linear prepolymer based on polypropylene ether glycol and diphenylmethane diisocyanate (MDI). It contains isocyanate groups.

Desmodur® W Monomeric cycloaliphatic diisocyanate

Desmodur® W/l Monomeric cycloaliphatic diisocyanate

Desmodur® XP 2404 Desmodur XP 2404 is a mixture of monomeric polyisocyanates

Desmodur® XP 2406 Aliphatic polyisocyanate prepolymer based on isophorone diisocyanate

Desmodur® XP 2489 Aliphatic polyisocyanate Desmodur® XP 2505 Desmodur XP 2505 is a prepolymer containing ether groups based on

diphenylmethane-4,4 '-diisocyanates (MDI) with isomers and higher functional homologues (PMDI).

Desmodur® XP 2551 Aromatic polyisocyanate based on diphenylmethane diisocyanate

Desmodur® XP 2565 Low-viscosity, aliphatic polyisocyanate resin based on isophorone diisocyanate.

Desmodur® XP 2580 Aliphatic polyisocyanate based on hexamethylene diisocyanate

Desmodur® XP 2599 Aliphatic prepolymer containing ether groups and based on hexamethylene-1,6- diisocyanate (HDI)

Desmodur® XP 2617 Desmodur XP 2617 is a largely linear NCO prepolymer based on hexamethylene

diisocyanate.

Desmodur® XP 2665 Aromatic polyisocyanate prepolymer based on diphenylmethane diisocyanate (MDI).

Desmodur® XP 2675 Aliphatic polyisocyanate (highly functional HDI trimer)

Desmodur® XP 2679 Aliphatic polyisocyanate (HDI allophanate trimer)

Desmodur® XP 2714 Silane-functional aliphatic polyisocyanate based on hexamethylene diisocyanate

Desmodur® XP 2730 Low-viscosity, aliphatic polyisocyanate (HDI uretdione)

Desmodur® XP 2731 Aliphatic polyisocyanate (HDI allophanate trimer)

Desmodur® XP 2742 Modified aliphatic Polyisocyanate (HDI-Trimer), contains Si02 -nanoparticles

TABLE 2

Additional isocyanates suitable for certain embodiments of the present invention are sold under the trade name Tolonate® (Perstorp). In certain embodiments, the isocyanates are selected from the group consisting of the materials shown in Table 3 :

TABLE 3 Additional isocyanates suitable for certain embodiments of the present invention include water-emulsifiable isocyanates sold under the trade name Easaqua® (Perstorp). Examples include Easaqua™ WAT; Easaqua™ WAT-1; Easaqua™ WT 1000; Easaqua™ WT 2102; Easaqua™ X D 401; Easaqua™ X D 803; Easaqua™ X M 501; Easaqua™ X M 502; Easaqua™ X WAT-3 ; and Easaqua™ X WAT-4.

C. Coreactants

In addition to the aliphatic polycarbonate polyols and isocyanate reagents described above, some compositions of the present invention comprise coreactants. Coreactants can include other types of polyols (e.g. polyether polyols, polyester polyols, acrylics, or other polycarbonate polyols), or small molecules with functional groups reactive toward isocyanates such as hydroxyl groups, amino groups, thiol groups, and the like. In certain embodiments, coreactants, comprise molecules with two or more functional groups reactive toward isocyanates.

In certain embodiments, coreactants comprise functional coreactants defined as coreactants containing, in addition to functional groups reactive toward isocyanates, additional functional groups that impart desired physical properties to the PUDs. In certain embodiments, functional coreactants comprise molecules that, when incorporated into the chain-extension process, impart hydrophilic characteristics to the resulting chain-extended composition. In certain embodiments, coreactants comprise molecules that, when incorporated into the chain-extension process, provide sites for cross-liriking of the prepolymer or the PUD.

In certain embodiments, functional coreactants comprise hydrophilic groups, ionic groups, or precursors to ionic groups any of which may act as internal emulsifiers and thereby aid in the formation of stable aqueous dispersions of the inventive compositions. In certain embodiments, such functional coreactants comprise precursors to ionic groups. In certain embodiments, functional coreactants comprise precursors to cationic groups. In certain embodiments, functional coreactants comprise precursors to anionic groups. Another group of water-dispersibility enhancing compounds of particular interest are side chain hydrophilic monomers. Some examples include alkylene oxide oligomers, polymers and copolymers as shown, for example, in published U.S. Patent Application No. 20030195293, the disclosure of which is incorporated herein by reference.

In certain embodiments, a coreactant comprises a polyhydric alcohol. In certain embodiments, a coreactant comprises a dihydric alcohol. In certain embodiments, the dihydric alcohol comprises a C_2-40 diol. In certain embodiments, the dihydric alcohol is selected from the group consisting of: 1,2-ethanediol, 1,2-propanediol, 1,3 -propanediol, 1,2- butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-l,3-diol, 2- butyl-2-ethylpropane-l,3-diol, 2-methyl-2,4-pentane diol, 2-ethyl-l,3-hexane diol, 2-methyl- 1,3 -propane diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12- dodecanediol, 2,2,4,4-tetramethylcyclobutane-l,3-diol, 1,3-cyclopentanediol, 1,2- cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1 ,2-cyclohexanedimethanol, 1,3- cyclohexanedimethanol, 1 ,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, isosorbide, glycerol monoesters, glycerol monoethers, trimethylolpropane monoesters,

trimethylolpropane monoethers, pentaerythritol diesters, pentaerythritol diethers, and alkoxylated derivatives of any of these.

In certain embodiments, a coreactant comprises a dihydric alcohol selected from the group consisting of: diethylene glycol, Methylene glycol, tetraethylene glycol, higher poly(ethylene glycol), such as those having number average molecular weights of from 220 to about 2000 g/mol, dipropylene glycol, tripropylene glycol, and higher poly(propylene glycols) such as those having number average molecular weights of from 234 to about 2000 g/mol.

In certain embodiments, a coreactant comprises an alkoxylated derivative of a compound selected from the group consisting of: a diacid, a diol, or a hydroxy acid. In certain embodiments, the alkoxylated derivatives comprise ethoxylated or propoxylated compounds.

In certain embodiments, a coreactant comprises a polymeric diol. In certain embodiments, a polymeric diol is selected from the group consisting of poly ethers, polyesters, hydroxy-terminated polyolefins, polyether-copolyesters, polyether

polycarbonates, polycarbonate-copolyesters, and alkoxylated analogs of any of these. In certain embodiments, the polymeric diol has an average molecular weight less than about 2000 g/mol

In some embodiments, a coreactant comprises a triol or higher polyhydric alcohol. In certain embodiments, a coreactant is selected from the group consisting of: glycerol, 1,2,4- butanetriol, 2-(hydroxymethyl)-l,3-propanediol; hexane triols, trimethylol propane, trimethylol ethane, trimethylolhexane, 1,4-cyclohexanetrimethanol, pentaerythritol mono esters, pentaerythritol mono ethers, and alkoxylated analogs of any of these. In certain embodiments, alkoxylated derivatives comprise ethoxylated or propoxylated compounds.

In some embodiments, a coreactant comprises a polyhydric alcohol with four to six hydroxy groups. In certain embodiments, a coreactant comprises dipentaerithrotol or an alkoxylated analog thereof. In certain embodiments, coreactant comprises sorbitol or an alkoxylated analog thereof.

In certain embodiments, a functional coreactant comprises a polyhydric alcohol containing one or more moieties that can be converted to an ionic functional group. In certain embodiments, the moiety that can be converted to an ionic functional group is selected from the group consisting of: carboxylic acids, esters, anhydrides, sulfonic acids, sulfamic acids, phosphates, and amino groups.

In certain embodiments, a coreactant comprises a hydroxy-carboxylic acid having the general formula (HO)_xQ(COOH)_j,, wherein Q is a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x and > are each integers from 1 to 3. In certain embodiments, a coreactant comprises a diol carboxylic acid. In certain embodiments, a coreactant comprises a bis(hydroxylalkyl) alkanoic acid. In certain embodiments, a coreactant comprises a bis(hydroxylmethyl) alkanoic acid. In certain embodiments the diol carboxylic acid is selected from the group consisting of 2,2 bis-(hydroxymethyl)-propanoic acid (dimethylolpropionic acid, DMPA) 2,2-bis(hydroxymethyl) butanoic acid

(dimetbylolbutanoic acid; DMBA), dihydroxysuccinic acid (tartaric acid), and 4,4'- bis(hydroxyphenyl) valeric acid. In certain embodiments, a coreactant comprises an N,N- bis(2-hydroxyalkyl)carboxylic acid.

In certain embodiments, a coreactant comprises a polyhydric alcohol containing a sulfonic acid functional group. In certain embodiments, a coreactant comprises a diol sulfonic acid. In certain embodiments, a polyhydric alcohol containing a sulfonic acid is selected from the group consisting of: 2-hydroxymethyl-3-hydroxypropane sulfonic acid, 2- butene-l,4-diol-2-sulfonic acid, and materials disclosed in U.S. Pat. No. 4,108,814 and US Pat. App. Pub. No. 2010/0273029 the entirety of each of which is incorporated herein by reference.

In certain embodiments, a coreactant comprises a polyhydric alcohol containing a sulfamic acid functional group. In certain embodiments, a polyhydric alcohol containing a sulfamic acid is selected from the group consisting of: [N,N-bis(2-hydroxyalkyl)sulfamic acid (where each alkyl group is independently a C_2-6 straight chain, branched or cyclic aliphatic group) or epoxide adducts thereof (the epoxide being ethylene oxide or propylene oxide for instance, the number of moles of epoxide added being 1 to 6) also epoxide adducts of sulfopolycarboxylic acids [e.g. sulfoisophthalic acid, sulfosuccinic acid, etc.], and aminosulfonic acids [e.g. 2-aminoethanesulfonic acid, 3-aminopropanesulfonic acid, etc.].

In certain embodiments, a coreactant comprises a polyhydric alcohol containing a phosphate group. In certain embodiments, a coreactant comprises a bis (2-hydroxalkyl) phosphate (where each alkyl group is independently a C_2-6 straight chain, branched or cyclic aliphatic group). In certain embodiments, a coreactant comprises bis (2-hydroxethyl) phosphate.

In certain embodiments, a coreactant comprises a polyhydric alcohol comprising one or more amino groups. In certain embodiments, a coreactant comprises an amino diol. In certain embodiments, a coreactant comprises a diol containing a tertiary amino group. In certain embodiments, an amino diol is selected from the group consisting of: diethanolamine (DEA), N-methyldiethanolamine (MDEA), N-ethyldiethanolamine (EDEA), N- butyldiethanolamine (BDEA), N,N-bis(hydroxyethyl)-a-amino pyridine, dipropanolamine, diisopropanolamine (DIP A), N-methyldiisopropanolamine, Diisopropanol-p-toluidine, N,N- Bis(hydroxyethyl)-3-cUoroaniline, 3-diethylaminopropane- 1,2 -diol, 3- dimethylaminopropane-l,2-diol and N-hydroxyethylpiperidine. In certain embodiments, a coreactant comprises a diol containing a quaternary amino group. In certain embodiments, a coreactant comprising a quaternary amino group is an acid salt or quaternized derivative of any of the amino alcohols described above. Compounds having at least one crosslinkable functional group can also be incorporated into the prepolymers of the present invention, if desired. Examples of such compounds include those having carbonyl, amine, epoxy, acetoacetoxy, urea-formaldehyde, auto-oxidative groups that crosslink via oxidization, ethylenically unsaturated groups optionally with U.V. activation, olefinic and hydrazide groups, blocked isocyanates, and the like, and mixtures of such groups and the same groups in protected forms (so crosslinking can be delayed until the composition is in its application (e.g., applied to a substrate) and coalescence of the particles has occurred) which can be reversed back into original groups from which they were derived (for crosslinking at the desired time).

D. Prepolymers

As mentioned above, in certain embodiments this invention encompasses novel prepolymers containing aliphatic polycarbonate polyol segments. In certain embodiments, these prepolymers are the result of reaction of the aliphatic polycarbonate polyols with di- or poly-isocyanates, optionally in the presence of one or more coreactants.

The formation of prepolymers is shown conceptually in Scheme 3 below:

ho ^{C P0lyCarbOnate} chain extending reagent functionalized coreactant

Prepolymer

Scheme 3

In Scheme 3, each -XH represents a functional group on the coreactant capable of reacting with an isocyanate group (for example -OH, -NHR, -SH, etc.), and -G represents optionally present hydrophilic functional group, a cross-linkable functional group or a precursor thereof. As depicted in Scheme 3, the reaction of the chain extending reagent

with the -OH groups of the aliphatic polycarbonate polyol and, if present, the -XH groups on the coreactant, leads to an oligomeric prepolymer composition having a plurality of segments joined by urethane (carbamate) linkages. Each prepolymer chain resulting from this reaction may contain a variable number of polyol segments and incorporate a variable number of coreactants. The compositional abundance and average chain length of the prepolymers can be controlled using methods known in the art such as by changing the stoichiometry of the reagents and/or by modifying the reaction conditions employed. Scheme 3 therefore represents a simplification and it is to be understood that the prepolymer compositions described herein may contain a complex mixture of random copolymers comprising a statistical distribution of a vast number of chain compositions.

While Scheme 3 shows formation of a linear prepolymer, the present invention also encompasses branched and crosslinked prepolymers. These materials result when any of the reactants involved comprises three or more reactive sites (for example a branched polyol, a triisocyanate, or a triol coreactant would all lead to branched structures). The degree of branching or cross-linking in the prepolymers can be controlled using methods known in the art, for example by varying the quantities and identities of the tri- or higher-functional reactants included in the prepolymer and/or by modifying the reaction conditions employed during the prepolymer formation.

In certain embodiments, a prepolymer of the present invention comprises essentially linear oligomers of straight-chain aliphatic polycarbonate polyols (e.g. polyols having two -OH end groups such as those of formula PI where x+y = 2) and one or more diisocyanates, where the prepolymer optionally contains segments derived from one or more coreactants having two functional groups capable of reaction with an isocyanate. In certain embodiments, such linear oligomers are represented by structure Ol:

wherein each of R¹, R², R³,

, n, and n' is as defined above and described in classes and subclasses herein, temm represents the carbon skeleton of any of the diisocyanates defined above and described in classes and subclasses herein,

ZZI represents the carbon skeleton of any of the coreactants defined above and described in classes and subclasses herein,

-X- is -0-, -NR-, or -S-;

y" is, independently at each occurrence, 0 or 1 ;

m is an integer greater than zero, and

p is zero or greater.

In certain embodiments, in prepolymers of formula Ol, e&c y" is zero (e.g. the aliphatic polycarbonate polyol is one formed from a diol chain transfer agent as described for polyols of formula P2 above). In other embodiments, in prepolymers of formula Ol, one >" is zero and the other;/" is one (e.g. the aliphatic polycarbonate polyol is one formed from a hydroxyacid chain transfer agent as described for polyols of formula P6 above). In certain embodiments, in prepolymers of formula Ol, eachy" is one (e.g. the aliphatic polycarbonate polyol is one formed from a dicarboxylic acid chain transfer agent as described for polyols of formula P8 above).

In certain embodiments, in prepolymers of formula Ol, each -X- is an oxygen atom (e.g. where a coreactant comprises a dihydric alcohol). In other embodiments, each -X- is an -NR- group (e.g. where a coreactant comprises a diamine). In certain embodiments, the -X- groups present represent a mixture of oxygen and nitrogen atoms.

In certain embodiments, the prepolymer comprises branched or cross-linked oligomers of a difunctional aliphatic polycarbonate polyol and a polyisocyanate having more than two isocyanate groups, where the prepolymer optionally contains segments derived from one or more difunctional coreactants. In certain embodiments, such branched oligomers comprise compounds represented by structure 02:

wherein each of R, R¹, R², R³, R⁴, X, Θ, Β»ϋ, and m, n, η',ρ, and/' is as defined above and described in classes and subclasses herein, and z is an integer greater than 2.

In certain embodiments, the prepolymer comprises branched or cross-linked oligomers of a branched aliphatic polycarbonate polyol having more than two -OH end groups and a polyisocyanate having at least two isocyanate groups, where the prepolymer optionally contains segments derived from one or more difunctional coreactants. In certain embodiments, such branched oligomers comprise compounds represented by structure 03:

wherein each of R¹, R², R³, R⁴, X, Θ, and m, n,p, z, and; " is as defined above and described in classes and subclasses herein, and n" is at each occurrence, independently an integer from about 3 to about 1,000, and may be the same as or different from n or n'.

In certain embodiments, the prepolymer comprises branched or cross-linked oligomers of an aliphatic polycarbonate polyol, a polyisocyanate having at least two isocyanate groups, and one or more coreactants having more than two function groups reactive toward isocyanates. In certain embodiments, such branched oligomers comprise compounds represented by structure 04:

wherein each of R¹, R², R³, R⁴, X, Θ , , ^Z^^> , and m, n, ri, p, z, and /' is as

defined above and described in classes and subclasses herein.

In certain embodiments, the prepolymer comprises complex branched oligomers of formula 05 derived from an aliphatic polycarbonate polyol having more than two hydroxyl groups and a polyisocyanate having more than two isocyanate groups, where the prepolymer optionally contains segments derived from one or more difunctional coreactants. In certain embodiments, the prepolymer comprises complex branched oligomers of formula 06 comprising an aliphatic polycarbonate polyol having more than two hydroxyl groups, a diisocyanate and a polyfunctional coreactant having more than two functional groups reactive toward isocyanates. In certain embodiments, the prepolymer comprises complex branched oligomers of formula 07 comprising an aliphatic polycarbonate polyol, a polyisocyanate having more than two isocyanate groups, and a polyfunctional coreactant having more than two functional groups reactive toward isocyanates. In certain

embodiments, the prepolymer comprises complex branched oligomers of formula 08 comprising an aliphatic polycarbonate polyol having more than two hydroxyl groups, a polyisocyanate having more than two isocyanate groups, and a polyfunctional coreactant having more than two functional groups reactive toward isocyanates.

In certain embodiments, prepolymers comprise mixtures containing linear oligomers of formula Ol along with smaller amounts of any one or more branched oligomers of formulae 02 through 08. In certain embodiments, prepolymers comprise linear oligomers of formula Ol with essentially no cross-linking or branching.

In certain embodiments, for prepolymers of formulae Ol through 08, the prepolymer comprises aliphatic polycarbonate segments derived from any of the polyols of formulae P2a through P2r-a as defined above and described in classes and subclasses herein, or from mixtures of any two or more of these. In certain embodiments, for prepolymers of formulae Ol through 08, the prepolymer comprises aliphatic polycarbonate segments derived from any of the polyols of formulae Ql through Q4 as defined above and described in classes and subclasses herein, or from mixtures of any two or more of these.

In certain embodiments, for prepolymers of formulae 05, 06, and 08, the prepolymer further comprises aliphatic polycarbonate segments derived from any of the polyols of formulae P3, P4, or P5 as defined above and described in classes and subclasses herein, or from mixtures of any two or more of these.

In certain embodiments, for prepolymers of formulae Ol through 08, the prepolymer further comprises segments derived from any one or more of the coreactants described hereinabove. In certain embodiments, a coreactant comprises an alcohol (e.g. at least one - X- in any of structures 01-04 is -0-). In certain embodiments, for prepolymers of formulae Ol through 08, the prepolymer comprises coreactant segments having one or more hydrophilic functional groups. In certain embodiments, such hydrophilic functional groups are precursors to anionic groups. In certain embodiments, the precursors to anionic groups present on coreactant segments are selected from the group consisting of: carboxylic acids, esters, anhydrides, sulfonic acids, sulfamic acids, phosphates.

In certain embodiments, for prepolymers of formulae Ol through 08, the prepolymer comprises coreactant segments having one or more carboxylic acid groups. In certain embodiments, such coreactant segments are derived from carboxylic acid diols. In certain embodiments, such coreactant segments are derived from a bis(hydroxylalkyl) alkanoic acid.

In certain embodiments, such coreactant segments are derived from a bis(hydroxylmethyl) alkanoic acid. In certain embodiments, such coreactant segments are derived from a compound selected from the group consisting of DMPA; DMBA, tartaric acid, and 4,4'- bis(hydroxyphenyl) valeric acid. In certain embodiments, prepolymers of formulae Ol through 08, contain coreactant segments derived from DMPA. In certain embodiments, prepolymers of formulae Ol through 08, contain coreactant segments derived from DMBA.

In certain embodiments, for prepolymers of formulae Ol through 08, the prepolymer comprises coreactant segments bearing one or more carboxylate salts. In certain

embodiments, a coreactant segment comprising a carboxylate salt is derived from any of the carboxylic acid-containing coreactant segments described above by treating them with a base. In certain embodiments the base comprises a metal salt. In other embodiments, the base comprises an amine.

In certain embodiments, for prepolymers of formulae Ol through 08, the prepolymer comprises coreactant segments having one or more amino groups. In certain embodiments, such coreactant segments are derived from amine diols. In certain embodiments, such coreactant segments are derived from a diol containing a tertiary amino group. In certain embodiments, such coreactant segments are derived from an amino diol selected from the group consisting of: diethanolamine (DEA), N-methyldiethanolamine (MDEA), N- ethyldiethanolamine (EDEA), N-butyldiethanolamine (BDEA), N,N-bis(hydroxyethyl)-a- amino pyridine, dipropanolamine, diisopropanolamine (DIP A), N- methyldiisopropanolamine, Diisopropanol-p-toluidine, N^V-Bis(hydroxyethyl)-3 - chloroaniline, 3-diethylaminopropane-l,2-diol, 3-dimethylaminopropane-l,2-diol andN- hydroxyethylpiperidine. In certain embodiments, prepolymers of formulae Ol through 08, contain coreactant segments derived from DEA. In certain embodiments, prepolymers of formulae Ol through 08, contain coreactant segments derived from MDEA. In certain embodiments, prepolymers of formulae Ol through 08, contain coreactant segments derived from EDEA. In certain embodiments, prepolymers of formulae Ol through 08, contain coreactant segments derived from BDEA. In certain embodiments, prepolymers of formulae Ol through 08, contain coreactant segments derived from DIP A.

In certain embodiments, for prepolymers of formulae Ol through 08, the prepolymer comprises coreactant segments having one or more quaternary amino groups. In certain embodiments, a coreactant segment comprising a quaternary amino group is derived from any of the amine-containing coreactant segments described above by creating an acid salt or quaternized derivative of any of the amine-containing coreactant segments described in the previous paragraph.

In certain embodiments, for prepolymers of formulae Ol through 08, the prepolymer comprises coreactant segments derived from hydrophilic poly ether polyols. In certain embodiments, such hydrophilic poly ether polyols are oligomers of ethylene oxide and/or propylene oxide. In certain embodiments, the hydrophilic polyether polyols are rich in EO repeat units.

In certain embodiments, the prepolymers contain a plurality of different coreactant segments derived from two or more different coreactants including mixtures of two or more of any of the coreactants above and described in the classes and subclasses herein.

In certain embodiments, where the prepolymers contain segments derived from coreactants, the molar ratio of aliphatic polycarbonate segments to coreactant segments in the prepolymer composition varies from about 10,000:1 to about 1:1. In certain embodiments, the molar ratio of aliphatic polycarbonate segments to coreactant segments varies from about 5,000:1 to about 5:1. In certain embodiments, the molar ratio of aliphatic polycarbonate segments to coreactant segments varies from about 1,000:1 to about 10:1. In certain embodiments, the molar ratio of aliphatic polycarbonate segments to coreactant segments varies from about 500:1 to about 10:1. In certain embodiments, the molar ratio of aliphatic polycarbonate segments to coreactant segments varies from about 500:1 to about 20:1. In certain embodiments, the molar ratio of aliphatic polycarbonate segments to coreactant segments varies from about 200:1 to about 50:1. In certain embodiments, the molar ratio of aliphatic polycarbonate segments to coreactant segments is about 200: 1 , about 100: 1 , about 50:1, about 30:1, about 20:1, about 10:1 or about 5:1. In some embodiments, a prepolymer may contain more than one type of coreactant segment, in which case the ratios above may be taken to describe the ratio of the polycarbonate segments to any single coreactant segment.

In certain embodiments, for prepolymers of formulae Ol through 08, urethane linkages in the prepolymer are derived from aliphatic diisocyanates, aromatic diisocyanates, oligomeric diisocyanates, or difunctional isocyanate prepolymers.

In certain embodiments, for prepolymers of formulae Ol through 08, the prepolymer comprises urethane linkages derived from one or more aliphatic diisocyanates. In certain embodiments, the prepolymer comprises urethane linkages derived from diisocyanates selected from the group consisting of: HDI, IPDI, H₁₂MDI, H6-XDI, TMDI, 1 ,4-cyclohexyl diisocyanate, 1,4-tetramethylene diisocyanate, trimethylhexane diisocyanate, and mixtures of any two or more of these. In certain embodiments, the prepolymer comprises urethane linkages derived from diisocyanates selected from the group consisting of: HDI, IPDI, H₁₂MDI and mixtures of two or more of these. In certain embodiments, the prepolymer comprises urethane linkages derived from HDI. In certain embodiments, the prepolymer comprises urethane linkages derived from IPDI. In certain embodiments, the prepolymer comprises urethane linkages derived from H₁₂MDI. In certain embodiments, the prepolymer comprises urethane linkages derived from H6-XDI. In certain embodiments, the prepolymer comprises urethane linkages derived from TMDI. In certain embodiments, the prepolymer comprises urethane linkages derived from oligomers or derivatives of any of the above aliphatic isocyanates. In certain embodiments, the prepolymer comprises urethane linkages derived from biurets of any of the above aliphatic isocyanates.

In certain embodiments, for prepolymers of formulae Ol through 08, the prepolymer comprises urethane linkages derived from one or more aromatic diisocyanates. In certain embodiments, the prepolymer comprises urethane linkages derived from diisocyanates selected from the group consisting of: 2,4-TDI, 2,6-TDI, MDI, XDI, TMXDI, and mixtures of any two or more of these. In certain embodiments, the prepolymer comprises urethane linkages derived from TDI or MDI. In certain embodiments, the prepolymer comprises urethane linkages derived from TDI. In certain embodiments, the prepolymer comprises urethane linkages derived from 2,4-TDI. In certain embodiments, the prepolymer comprises urethane linkages derived from 2,6-TDI. In certain embodiments, the prepolymer comprises urethane linkages derived from H6-XDI. In certain embodiments, the prepolymer comprises urethane linkages derived from MDI. In certain embodiments, the prepolymer comprises urethane linkages derived from XDI. In certain embodiments, the prepolymer comprises urethane linkages derived from TMXDI. In certain embodiments, the prepolymer comprises urethane linkages derived from oligomers or derivatives of any of the above aromatic isocyanates. In certain embodiments, the prepolymer comprises urethane linkages derived from biurets of any of the above aromatic isocyanates.

In certain embodiments, for prepolymers of formulae Ol through 08, the prepolymer comprises covalently-linked isocyanate groups. Compositions having this property may be produced using methods known in the art. In particular, control of the molar ratios of the reagents during prepolymer formation such that there is a molar excess of the polyfunctional isocyanate relative to the isocyanate-reactive groups on the aliphatic polycarbonate polyol and coreactants (if any) will favor oligomers where the chain ends are capped with an isocyanate resulting from partial reaction of a polyisocyanate molecule.

In certain embodiments, a majority of chain ends in prepolymers of the present invention comprise isocyanate groups. In certain embodiments, at least 60%, at least 70%, at least 80%, at least 85% or at least 90% of chain ends comprise isocyanate groups. In certain embodiments, at least 92%, at least 95%, at least 96%, at least 97% or at least 98% of chain ends comprise isocyanate groups. In certain embodiments, at least 99% of chain ends comprise isocyanate groups. In certain embodiments, essentially all of the chain ends in prepolymers of the present invention comprise isocyanate groups.

In certain embodiments, the present invention provides novel compositions of matter comprising prepolymers of formula Ol comprising poly(propylene carbonate) (PPC) segments. In certain embodiments, prepolymers of formula Ol contain segments of formula Ol-al

wherein each of _t - Y, and n is as defined above and described in classes and subclasses herein. In certain embodiments, the present invention provides novel compositions of matter comprising prepolymers of formula Ol comprising poly(ethylene carbonate) (PEC) segments. In certain embodiments such prepolymers contain segments of formula 01-a2

wherein ea

₍ -Y, and n is as defined above and described in classes and subclasses herein.

In certain embodiments, prepolymers of formula Ol contain segments derived from polyols of formula Ql, Q2, Q3, or Q4, as defined above and described in the classes and subclasses herein, or from mixtures of any two or more of these.

In certain embodiments, the present invention provides novel compositions of matter comprising prepolymers of formula Ol, where the polyol segments are derived from one or more aliphatic polycarbonate polyol compositions selected from the group consisting of:

Poly(propylene carbonate) of formula Ql having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 3 and about 15), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

98% -OH end groups;

Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 3.5 and about 4.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 8 and about 9.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 13 and about 15), a

98% -OH end groups;

polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98%) -OH end groups;

polydisperisty index less than about 1.25, at least 95%> carbonate linkages, and at least

98% -OH end groups;

Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 4 and about 16), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 4 and about 5), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;

polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least

98% -OH end groups;

Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 500 g/mol (e.g. n is on average between about 4 and about 5), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 4 and about 5), a

Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 10 and about 11), a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; and

98% -OH end groups.

In certain embodiments, the present invention provides prepolymers of formula Ol comprising PPC segments in combination with coreactant segments derived from carboxylic acid diols. In certain embodiments, such prepolymers comprise fragments having a structure Ol-bl:

Ol-bl wherein each of n, Θ, and ^ Z ^⁵, is as defined above and described in classes and subclasses herein.

In certain embodiments, the present invention provides prepolymers of formula Ol comprising PPC segments in combination with coreactant segments derived from 2,2' dimethylolpropionic acid, (DMPA) In certain embodiments, such prepolymers comprise fragments having a structure Ql-b2:

01-b2 wherein each of n, f) and WSSM _{1S as} defined above and described in classes and

subclasses herein.

In certain embodiments, the present invention provides prepolymers of formula Ol comprising PPC segments in combination with coreactant segments derived from 2,2- bis(hydroxymethyl) butanoic acid (DMBA). In certain embodiments, such prepolymers comprise fragments having a structure 01-b3:

01-b3 wherein each of n, and H-BHis as defined above and described in classes and subclasses herein.

In certain embodiments, the present invention provides prepolymers of formula Ol comprising PPC segments in combination with coreactant segments derived from carboxylic acid diols, and urethane linkages derived from aliphatic isocyanates. In certain embodiments, the present invention provides prepolymers of formula Ol comprising PPC segments in combination with coreactant segments derived from carboxylic acid diols, and urethane linkages derived from one or more aliphatic isocyanates selected from the group consisting of: HDI, IPDI, H₁₂MDI, H6-XDI, TMDI, 1,4-cyclohexyl diisocyanate, 1,4-tetramethylene diisocyanate, and trimethylhexane diisocyanate.

In certain embodiments, the present invention provides prepolymers of formula Ol comprising fragments having any of structures 01-b4 through 01-b8, wherein each of n and is as defined above and described in classes and subclasses herein.

01-b6 [ R8 = -CH₃, or -C₂H₅ ]

01-b7 [ R8 = -CH_3> or -C₂H₅ ]

01-b8 [ RS = -CH₃, or -C₂H₅ ]

In certain embodiments, the present invention provides prepolymers of formula Ol comprising PPC segments in combination with coreactant segments derived from carboxylic acid diols, and urethane linkages derived from aromatic isocyanates. In certain embodiments, the present invention provides prepolymers of formula Ol comprising PPC segments in combination with coreactant segments derived from carboxylic acid diols, and urethane linkages derived from one or more aromatic isocyanates selected from the group consisting of: TDI, MDI, XDI, and TMXDI.

In certain embodiments, the present invention provides prepolymers of formula Ol comprising fragments having any of structures 01-b9 through 01- 2, wherein each of n and is as defined above and described in classes and subclasses herein.

01-bl2 [ RS = -CH₃, or -C₂H₅ ]

In certain embodiments, the present invention provides prepolymers of formula Ol comprising PEC segments in combination with coreactant segments derived from carboxylic acid diols. In certain embodiments, such prepolymers comprise fragments having any of structures Ol-bl through 01-bl2, where the PPC segments are substituted for PEC, or PPC- co-PEC segments: such compounds may be designated 01-bl3 through 01-b25 where the non-polycarbonate segments of 01-bl3 correspond to those in Ol-bl, those in 01-bl4 correspond to 01-b2, and so on.

In certain embodiments, the present invention provides prepolymers analogous to those depicted in formulae Ol-al through 01-b25 but comprising polycarbonate polyol segments derived from chain transfer agents having one or more carboxylic acid groups. The specific structures of these compounds can be ascertained by substituting some or all of the polycarbonate-polyol-derived segments in compounds Ol-al through 01-b25 with poly(propylene carbonate) or poly(ethylene carbonate) conforming to structures P6 or P8.

In certain embodiments, the present invention provides prepolymers comprising carboxylate salts derived from neutralization of the pendant carboxyl groups to convert the carboxyl groups to carboxylate anions, thus having a water-dispersibility enhancing effect. Suitable neutralizing agents include tertiary amines, metal hydroxides, ammonium

hydroxide, phosphines, and other agents well known to those skilled in the art. Tertiary amines and ammonium hydroxide are preferred, such as triethyl amine (TEA), dimethyl ethanolamine (DMEA), N-methyl morpholine, and the like, and mixtures thereof. It is recognized that primary or secondary amines may be used in place of tertiary amines, if they are sufficiently hindered to avoid interfering with the chain extension process. In certain embodiments, the present invention provides prepolymers comprising carboxylate salts derived from any of the fragments of formulae Ol-bl through 01-b25. In certain

embodiments such carboxylate salts are alkali earth metal salts. In certain embodiments, such salts are sodium salts. In certain embodiments, such salts are ammonium salts.

In certain embodiments, the present invention provides prepolymers of formula Ol comprising PPC segments in combination with coreactant segments derived from amino diols. In certain embodiments, such prepolymers comprise fragments having a structure Ol- cl:

Ol-cl wherein each of n, , _s and ^^ZZI^ is as defined above and described in classes and subclasses herein, and

at each occurrence Ri and R₂ is independently selected from the group consisting of:

optionally substituted C_1-6 aliphatic; optionally substituted aryl, and a substituted carbamoyl group, where Rr and R₂ may be optionally taken together with intervening atoms to form one or more optionally substituted saturated or unsaturated rings optionally containing one or more additional heteroatoms, and where ¾ and R₂ may constitute part of the oligomeric chain (e.g. as in the case of hydroxyl alkyl amine-derived materials).

In certain embodiments, where prepolymers comprise fragments having a structure Ol-cl, the amine-bearing segment is derived from an amino diol selected from the group consisting of: diethanolamine (DEA), N-methyldiethanolamine (MDEA), N- ethyldiethanolamine (EDEA), N-butyldiethanolamine (BDEA), N,N-bis(hydroxyethyl)-a- amino pyridine, dipropanolamine, diisopropanolamine (DIP A), N- methyldiisopropanolamine, Diisopropanol-p-toluidine, N,N-Bis(hydroxyethyl)-3 - chloroaniline, 3 -diethylaminopropane- 1 ,2-diol, 3 -dimethylaminopropane- 1 ,2-diol.

In certain embodiments, such prepolymers comprise fragments having a structure Ol- cl:

01-c2 R^{k =} methyl, ethyl, propyl, n-butyl, 2-pyridyl,

phenyl, benzyl, m-chlorophenyl, or p-methylphenyl wherein each of n, © , and Η^β _1S as defined above and described in classes and

subclasses herein.

In certain embodiments, such prepolymers comprise fragments having a structure Ol- c3:

01-c3 ^{k =} methyl, ethyl, propyl, rc-butyl, 2-pyridyl,

phenyl, benzyl, m-chlorophenyl, or p-methylphenyl wherein each of n, (f) , and is as defined above and described in classes and subclasses herein.

In certain embodiments, such prepolymers comprise fragments having a structure Ol- c4:

O l-c4 R^s = methyl or ethyl wherein each of n, © , and BBB i_s as defined above and described in classes and

subclasses herein.

In certain embodiments, the present invention encompasses compounds of structure

Ol-cl, comprising any of the urethane linkages shown in structures 01-b4 through 01- 2 these fragment structures may be referred to as fragments 01-c5 through 01-cl3, where the non coreactant segments in 01-c5 correspond to those in 01-b4, those in 01-c6 correspond to 01-b5, and so forth.

In certain embodiments, the present invention provides prepolymers of formula Ol comprising PEC segments in combination with coreactant segments derived from carboxylic acid diols. In certain embodiments, such prepolymers comprise fragments having any of structures Ol-cl through 01-cl3, where the PPC segments are substituted for PEC, or PPC- co-PEC segments.

In certain embodiments, the present invention provides prepolymers comprising ammonium salts derived from any of the fragments of formulae Ol-cl through 01-cl3 (or from their PEC counterparts). In certain embodiments such ammonium salts are quaternized ammonium salts formed by treating the amine with alkylating agents such as alkyl halides (e.g. methyl iodide, bromomethane, benzyl chloride, or allyl chloride), alkyl sulfates (e.g. methyl sulfate or ethyl sulfate) and the like. In certain embodiments, such salts are formed by protonating the amine with a strong acid.

In certain embodiments, the present invention provides prepolymers analogous to those depicted in formulae Ol-cl through 01-cl3 but comprising polycarbonate polyol segments derived from chain transfer agents having one or more carboxylic acid groups. The specific structures of these compounds can be ascertained by substituting some or all of the polycarbonate-polyol-derived segments in compounds Ol-cl through 01-cl3 with poly(propylene carbonate) or poly(ethylene carbonate) conforming to structures P6 or P8.

In certain embodiments, the present invention encompasses solutions of any of the above-described prepolymers. In certain embodiments, such solutions comprise one or more non-protic polar organic solvents. In some embodiments the solvent comprises a ketone. In certain embodiments, the solvent comprises acetone or 2-butanone. In other embodiments, the solvent comprises an amide. In certain embodiments the solvent comprises N- methylpyrrolidone (NMP).

E. Aqueous dispersions and higher polymers

In certain embodiments, the present invention encompasses aqueous dispersions comprising any of the above-described prepolymers. In certain embodiments, such aqueous dispersions comprise emulsions of the prepolymers in substantially unmodified form, while in other embodiments, the aqueous dispersions contain higher polymers formed by the reaction of the isocyanate groups present on the prepolymers with chain-extending agents. If such higher polymers are present, they may be formed in situ by inclusion of suitable chain- extending reagents during or after formation of the dispersion, or they may be foraied prior to dispersion.

A large number of methods are known in the art for producting aqueous emulsions of PUDs and/or isocyanate prepolymers. In certain embodiments, aqueous dispersions of the present invention are formed by one of several methods including:

a) Dispersing the prepolymer by shear forces with emulsifiers (external emulsifiers, such as surfactants, or internal emulsifiers having anionic and/or cationic groups as part of or pendant to the polyurethane backbone, and/or as end groups on the polyurethane backbone). b) The acetone process. A prepolymer is formed with or without the presence of acetone, MEK, and/or other polar solvents that are non-reactive and easily distilled. The prepolymer is further diluted in said solvents as necessary, and chain extended with an active hydrogen-containing compound. Water is added to the chain-extended polyurethane, and the solvents are distilled off. A variation on this process would be to chain extend the prepolymer after its dispersion into water. c) Melt dispersion process. An isocyanate-terminated prepolymer is formed, and then reacted with an excess of ammonia or urea to form a low molecular weight oligomer having terminal urea or biuret groups. This oligomer is dispersed in water and chain extended by methylolation of the biuret groups with formaldehyde.

d) Ketazine and ketimine processes. Hydrazines or diamines are reacted with ketones to form ketazines or ketimines. These are added to a prepolymer, and remain inert to the isocyanate. As the prepolymer is dispersed in water, the hydrazine or diamine is liberated, and chain extension takes place as the dispersion is taking place.

e) Continuous process polymerization. An isocyanate-terminated prepolymer is formed. This prepolymer is pumped through high shear mixing head(s) and dispersed into water and then chain extended at said mixing head(s), or dispersed and chain extended simultaneously at said mixing head(s). This is accomplished by multiple streams consisting of prepolymer (or neutralized prepolymer), optional neutralizing agent, water, and optional chain extender and/or surfactant.

f) Reverse feed process. Water and optional neutralizing agent(s) and/or extender amine(s) are charged to the prepolymer under agitation. The prepolymer can be neutralized before water and/or diamine chain extender are added.

g) Solution polymerization.

h) Bulk polymerization, including but not limited to extrusion processes.

Additional details, methods and reagents suitable for producing emulsions of the present invention are disclosed in: D. Dieterich, "Aqueous Emulsions, Dispersions and Solutions of Polyurethanes; Synthesis and Properties," Progress in Organic Coatings, vol: 9, pp. 281-340 (1981) the entirety of which is incorporated herein by reference.

In some embodiments, the higher polymers are formed by chain extension with suitable chain-extending agents. Suitable chain-extending agents can contain hydroxyl, thio, or amino groups in any combination. Examples of chain-extending agents can be found, for example, in US Pat. No. 7,342,068, which is incorporated herein by reference. It is also known that chain extension can also be accomplished by permitting the reaction of an isocyanate functional group on the polyurethane prepolymer with water via a mechanism believed to generate amine functional group on the prepolymer which promptly reacts with another isocyanate functional group of the prepolymer to give a self-extended polymer. In certain embodiments, the formation of higher polymers conforms to the reaction shown in Scheme 4:

Scheme 4

As shown in Scheme 4, an isocyanate-terminated prepolymer of formula Ol (or any other isocyanate-terminated prepolymer composition described above and in the classes and subclasses herein) is reacted with a chain-extending reagent having two (or more) -ZH groups, where each -ZH is independently selected from the group consisting of -OH, -C(0)OH, -SH, or -NHR to form a higher polymer comprising segments of formula HI.

In certain embodiments, a chain extender is selected from the group consisting of: water, inorganic or organic polyamines having an average of about 2 or more primary and/or secondary amine groups, polyalcohols, ureas, and combinations of any two or more of these. In certain embodiments, a chain extender is selected from the group consisting of: diethylene triamine (DETA), ethylene diamine (EDA), meta-xylylenediamine (MXDA), aminoethyl ethanolamine (AEEA), 2-methyl pentane diamine, and the like, and mixtures thereof. Also suitable for practice in the present invention are propylene diamine, butylene diamine, hexamethylene diamine, cyclohexylene diamine, phenylene diamine, tolylene diamine, 3,3- dichlorobenzidene, 4,4'-methylene-bis-(2-chloroaniline), 3,3-dichloro-4,4-diamino diphenylmethane, and sulfonated primary and/or secondary amines. In certain embodiments, a chain extender is selected from the group consisting of: hydrazine, substituted hydrazines, hydrazine reaction products, and the like, and mixtures thereof. In certain embodiments, a chain extender is a polyalcohol including those having from 2 to 12 carbon atoms, preferably from 2 to 8 carbon atoms, such as ethylene glycol, diethylene glycol, neopentyl glycol, butanediols, hexanediol, and the like, and mixtures thereof. Suitable ureas include urea and its derivatives, and the like, and mixtures thereof. In certain embodiments, chain-extending agents containing at least one basic nitrogen atom are selected from the group consisting of: mono-, bis- or polyalkoxylated aliphatic, cycloaliphatic, aromatic or heterocyclic primary amines, N-methyl diethanolamine, N-ethyl diethanolamine, N-propyl diethanolamine, N-isopropyl diethanolamine, N-butyl

diethanolamine, N-isobutyl diethanolamine, N-oleyl diethanolamine, N-stearyl

diethanolamine, ethoxylated coconut oil fatty amine, N-allyl diethanolamine, N-methyl diisopropanolamine, N-ethyl diisopropanolamine, N-propyl diisopropanolamine, N-butyl diisopropanolamine, cyclohexyl diisopropanolamine, N,N-diethoxylaniline, N,N-diethoxyl toluidine, N,N-diethoxyl-l-aminopyridine, Ν,Ν'-diethoxyl piperazine, dimethyl-bis-ethoxyl hydrazine, N,N'-bis-(2-hydroxyethyl)-N,N'-diethylhexahydr op-phenylenediamine, N- 12- hydroxyethyl piperazine, polyalkoxylated amines, propoxylated methyl diethanolamine, N- methyl-N,N-bis-3 -aminopropylamine, N-(3 -aminopropyl)-N,N'-dimethyl ethylenediamine, N-(3-aminopropyl)-N-methyl ethanolamine, N,N'-bis-(3-aminopropyl)-N,N'-dimethyl ethylenediamine, N,N'-bis-(3-aminopropyl)-piperazine, N-(2-aminoethyl)-piperazine, N, N'- bisoxyethyl propylenediamine, 2,6-diaminopyridine, diethanolaminoacetamide,

diethanolamidopropionamide, Ν,Ν-bisoxyethylphenyl thiosemicarbazide, N,N-bis- oxyethylmethyl semicarbazide, p,p'-bis-aminomethyl dibenzyl methylamine, 2,6- diaminopyridine, 2-dimethylaminomethyl-2-methylpropanel, 3-diol. In certain embodiments, chain-extending agents are compounds that contain two amino groups. In certain

embodiments, chain-extending agents are selected from the group consisting of: ethylene diamine, 1,6-hexamethylene diamine, and 1,5-diamino-l-methyl-pentane.

In some embodiments, the higher polymers are formed by chain extension of any of the above-described prepolymers with polyamines, the end result is a higher molecular weight polyurethane/urea dispersion.

In certain embodiments, such polyurethane/urea dispersions comprise polymer chains of structure HI:

Hla wherein, each -^ group represents any one or more of the prepolymer compositions as defined above and described in the classes and subclasses herein including any of the prepolymer compositions described by structures Ol-al through 01-cl3,

each !^{chain ExteDder}l group represents a structure derived from any one or more of the diamine cross-linking agents described above, and

-R, is independently at each occurrence, -H or an optionally substituted C_1-8 aliphatic group.

In certain embodiments, inventive PUD's further contain branched structures derived by chain-extension with reagents having three or more groups reactive toward the isocyanate groups of the prepolymers. In certain embodiments, inventive PUDs contain branched structures resulting from inclusion of any of the branched prepolymer compositions described hereinabove.

The aqueous polyurethane dispersions disclosed herein may comprise water and from about 15 to about 75 weight percent solids, wherein the solids comprise a polyurethane polymer or prepolymer as described above and in the classes and subclasses herein. In certain embodiments, the aqueous polyurethane dispersion contains about 20 to about 60 weight percent solids. In certain embodiments, the aqueous polyurethane dispersion contains about 30 to about 40 weight percent solids. In certain embodiments, the aqueous polyurethane dispersion contains about 30, about 40, about 45, about 50 about 55, or about 60 weight percent solids. The aqueous polyurethane dispersions may be further diluted to any proportion.

In certain embodiments, the particle size of the polyurethane polymer phase contained within the aqueous polyurethane dispersion is less than about 3 microns. In certain embodiments, the particle size of the polyurethane polymer phase contained within the aqueous polyurethane dispersion is less than about 2.5, less than about 2, less than about 1.5, or less than about 1 micron. In certain embodiments, the particle size of the polyurethane polymer phase contained within the aqueous polyurethane dispersion is and more preferably less than about 1 micron.

In certain embodiments, the polyurethane polymer contained within the aqueous polyurethane dispersion has a free isocyanate functionality of approximately zero.

In certain embodiments, the viscosity of the aqueous polyurethane dispersion may range from about 40 to about 12,000 cps. In certain embodiments, the viscosity of the aqueous polyurethane dispersion ranges from about 100 to about 4,000 cps. In certain embodiments, the viscosity of the aqueous polyurethane dispersion ranges from about 200 to about 1 ,200 cps. The aqueous polyurethane dispersion will preferably remain storage stable and fully dispersed within the aqueous media for extended periods of time.

In certain embodiments, inventive polyurethane dispersions further comprise additives as are well known in the art. Typical additives include pigments, fillers, stabilizers curing agents and the like. Other additives well known to those skilled in the art can be used to aid in preparation of the dispersions of this invention. Such additives include surfactants, stabilizers, defoamers, antimicrobial agents, antioxidants, UV absorbers, carbodiimides, and the like.

Additives such as activators, curing agents, stabilizers such as Stabaxol™ P200, colorants, pigments, neutralizing agents, thickeners, non-reactive and reactive plasticizers, coalescing agents such as di(propylene glycol) methyl ether (DPM), waxes, slip and release agents, antimicrobial agents, surfactants such as Pluronic™ F68-LF and IGEPAL™ CO630 and silicone surfactants, metals, antioxidants, UV stabilizers, antiozonants, and the like, can optionally be added as appropriate before and/or during the processing of the dispersions of this invention into finished products as is well known to those skilled in the art. Additives may be used as appropriate in order to make articles or to treat (such as by impregnation, saturation, spraying, coating, or the like) porous and non-porous substrates such as papers, non- woven materials, textiles, leather, wood, concrete, masonry, metals, house wrap and other building materials, fiberglass, polymeric articles, personal protective equipment (such as hazardous material protective apparel, including face masks, medical drapes and gowns, and firemen's turnout gear), and the like. Applications include papers and non-wovens; fibrous materials; films, sheets, composites, and other articles; inks and printing binders; flock and other adhesives; and personal care products such as skin care, hair care, and nail care products; livestock and seed applications; and the like.

Suitable surfactants include a wide variety of nonionic, cationic, anionic, and zwitterionic surfactants, such as those disclosed in McCutcheon's Detergents and

Emulsifiers, North American Edition (1986), Allured Publishing Corporation; and in U.S. Pat. Nos. 3,755,560; 4,421,769; 4,704,272; 4,741,855; 4,788,006; and 5,011,681 each of which is incorporated herein by reference. Examples of suitable surfactants include silicone esters, alkyl and alkenyl sulfates; alkyl and alkenyl ethoxylated sulfates (preferably having an average degree of ethoxylation from 1 to about 10); succinamate surfactants such as alkylsulfosuccinamates and dialkyl esters of sulfosuccinic acid; neutralized fatty acid esters of isethionic acid; and alkyl and alkenyl sulfonates, such as olefin sulfonates and beta-alkoxy alkane sulfonates; and the like. Preferred are alkyl and alkenyl sulfates and alkyl and alkenyl ethoxylated sulfates, such as the sodium and ammonium salts of C ₁₂ -C ₁₈ sulfates and ethoxylated sulfates with a degree of ethoxylation from 1 to about 6, and more preferably from 1 to about 4, such as lauryl sulfate and laureth (3.0) sulfate sodium 3-dodecylaminopropionate; N-alkyltaurines such as prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. No. 2,658,072; N-higher alkyl aspartic acids such as produced according to the teaching of U.S. Pat. No. 2,438,091; and the products sold under the trade name "Miranol" and described in U.S. Pat. No. 2,528,378; and the like. Other suitable surfactants include alkyl (preferably C ₆ -C ₂₂ and more preferably C_8-12 ) amphoglycinates; alkyl (preferably C ₆ -C ₂₂ and more preferably C ₈ -C i₂ ) amphopropionates; and the like. Mixtures can also be used.

Suitable zwitterionic surfactants for use in the present compositions include those broadly described as derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, wherein which the aliphatic radicals can be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and another substituent contains an anionic water-dispersibility enhancing group, such as carboxy, sulfonate, sulfate, phosphate, phosphonate, and the like. Classes of zwitterionics include alkyl amino sulfonates, alkyl betaines and alkyl amido betaines, stearamido propyl dimethyl amine, diethyl amino ethyl stearamide, dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine, tridecyl amine, ethyl stearylamine, N- tallowpropane diamine, ethoxylated (5 moles ethylene oxide) stearylamine, dihydroxy ethyl stearylamine, arachidylbehenylamine, and the like. Mixtures can also be used.

Suitable viscosity adjusters include isopropyl alcohol, ethanol, sorbitol, propylene glycol, diethylene glycol, triethylene glycol, dimethyl ether, butylene glycol, and the like, and mixtures thereof.

Suitable plasticizers include ester derivatives of such acids and anhydrides as adipic acid, azelaic acid, benzoic acid, citric acid, dimer acids, fumaric acid, isobutyric acid, isophthalic acid, lauric acid, linoleic acid, maleic acid, maleic anyhydride, melissic acid, myristic acid, oleic acid, palmitic acid, phosphoric acid, phthalic acid, ricinoleic acid, sebacic acid, stearic acid, succinic acid, 1,2-benzenedicarboxylic acid, and the like, and mixtures thereof. Also suitable are epoxidized oils, glycerol derivatives, paraffin derivatives, sulfonic acid derivatives, and the like, and mixtures thereof and with the aforesaid derivatives.

Specific examples of such plasticizers include diethylhexyl adipate, heptyl nonyl adipate, diisodecyl adipate, the adipic acid polyesters sold by Solutia as the Santicizer series, dicapryl adipate, dimethyl azelate, diethylene glycol dibenzoate and dipropylene glycol dibenzoate (such as the K-Flex® esters from Noveon, Inc.), polyethylene glycol dibenzoate, 2,2,4- trimethyl- 1 ,3-pentanediol monoisobutyrate benzoate, 2,2,4-trimethyl- 1 ,3-pentanediol diisobutyrate, methyl (or ethyl, or butyl) phthalyl ethyl glycolate, triethyl citrate, dibutyl fumarate, 2,2,4-trimethyl- 1, 3 -pentanediol diisobutyrate, methyl laurate, methyl linoleate, din-butyl maleate, tricapryl trimellitate, heptyl nonyl trimellitate, triisodecyl trimellitate, triisononyl trimellitate, isopropyl myristate, butyl oleate, methyl palmitate, tricresyl phosphate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, di-2- ethylhexyl phthalate, octyl decyl phthalate, diisodecyl phthalate, heptyl nonyl phthalate, diundecyl phthalate, ditridecyl phthalate, dicyclohexyl phthalate, diphenyl phthalate, butyl benzyl phthalates such as the n-butylbenzyl ester of o-phthalic acid, isodecyl benzyl phthalate, alkyl (C ₇ /C 9 ) benzyl phthalate, dimethoxyethyl phthalate, 7-(2,6,6,8-tetramethyl- 4-oxa-3-oxo-nonyl) benzyl phthalate, di-2-ethylhexyl sebacate, butyl ricinoleate, dimethyl sebacate, methyl stearate, diethyl succinate, the butyl phenylmethyl ester of 1,2- benzenedicarboxylic acid, epoxidized linseed oil, glycerol triacetate, cUoroparaffins having about 40% to about 70% CI, o,p-toluenesulfonamide, N-ethyl p-toluene sulfonamide, N- cyclohexyl p-toluene sulfonamide, sulfonamide-formaldehyde resin, and the like, and mixtures thereof. Other suitable plasticizers known to those skilled in the art include castor oil, sunflower seed oil, soybean oil, aromatic petroleum condensate, partially hydrogenated terphenyls, silicone plasticizers such as dimethicone copolyol esters, dimethiconol esters, silicone carboxylates, guerbet esters, and the like, alone or as mixtures with other

plasticizers.

Examples of suitable reactive plasticizers include compositions and mixtures having ethylenic unsaturation, such as triallyl trimellitate (TATM), Stepanol PD-200LV (a mixture of (1) unsaturated oil and (2) polyester diol reaction product of o-phthalic acid and diethylene glycol from Stepan Company), and the like, and mixtures thereof. Other suitable reactive plasticizers include epoxidized plasticizers, including certain monofuctional and

polyfunctional glycidyl ethers such as Heloxy® Modifier 505 (polyglycidyl ether of castor oil) and Heloxy® Modifier 71 (dimer acid diglycidyl ether) from Shell Chemical Company, and the like, and mixtures thereof.

Examples of suitable flame retardant plasticizers include phosphorus-based plasticizers such as cyclic phosphates, phosphites, and phosphate esters, exemplified by Pliabrac™ TCP (tricresyl phosphate), Pliabrac™ TXP (trixylenyl phosphate), Antiblaze™ N (cyclic phosphate esters), Antiblaze™ TXP (tar acid, cresol, xylyl, phenol phosphates), and Antiblaze™ 524 (trixylyl phosphate) from Albright & Wilson Americas; Firemaster™ BZ 54 (halogenated aryl esters) from Great Lakes Chemicals; chlorinated biphenyl, 2-ethylhexyl diphenyl phosphate, isodecyl diphenyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, p-t-butylphenyl diphenyl phosphate, triphenyl phosphite, and the like. Other examples of phosphorus-based plasticizers include chlorinated alkyl phosphate esters such as Antiblaze™ 100 (chloro alkyl diphosphate ester) from Albright & Wilson Americas; alkyl phosphates and phosphites such as tributyl phosphate, tri-2-ethylhexyl phosphate, and triisoctyl phosphite; other organophosphates and organophosphites such as tributoxy ethylphosphate; other phosphates and phosphonates such as chlorinated diphosphate and chlorinated polyphosphonate; and the like. Mixtures can also be used.

Examples of suitable wetting, emulsifying, and conditioning plasticizers include alkyloxylated fatty alcohol phosphate esters such as oleth-2 phosphate, oleth-3 phosphate, oleth-4 phosphate, oleth-10 phosphate, oleth-20 phosphate, ceteth-8 phosphate, ceteareth-5 phosphate, ceteareth-10 phosphate, PPG ceteth-10 phosphate, and the like.

The inventive polyurethane dispersions described herein can also be provided as blends w/ other dispersions. Examples of other dispersions that may be added to

compositions of the present invention include those described in US 4,636,546,

DE3,718,520, DE 4,122,265, JP 04-081,405, each of which is incorporated herein by reference. F. Coatings, adhesives and articles of manufacture

In another aspect, the present invention encompasses coatings and adhesives containing or derived from the novel materials described hereinabove. The invention encompasses both the formulated coatings and adhesives as applied, and the cured coatings and adhesives.

In certain embodiments, the polyurethane dispersions of the present invention are suitable for use as protective coatings. The polyurethane coatings of this invention which contain the aliphatic polycarbonates as described above have certain advantages over existing materials. In certain embodiments, the coatings have unexpected and excellent hardness. As such, these coatings can be useful to protect materials such as wood, metal, stone, masonry, plastic, composites, fabrics, and the like. In certain embodiments, the coatings have excellent UV stability. As such, these coatings can be useful to protect materials such as wood, metal, stone, masonry, plastic, composites, fabrics, and the like. In certain embodiments, the present invention encompasses such coatings and coated articles.

In other embodiments, the polyurethane dispersions of the present invention are suitable for use as adhesives. In certain embodiments, the present invention encompasses polyurethane adhesives containing any of the polyurethane dispersions or prepolymers described hereinabove, as well as articles of manufacture in which parts are joined using the novel adhesives. II. Methods of Making

In another aspect, the present invention encompasses methods of making the prepolymer compositions and polyurethane dispersions described above.

In certain embodiments, methods of the present invention include the steps of:

a) providin an aliphatic polycarbonate polyol of formula PI,

1 /1 \ J

wherein, R , R , R , R , Y, n, , x andy are at each occurrence as defined above and described in the classes and subclasses herein,

b) contacting the aliphatic polycarbonate polyol with one or more reagents having a

plurality of isocyanate groups, optionally in the presence of one or more coreactants capable of reacting with isocyanate groups, where the coreactants are selected from any of those disclosed hereinabove; and

c) allowing the polyol to react with the reagent having a plurality of isocyanate groups to form a prepolymer.

In certain embodiments of the methods, the aliphatic polycarbonate polyol provided in step (a), the reagents having a plurality of isocyanate groups provided in step (b), and the optional coreactants utilized in step (b) are independently selected from any of the specific embodiments of those materials defined above and described in the classes and subclasses herein.

In certain embodiments, the aliphatic polycarbonate polyol provided in step (a) is selected from the group consisting of P2, P3, P4, P5, P6, P7, P8 and mixtures of two or more of these, where P2-P8 are as defined above and described in the classes and subclasses herein.

In certain embodiments, the aliphatic polycarbonate polyol provided in step (a) is selected from the group consisting of compounds P2a through P2r-a where each P2

compound is as defined above and described in the classes and subclasses herein.

In certain embodiments, the the aliphatic polycarbonate polyol provided in step (a) is selected from the group consisting of Ql, Q2, Q3, Q4, and mixtures of any of these.

In certain embodiments, the the aliphatic polycarbonate polyol provided in step (a) is selected from the group consisting of:

98%o -OH end groups;

Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 2,000 g/mol (e.g. n is on average between about 8 and about 9.5), a

polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups; Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 13 and about 15), a

Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 1,000 g/mol (e.g. n is on average between about 3.5 and about 4.5), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least

98% -OH end groups;

Poly (propylene carbonate) of formula Q2 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 13 and about 15), a

Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol (e.g. each n is between about 4 and about 16), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98%) -OH end groups;

98% -OH end groups;

polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; and Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 3,000 g/mol (e.g. n is on average between about 15 and about 17), a

In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) is selected from the group consisting of: aliphatic diisocyanates, aromatic

diisocyanates, oligomeric diisocyanates, and difunctional isocyanate prepolymers.

In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises one or more aliphatic diisocyanates. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) is selected from the group consisting of: HDI, IPDI, H₁₂MDI, H6-XDI, TMDI, 1 ,4-cyclohexyl diisocyanate, 1,4- tetramethylene diisocyanate, trimethylhexane diisocyanate, and mixtures of any two or more of these. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) is selected from the group consisting of: HDI, IPDI, H₁₂MDI and mixtures of two or more of these. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises HDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises IPDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises H₁₂MDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises H6-XDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises TMDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises oligomers or derivatives of any of the above aliphatic isocyanates. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises biurets of any of the above aliphatic isocyanates.

In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises one or more aromatic diisocyanates. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) is selected from the group consisting of: 2,4-TDI, 2,6-TDI, MDI, XDI, TMXDI, and mixtures of any two or more of these. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) is selected from the group consisting of: TDI and MDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises TDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises 2,4-TDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises 2,6-TDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises H6-XDI. In certain

embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises MDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises XDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises TMXDI. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises oligomers or derivatives of any of the above aromatic isocyanates. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises biurets of any of the above aromatic isocyanates.

In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises any one or more of the materials in Table 1. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises any one or more of the materials in Table 2. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) comprises any one or more of the materials in Table 3. In certain embodiments, the reagent having a plurality of isocyanate groups utilized in step (b) is selected from the group consisting of: Easaqua™ WAT; Easaqua™ WAT-1 ;

Easaqua™ WT 1000; Easaqua™ WT 2102; Easaqua™ X D 401; Easaqua™ X D 803;

Easaqua™ X M 501; Easaqua™ X M 502; Easaqua™ X WAT-3; and Easaqua™ X WAT-4.

In certain embodiments, the method further includes controlling the ratio of the aliphatic polycarbonate polyol and, if present, the one or more coreactants, to the reagents having a plurality of isocyanate groups such that there is a molar excess of isocyanate groups.

In certain embodiments, the step of contacting aliphatic polycarbonate polyol with the reagent having a plurality of isocyanate groups is performed in the presence of a solvent. In certain embodiments, the step is performed in a non-protic polar organic solvent. In certain embodiments, the step is performed in acetone. In certain embodiments, the step is performed in NMP. In certain embodiments, where the prepolymer is formed in an organic solvent, the method further comprises mixing the solution of prepolymer thus formed with water and then distilling off at least a portion of the organic solvent.

In certain embodiments, step (b) further includes providing one or more catalysts. In certain embodiments, catalysts provided in step (b) include tin based materials. In certain embodiments, catalysts provided in step (b) are selected from the group consisting of di-butyl tin dilaurate, dibutylbis(lauryltliio)stannate, dibutyltinbis(isooctylmercapto acetate) and dibutyltinbis(isooctylmaleate), tin octaoate and mixtures of any of these. In certain embodiments, catalysts provided in step (b) include tertiary amines. In certain embodiments, catalysts provided in step (b) are selected from the group consisting of: DABCO,

pentametyldipropylenetriamine, bis(dimethylamino ethyl ether),

pentamethyldiethylenetriamine, DBU phenol salt, dimethylcyclohexylamine, 2,4,6-tris(N,N- dimethylaminomethyl)phenol (DMT-30), l,3,5-tris(3-dimethylaminopropyl)hexahydro-s- triazine, ammonium salts and combinations of any of these.

In certain embodiments, one or more coreactants are provided in step (b). In certain embodiments, the coreactant provided is selected from the group consisting of: other types of polyols (e.g. polyether polyols, polyester polyols, acrylics, or other polycarbonate polyols), and small molecules with functional groups reactive toward isocyanates such as hydroxyl groups, amino groups, thiol groups, and the like. In certain embodiments, coreactants, comprise molecules with two or more functional groups reactive toward isocyanates.

In certain embodiments, a coreactant provided in step (b) comprises a polyhydric alcohol. In certain embodiments, a coreactant provided in step (b) comprises a dihydric alcohol. In certain embodiments, the dihydric alcohol provided in step (b) comprises a C_2-40 diol. In certain embodiments, the dihydric alcohol provided in step (b) is selected from the group consisting of: 1,2-ethanediol, 1 ,2-propanediol, 1,3 -propanediol, 1,2-butanediol, 1,3- butanediol, 1 ,4-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-l,3-diol, 2-butyl-2- ethylpropane-l,3-diol, 2-methyl-2,4-pentane diol, 2-ethyl-l,3-hexane diol, 2-methyl-l,3- propane diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12- dodecanediol, 2,2,4,4-tetramethylcyclobutane-l,3-diol, 1,3-cyclopentanediol, 1,2- cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3- cyclohexanedimethanol, 1 ,4-cyclohexanedimethanol, 1 ,4-cyclohexanediethanol, isosorbide, glycerol monoesters, glycerol monoethers, trimethylolpropane monoesters, trimethylolpropane monoethers, pentaerythritol diesters, pentaerythritol diethers, and alkoxylated derivatives of any of these.

In certain embodiments, a coreactant provided in step (b) comprises a dihydric alcohol selected from the group consisting of: diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly(ethylene glycol), such as those having number average molecular weights of from 220 to about 2000 g/mol, dipropylene glycol, tripropylene glycol, and higher poly(propylene glycols) such as those having number average molecular weights of from 234 to about 2000 g/mol.

In certain embodiments, a coreactant provided in step (b) comprises an alkoxylated derivative of a compound selected from the group consisting of: a diacid, a diol, or a hydroxy acid. In certain embodiments, the alkoxylated derivatives comprise ethoxylated or propoxylated compounds.

In certain embodiments, a coreactant provided in step (b) comprises a polymeric diol. In certain embodiments, the polymeric diol provided in step (b) is selected from the group consisting of polyethers, polyesters, hydroxy-tenninated polyolefins, polyether-copolyesters, polyether polycarbonates, polycarbonate-copolyesters, and alkoxylated analogs of any of these. In certain embodiments, the polymeric diol has an average molecular weight less than about 2000 g/mol

In some embodiments, a coreactant provided in step (b) comprises a triol or higher polyhydric alcohol. In certain embodiments, a coreactant provided in step (b) is selected from the group consisting of: glycerol, 1 ,2,4-butanetriol, 2-(hydroxymethyl)- 1,3 -propanediol; hexane triols, trimethylol propane, trimethylol ethane, trimethylolhexane, 1,4- cyclohexanetrimethanol, pentaerythritol mono esters, pentaerythritol mono ethers, and alkoxylated analogs of any of these. In certain embodiments, alkoxylated derivatives comprise ethoxylated or propoxylated compounds.

In some embodiments, a coreactant provided in step (b) comprises a polyhydric alcohol with four to six hydroxy groups. In certain embodiments, a coreactant present in step (b) comprises dipentaerithrotol or an alkoxylated analog thereof. In certain embodiments, coreactant present in step (b) comprises sorbitol or an alkoxylated analog thereof. In certain embodiments, a functional coreactant provided in step (b) comprises a polyhydric alcohol containing one or more moieties that can be converted to an ionic functional group. In certain embodiments, the moiety that can be converted to an ionic functional group is selected from the group consisting of: carboxylic acids, esters, anhydrides, sulfonic acids, sulfamic acids, phosphates, and amino groups.

In certain embodiments, a coreactant provided in step (b) comprises a hydroxy- carboxylic acid having the general formula (HO)_xQ(COOH¾,, wherein Q is a straight or branched hydrocarbon radical containing 1 to 12 carbon atoms, and x andy are each integers from 1 to 3. In certain embodiments, a coreactant provided in step (b) comprises a diol carboxylic acid. In certain embodiments, a coreactant provided in step (b) comprises a bis(hydroxylalkyl) alkanoic acid. In certain embodiments, a coreactant provided in step (b) comprises a bis(hydroxylmethyl) alkanoic acid. In certain embodiments the diol carboxylic acid provided in step (b) is selected from the group consisting of 2,2 bis-(hydroxymethyl)- propanoic acid (dimethylolpropionic acid, DMPA) 2,2-bis(hydroxymethyl) butanoic acid (dimethylolbutanoic acid; DMBA), dihydroxysuccinic acid (tartaric acid), and 4,4'- bis(hydroxyphenyl) valeric acid. In certain embodiments, a coreactant comprises an N,N- bis(2-hydroxyalkyl)carboxylic acid.

In certain embodiments, a coreactant provided in step (b) comprises a polyhydric alcohol containing a sulfonic acid functional group. In certain embodiments, a coreactant comprises a diol sulfonic acid. In certain embodiments, a polyhydric alcohol containing a sulfonic acid is selected from the group consisting of: 2-hydroxymethyl-3-hydroxypropane sulfonic acid, 2-Butene-l,4-diol-2-sulfonic acid, and materials disclosed in U.S. Pat. No. 4,108,814 and US Pat. App. Pub. No. 2010/0273029 the entirety of each of which is incorporated herein by reference.

In certain embodiments, a coreactant provided in step (b) comprises a polyhydric alcohol containing a sulfamic acid functional group. In certain embodiments, a polyhydric alcohol containing a sulfamic acid is selected from the group consisting of: [N,N-bis(2- hydroxyalkyl)sulfamic acid (where each alkyl group is independently a C_2-6 straight chain, branched or cyclic aliphatic group) or epoxide adducts thereof (the epoxide being ethylene oxide or propylene oxide for instance, the number of moles of epoxide added being 1 to 6) also epoxide adducts of sulfopolycarboxylic acids [e.g. sulfoisophthalic acid, sulfosuccinic acid, etc.], and aminosulfonic acids [e.g. 2-aminoethanesulfonic acid, 3- aminopropanesulfonic acid, etc.].

In certain embodiments, a coreactant a coreactant provided in step (b) comprises a polyhydric alcohol containing a phosphate group. In certain embodiments, a coreactant comprises a bis (2-hydroxaikyl) phosphate (where each alkyl group is independently a C_2-6 straight chain, branched or cyclic aliphatic group). In certain embodiments, a coreactant a coreactant provided in step (b) comprises bis (2-hydroxethyl) phosphate.

In certain embodiments, a coreactant a coreactant provided in step (b) comprises a polyhydric alcohol comprising one or more amino groups. In certain embodiments, a coreactant a coreactant provided in step (b) comprises an amino diol. In certain

embodiments, a coreactant a coreactant provided in step (b) comprises a diol containing a tertiary amino group. In certain embodiments, a coreactant provided in step (b) is selected from the group consisting of: diethanolamine (DEA), N-methyldiethanolamine (MDEA), N- ethyldiethanolamine (EDEA), N-butyldiethanolamine (BDEA), N,N-bis(hydroxyethyl)-a- amino pyridine, dipropanolarnine, diisopropanolamine (DIP A), N- methyldiisopropanolamine, Diisopropanol-p-toluidine, N,N-Bis(hydroxyethyl)-3 - chloroaniline, 3-diethylaminopropane-l,2-diol, 3-dimethylaminopropane-l,2-diol and iV- hydroxyethylpiperidine. In certain embodiments, a coreactant a coreactant provided in step (b) comprises a diol containing a quaternary amino group. In certain embodiments, a coreactant . a coreactant provided in step (b) is an acid salt or quatemized derivative of any of the amino alcohols described above.

Compounds having at least one crosslinkable functional group can also be provided in step (b), if desired. Examples of such compounds include those having carbonyl, amine, epoxy, acetoacetoxy, urea-formaldehyde, auto-oxidative groups that crosslink via oxidization, ethylenically unsaturated groups optionally with UV light activation, olefinic and hydrazide groups, blocked isocyanates, and the like, and mixtures of such groups and the same groups in protected forms. In certain embodiments, a functional coreactant is provided in step (b), wherein the functional coreactant provides hydrophilic characteristics to the resulting chain-extended composition.

In certain embodiments, a functional coreactant is provided in step (b) comprises hydrophilic groups, ionic groups, or precursors to ionic groups any of which may act as internal emulsifiers and thereby aid in the formation of stable aqueous dispersions of the inventive compositions. In certain embodiments, such functional coreactants comprise precursors of ionic groups. In certain embodiments, functional coreactants comprise precursors of cationic groups. In certain embodiments, functional coreactants comprise precursors of anionic groups.

In certain embodiments, where a coreactant provided in step (b) contains a precursor of an ionic group, the method further comprises a step after step (c) of treating the prepolymer with a reagent to convert the precursor of an ionic group into an ionic group.

In certain embodiments, a coreactant provided in step (b) comprises a carboxylic acid moiety and the method further comprises a step of treating the prepolymer with a base to form a carboxylate salt.

In certain embodiments, a coreactant provided in step (b) comprises an amine moiety and the method further comprises a step of treating the prepolymer with an acid or an alkylating agent to form an ammonium salt.

In certain embodiments, methods of the present invention further comprise the step of dispersing the prepolymer from step (c) in water.

In certain embodiments, the step of dispersing the prepolymer is performed in the presence of one or more chain-extending reagents wherein the chain extending reagents have a plurality of functional groups reactive toward isocyanates. In certain embodiments, the chain extending reagent is dissolved in the aqueous phase prior to or during the step of dispersing the prepolymer.

In certain embodiments, the method includes dispersing the prepolymer from step (c) into water in the presence of a polyamine compound.

In certain embodiments, the method includes dispersing the prepolymer from step (c) into water in the presence of a compound selected from the group consisting of: mono-, bis- or polyalkoxylated aliphatic, cycloaliphatic, aromatic or heterocyclic primary amines, N- methyl diethanolamine, N-ethyl diethanolamine, N-propyl diethanolamine, N-isopropyl diethanolamine, N-butyl diethanolamine, N-isobutyl diethanolamine, N-oleyl

diethanolamine, N-stearyl diethanolamine, ethoxylated coconut oil fatty amine, N-allyl diethanolamine, N-methyl diisopropanolamine, N-ethyl diisopropanolamine, N-propyl diisopropanolamine, N-butyl diisopropanolamine, cyclohexyl diisopropanolamine, N,N- diethoxylaniline, Ν,Ν-diethoxyl toluidine, N,N-diethoxyl-l-aminopyridine, N,N'-diethoxyl piperazine, dimethyl-bis-ethoxyl hydrazine, N,N'-bis-(2-hydroxyethyl)-N,N'-diethylhexahydr op-phenylenediamine, N-12-hydroxyethyl piperazine, polyalkoxylated amines, propoxylated methyl diethanolamine, N-methyl-N,N-bis-3 -aminopropylamine, N-(3 -aminopropyl)-N,N'- dimethyl ethylenediamine, N-(3-aminopropyl)-N-methyl ethanolamine, N,N'-bis-(3- aminopropyl)-N,N'-dimethyl ethylenediamine, N,N'-bis-(3-aminopropyl)-piperazine, N-(2- aminoethyl)-piperazine, N, N'-bisoxyethyl propylenediamine, 2,6-diaminopyridine, diethanolaminoacetamide, diethanolamidopropionamide, N,N-bisoxyethylphenyl

thiosemicarbazide, Ν,Ν-bis-oxyethylmethyl semicarbazide, p,p'-bis-aminomethyl dibenzyl methylamine, 2,6-diaminopyridine, 2-dimethylaminomethyl-2-methylpropanel, 3-diol. In certain embodiments, chain-extending agents are compounds that contain two amino groups. In certain embodiments, chain-extending agents are selected from the group consisting of: ethylene diamine, 1,6-hexamethylene diamine, and 1,5-diamino-l-methyl-pentane.

In certain embodiments, the method includes dispersing the prepolymer from step (c) into water in the presence of a compound selected from the group consisting of: diethylene triamine (DETA), ethylene diamine (EDA), meta-xylylenediamine (MXDA), aminoethyl ethanolamine (AEEA), 2-methyl pentane diamine, and mixtures thereof.

In certain embodiments, the method includes dispersing the prepolymer from step (c) into water in the presence of a compound selected from the group consisting of: propylene diamine, butylene diamine, hexamethylene diamine, cyclohexylene diamine, phenylene diamine, tolylene diamine, 3,3-dichlorobenzidene, 4,4'-methylene-bis-(2-cMoroaniline), 3,3- dichloro-4,4-diamino diphenylmethane, and sulfonated primary and/or secondary amines.

In certain embodiments, the method includes dispersing the prepolymer from step (c) into water in the presence of a polyalcohol. In certain embodiments, the polyalcohol has from 2 to 12 carbon atoms. In certain embodiments, the polyalcohol has from 2 to 8 carbon atoms. In certain embodiments, the method includes dispersing the prepolymer from step (c) into water in the presence of a compound selected from the group consisting of: ethylene glycol, diethylene glycol, neopentyl glycol, butanediols, hexanediol, and the like, and mixtures thereof.

In certain embodiments, the methods include a step of providing a chain extending reagent that contains blocked functional groups that are liberated on contact with water and which once liberated will react with isocyanates. In certain embodiments, methods of the present invention include combining the prepolymer with a blocked chain extending reagent. In certain embodiments the methods include a step of dispersing the combination of prepolymer and blocked chain extending reagent into water. In certain embodiments, the method includes dispersing the prepolymer from step (c) into water in the presence of a compound selected from the group consisting of: hydrazine, substituted hydrazines, hydrazine reaction products, and the like, and mixtures thereof.

In certain embodiments, methods of the present invention comprise the step of applying any of the above described polyurethane dispersions to a surface. In certain embodiments, such methods further include the step of allowing the water to evaporate from the dispersion.

EXAMPLES The present invention is illustrated by the following examples. It is to be understood that the particular examples, materials, amounts, and procedures are to be interpreted broadly in accordance with the scope and spirit of the invention as set forth herein.

Example I.

Synthesis of Polyurethane Dispersions Using Novel Polypropylene Carbonate Polyols

Aqueous polyurethane dispersions (PUDs) were synthesized using the NMP process incorporating novel polypropylene carbonate polyols for the first time. Aqueous PUDs were also synthesized using three commercial diols as controls. PUD synthesis was successful for all of the polyols, however, the PUDs from the lowest molecular weight polypropylene carbonate polyol were not shelf stable. Particle size, viscosity, percent resin, and pH of the polypropylene carbonate polyol based PUDs were within normal range as compared to commercial controls. Films of the PUDs were prepared for evaluation and cured at ambient conditions for several days as well as force-cured in an oven overnight. Films of the PUDs based on the polypropylene carbonate polyols were generally harder and more brittle than the control PUDs, especially for the samples which were force-cured as characterized by nanoindentation. Overall, the work showed that the polypropylene carbonate based polyols can be used to prepare aqueous PUDs.

Aqueous polyurethane dispersions (PUDs) have recently emerged to replace their solvent-based counterparts for a number of applications due to increasing health and environmental awareness. Waterborne PUDs are an important class of polymer dispersion that can be used in many industrial applications such as coatings for wood fmshing; glass fiber sizing; adhesives; automotive topcoats and other applications (see Keyvani, Advances in Polymer Technology, 2003, 22, 218-224). Research in the area of polyurethane technology has already spanned many decades, and the uses of polyurethanes for coatings applications and efforts to enhance knowledge pertaining to their structure-property relationships continue to expand due to the high performance characteristics of polyurethanes (see Madbouly et al., Macromolecules, 2005, 38, 4014-4023; Nasrullah et al., J. Coat.

Technol. Res., 2009, 6, 1-10; Nasrullah et al., Polymer Preprints (American Chemical Society, Division of Polymer Chemistry), 2007, 48, 175-176; Nanda et al., Macromolecules, 2006, 39, 7037-7043).

Polyurethanes are generally synthesized from isocyanates and polyols, and while the incorporation of amine functional chain extenders results in the formation of urea groups these tend to be included in the broad category of polyurethanes. Due to a large number of available isocyanates and polyols, it is possible to get a broad spectrum of excellent properties. Recently, Novomer has developed a novel process for the synthesis of low molecular weight polypropylene carbonate polyols from the metal-catalyzed

copolymerization of carbon dioxide (C0₂) with epoxides (see Allen et al., ACS Symp. Ser., 2006, 921, 116-129; Allen et al., J. Am. Chem. Soc, 2002, 124, 14284-14285; Coates et al., Angew. Chem., Int. Ed., 2004, 43, 6618-6639; Cohen et al, J. Am. Chem. Soc, 2005; 127, 10869-10878; Cohen et al, J. Polym. ScL, Part A: Polym. Chem., 2006; 44, 5182-5191; Qin et al., Angew. Chem., Int. Ed., 2003; 42, 5484-5487; Ritter, S.K., Chemical & Engineering News, 2007, 85, 11-17). C0₂ is safe, inert, highly abundant in atmosphere and low cost (see Ritter, S.K. Chemical & Engineering News, 2007, 85, 11-17). These polyols can potentially be used as a soft segment in polyurethanes, which would help cut production costs. The main focus of this work is to explore the synthesis of aqueous PUDs using these novel polypropylene carbonate polyols by traditional methods in the laboratory and to establish their physical and mechanical properties. The synthesized PUDs are compared with PUDs obtained using commercially available polyester and polycarbonate polyols. The outline of the synthesis of PUD is given in Scheme A. The synthesis involves formation of an isocyanate functional prepolymer followed by dispersion in water and chain extension to obtain the aqueous PUD (see Nasrallah et al., J. Coat. Technol. Res., 2009, 6, 1-10; Nasrallah et al., Polymer Preprints (American Chemical Society, Division of Polymer Chemistry), 2007, 48, 175-176).

Experimental

Materials. 3-Hydroxy-2-(hydroxymethyl)-2-methyl-propanoic acid

(dimethylolpropionic acid, DMPA) was supplied by Perstorp. N-Methyl-2-pyrrolidone

(NMP, Sigma-Aldrich, 99.5%), dibutyltin dilaurate (DBTDL, Aldrich, 95%), Irieraylamine (TEA, Aldrich, 99.5%), and emylenediamine (EDA, Aldrich, 99%) were used without further purification. Linear polyester polyol (Polyester PE 170HNA), polycarbonate polyester polyols (DESMOPHEN® C 2100 and DESMOPHEN® C 2200) and dicyclohexylmethane diisocyanate ( 1 , F -methylenebis [4-isocyanatocyclohexane]) were obtained from Bayer MaterialScience. Three novel poly(propylene carbonate) diols supplied by Novomer NOV 7E21 (Mw = 1100), NOV 94B0 (Mw = 2100), and NOV7DF1 (Mw = 2900) were used as received. DI water from the laboratory was used for the dispersion of the polyurethane.

Instrumentation and Measurements. Viscosity measurements were done using Brookfield DV-II+ Pro viscometer. The viscosity was measured at room temperature around 23 °C with spindle 06 at 100 rpm. The particle size was measured on water-diluted samples using Submicron Particle Sizer, NICOMP™ 380 and both Gaussian and Nicomp methods were used. An automated surface energy (SE) measurement unit manufactured by Symyx Discovery Tools, Inc and First Ten Angstroms was used to measure the SE of PUD coatings. Droplets of water and methylene iodide (MI) were deposited on the PUD coating separately and a CCD camera imaged the droplets and then automated image analysis was used to determine the contact angles (CA). Three droplets of water and MI were used for each measurement. SE was calculated from the CA data using the Owens- Wendt equation. Quasistatic Nanoindentation was performed using Hysitron Triboindenter (Hysitron

Incorporated) mounted with a Berkovich tip. The indenting was done in load control mode with the following operating parameters: a 5 second loading, a hold time of 5 seconds at the maximum load to allow visco-elastic dissipation, and a 5 second unloading. Maximum load was 300 uN and pre-load was set to 2 μΝ. Moduli of the samples were obtained from the unloading segment of a resulting force-depth curve using the Oliver and Pharr method. Dynamic mechanical analysis (DMA) was performed using a TA Instruments Q800 DMA in rectangular tension/compression geometry. Free films of the cured materials were obtained by removing the material from TEFLON^® covered aluminum substrate using a spatula. Sample size was 21 mm x 5 mm and film thickness was measured using a

MICROMASTER^® micrometer. The analysis was carried out from -75 °C to 100 °C at a frequency of 1 Hz and a ramp rate of 5 °C m T¹.

Scheme A. General schematic of aqueous PUD synthesis

General Experimental Procedure for PUD Synthesis. A general synthesis procedure followed for synthesis using the laboratory method. A one liter reactor vessel was fitted with an agitator, nitrogen inlet, and water condenser. The reactor was heated with an oil bath on a hotplate. The polyol, DMPA, diisocyanate, and NMP are charged and stirred at 250 rpm until the mixture becomes homogenous. Then DBTDL catalyst is added, the mixture is heated to 90 °C, and the temperature is controlled so that it does not go above 95 °C to avoid side reactions or exotherm. When the theoretical NCO content is reached, the mixture is cooled to 70 °C and TEA is added with an increase agitation to 500 rpm. The dispersing water is at room temperature and it is added under high agitation, 500 - 2200 rpm, over a 25 min period. Then, EDA and water are combined at ambient temperature at 25 °C, and added to the reaction mixture drop-wise over 10 - 15 min with agitation of 500 rpm. The agitation is continued for another 2 h to complete the water reaction with residual isocyanate and form the dispersion. Table 1 shows all the PUDs synthesized in 400 - 500 g quantities and they are good and stable. It is important to mention that the PUDs based on NOV 7E21-1 and NOV 7E21-2 became paste or solid cake in 2 weeks and 1 week, respectively, hence incomplete characterization was performed on these two PUDs.

Results and Discussion

PUD synthesis was performed using polypropylene carbonate polyols and

dicyclohexyhnethane diisocyanate using a traditional laboratory setup as shown in Table 4. Two iterations of PUDs were made with each of the polypropylene carbonate polyols. Three Bayer polyols were also used to synthesize PUDs for comparison and control. Once the PUDs were prepared, they were allowed to sit in the shelf overnight so that the froth is settled. The average particle size was measured with water-diluted samples of PUD and the particle size obtained for all the PUDs are given in Table 4. The particle sizes obtained for all the PUDs are less than 500 nm in most cases indicating that a stable dispersion is formed. One can notice that the particle size is very broad in the case of NOV 7E21-1 and NOV

94B0-1 in the first attempt of synthesis. Percent resin solids, pH and viscosities of the PUDs and values are also presented in Table 4.

Table 4. Characterization of Aqueous PUDs

NOV 7E21-1 4749 - 37.17 - - - -

NOV 7E21-2 203 - 38.79 66 53 45

NOV 94BO-1 433 8 48.46 80 65 51 46

NOV 94BO-2 371 8.5 47.83 80 63 47 48

NOV 7DF1-1 173 10 53.49 400 57 47 52

NOV 7DF1-2 201 9 55.44 280 53 46 54

Polyurethane coating films were also prepared by drawdown over microscope glass slides. Curing was achieved by allowing the coatings to lie horizontally overnight at ambient conditions. The water and MI contact angles and surface energies for PUD coatings cured at room temperature are given in Table 4. Another set of coatings were cured overnight at ambient conditions followed by an overnight heat treatment at 70 °C. These coatings were used for hardness measurements using Nanoindentation. The reduced modulus and hardness for PUD coatings are given in Figures 1 and 2, respectively. Both the reduced modulus and hardness are high for the polypropylene carbonate polyols compared to the control PUDs. PUD coating films were also prepared by drawdown over TEFLON^® sheets glued to aluminum panels and cured at room temperature (RT). Free films were obtained by releasing the coatings from the TEFLON^® sheet using a spatula at one edge of the coating. These free films were used to determine Tg and storage Modulus using DMA and the results are presented in Figures 3 and 4 respectively. Tg was obtained from the maximum peak in the tan δ curves. Additional characterization work such as tensile strength, Konig Pendulum

Hardness, Cross hatch adhesion test, and chemical and solvent resistance measurement using pencil hardness are in progress.

Conclusions

Aqueous PUDs were synthesized using novel polypropylene carbonate diols for the first time. Two of the three PUDs are shelf stable with most of the desired properties of a PUD. It is likely that adjustments to the PUD recipe can improve the stability of the PUD with the lowest MW polypropylene carbonate diol. Overall, the film properties indicate that the PUDs made with the polypropylene carbonate diols polyols are harder and more brittle than the control polyols as characterized by Nanoindentation. Introducing a slight amount of cross-linking into the PUD might help overcome some of these property limitations. More characterization work is in progress and will be discussed in future publication. Example II.

Synthesis and Characterization of Polyurethane Dispersions based on Novel Polyols Aqueous polyurethane dispersions (PUDs) were synthesized using the NMP process incorporating candidate polycarbonate polyols supplied by Novomer Inc. as well as three commercial controls. PUD synthesis was successful for all of the polyols, however, the PUDs from the lowest molecular weight candidate polyol was not shelf stable. Particle size and viscosity of the PUDs was within normal ranges. Films of the PUDs were prepared for evaluation and cured at ambient conditions for several days as well as force-cured in an oven overnight. Films of the PUDs based on the candidate polyols were generally harder and more brittle than the control PUDs, especially for the samples which were force-cured. The films from the PUDs could not survive treatment with high humidity. A variety of chemical resistance tests were carried out with the PUDs based on the polyols performing similar to the controls. Overall, the work showed that the polyols can be used to prepare aqueous PUDs. Optimization of the PUD composition can be undertaken to improve the film properties of the resulting coatings. Our objective was to synthesize and charachterize aqueous polyurethane dispersions (PUDs) using the candidate poly(propylene carbonate) diols.

Introduction

Aqueous polyurethane dispersions (PUDs) have recently emerged to replace their solvent-based counterparts for various applications due to increasing health and

environmental awareness. Organic solvent based polyurethanes are increasingly restricted in their traditional applications because of the demands of environmental regulations, abetment costs and safety. In contrast, aqueous PUDs are candidates with promise to replace them. Waterborne PUDs are an important class of polymer dispersion that can be used in many industrial applications such as coatings for wood finishing; glass fiber sizing; adhesives; automotive topcoats and other applications. The continuous need for reductions in both production costs and volatile organic compound emissions has speared an intense activity of research on the development of water-based polymer systems, particularly for coating and adhesive formulations. Novomer has developed an amorphous, colorless thermoplastic polymer i.e., polypropylene carbonate polyols which decomposes into environmentally benign products making it the perfect solution for broad applications in the electronics, brazing and ceramics industries. These novel polyols are produced from the metal-catalyzed copolymerization of carbon dioxide with epoxides. This example reports the synthesis of aqueous PUD using these polypropylene carbonate polyols by traditional method in the laboratory. The scheme for the synthesis of PUD is shown in Example I (Scheme A). The synthesis involves formation of an isocyanate functional prepolymer followed by dispersion in water and chain extension to obtain the aqueous PUD.

Research in the area of polyurethane technology has already spanned many decades, and the uses of polyurethanes are endless for coatings applications and efforts to enhance knowledge pertaining to their structure-property relationships continues due to the high performance characteristics of polyurethane. Polyurethanes are generally synthesized from isocyanates and polyols, and while the incorporation of amine functional chain extenders results in the formation of urea groups, these tend to be included in the broad category of polyurethanes. Due to a large number of available isocyanates and polyols, it is possible to get a broad spectrum of excellent properties. The primary focus of this example was the synthesis of PUDs using candidate poly(propylene carbonate) diols, and determination of the basic film properties of the PUDs. The synthesized PUDs are compared with the PUDs obtained using Bayer polyols such as polyester and polycarbonate polyester polyols. Experimental

Materials. 3-Hydroxy-2-(hydroxymethyl)-2-methyl-propanoic acid

(dimethylolpropionic acid, DMPA) was supplied by Perstorp. N-Methyl-2-pyrrolidone (NMP, Sigma-Aldrich, 99.5%), dibutyltin dilaurate (DBTDL, Aldrich, 95%), triethylamine (TEA, Aldrich, 99.5%), and ethylenediamine (EDA, Aldrich, 99%) were used without further purification. Linear polyester polyol (Polyester PE 170HNA), polycarbonate polyester polyols (DESMOPHEN^® C 2100 and DESMOPHEN^® C 2200) and dicyclohexylmethane diisocyanate (Ι,Γ-methylenebis [4-isocyanatocyclohexane]) were obtained from Bayer MaterialScience. Three novel poly(propylene carbonate) diols supplied by Novomer NOV 7E21 (Mw = 1100), NOV 94B0 (Mw = 2100), and NOV7DF1 (Mw = 2900) were used as received. DI water from the laboratory was used for the dispersion of the polyurethane. General Experimental Procedure. A general synthesis procedure was followed for synthesis using the laboratory method. A one liter reactor vessel was fitted with an agitator, nitrogen inlet, and water condenser. The reactor was heated with an oil bath on a hotplate. The polyol, DMPA, diisocyanate, and MP are charged and stirred at 250 rpm until the mixture becomes homogenous. Then DBTDL catalyst is added, the mixture is heated to 90 °C, and the temperature is controlled so that it does not go above 95 °C to avoid side reactions or exotherm. When the theoretical NCO content is reached, the mixture is cooled to 70 °C and TEA is added with an increase agitation to 500 rpm. The dispersing water is at room temperature and it is added under high agitation, 500 - 2200 rpm, over a 25 min period. Then, EDA and water are combined at ambient temperature at 25 °C, and added to the reaction mixture drop- wise over 10 - 15 min with agitation of 500 rpm. The agitation is continued for another 2 h to complete the water reaction with residual isocyanate and form the dispersion. During the synthesis, NCO titrations were performed to obtain the free NCO values. A aliquot of prepolymer was drawn from the reactor vessel, weighed, dissolved in toluene and reacted with 0.1 N dibutyl amine and titrated against 0.1 N HCl. Using the blank titer value, sample titer value and weight of prepolymer, free NCO values were calculated at different timings of PUD synthesis and these are listed in Table 5.

PUDs were synthesized in 400 - 500 g quantities. The expected yield and the obtained yield are listed in the Table 5. It is important to mention that NOV 7E21-1 and NOV 7E21-2 become paste or solid cake in 2 weeks and 1 week respectively.

5-MJN-372-090 NOV 503.05 / 91.14 20

2.65 3.06 / 90 551.98

7DF1-1

9-MJN-372-110 NOV 4.62 / 90 516.36 / 93.55 25

2.65 551.98

7DF1-2 3.11 / 120

Results and Discussion

The polyol starting materials have the following general structure:

NOV-7E21 is a polyol of formula Ql, and was characterized by the supplier, Novomer, as having an Mn of 1102 g/mol (i.e. n is, on average in the composition, about 4.8). The polymer has a PDI of 1.13, contains greater than 99% -OH end groups, and has no detectable ether linkages as determined by NMR.

NOV-94B0 is a polyol of formula Ql, and was characterized by the supplier,

Novomer, as having an Mn of 2107 g/mol (i.e. n is, on average in the composition, about

9.7). The polymer has a PDI of 1.06, contains greater than 99% -OH end groups, and has no detectable ether linkages as determined by NMR.

NOV-7DF1 is a polyol of formula Ql, and was characterized by the supplier, Novomer, as having an Mn of 2939 g/mol (i.e. n is, on average in the composition, about

13.8). The polymer has a PDI of 1.04, contains greater than 99% -OH end groups, and has no detectable ether linkages as determined by NMR.

The polyols NOV-7E21, NOV-94B0, and NOV-7DF1 were synthesized according to the following method: propylene oxide, chain transfer agent (CTA), cobalt catalyst E-2 and co-catalyst E-2c were added to a 2 gallon stainless steel autoclave and the polymerization was carried out according to the conditions disclosed in WO 2010028362.

E-2 E-2c

After the allotted reaction time, the reaction was quenched and the polyol was purified according to the conditions disclosed in WO 2010/033705 and WO 2010/033703, respectively. The ratios of the propylene oxide, catalyst complex and chain transfer agent were modified according to the description in WO 2010028362 to achieve the stated Mn values of the three polyol samples. A low catalyst to chain transfer agent ratio was maintained to produce polyols with a high percentage of -OH end-groups.

The polyols were further characterized by GPC to get the molecular weight (Mn) and molecular weight distribution (PDI). High throughput Symyx Rapid GPC was used for determining polymer Mn and PDI. The GPC system is equipped with 2 x PLgel Mixed-B columns (10 μιη particle size) and has high-speed columns and an evaporative light scattering detector (PL-ELS- 1000). Solutions of 1 mg mL^"1 sample in THF were prepared before run; calibration was carried out using polystyrene standards and THF was used as eluent at a flow rate of 2.0 mL min^"1. Mn and PDI were determined using EPOCH™ software. Mn and PDI of the control polyols from Bayer and candidate polyols are listed in Table 6.

Table 6. Characterization of polyols

The polyols were also characterized by differential scanning calorimetry (DSC) to get the Tg and the details are listed in Table 6. DSC experiments were performed utilizing a TA Instruments Q2000 DSC with a heat-cool-heat cycle. The sample size ranged from 4 mg to 10 mg. Temperature was ramped from -150 °C to 50 °C at 10 °C m T¹ in nitrogen for polyols. The control polyester polyol showed two transitions. Due to the low molecular weight, the polyol probably consists of hexanediol rich molecules and neopentyl glycol rich molecules. The Tgs of the control polycarbonate polyols are higher than that of the polyester. The candidate polyols exhibit a strong relationship between the molecular weight and the Tg. The highest MW candidate polyol has a Tg similar to the control polycarbonates. The polyols were also characterized using matrix-assisted laser desorption ionization time of flight (MALDI-TOF) mass spectrometry to obtain the molecular weight (Mri) and their distribution. MALDI-TOF mass spectra were recorded on a Bruker Ultraflex II spectrometer equipped with a 1.85 m linear flight tube and a Smart beam laser. All mass spectra were obtained in positive ion and reflectron mode. 2,5-Dihydroxybenzoic acid (10 mg/mL in THF) was used as a matrix, potassium trifluoroacetate (KTFA) (2 mg/mL) was used as the cationizing agent, and polymer samples were dissolved in THF (1-2 mg/mL). A 10 μΐ, portion of the matrix, 2 of the dopant, and 2

of the polymer were mixed together, and a 2 L sample solution was spotted on the target plate. All data were processed using Flex analysis. Analysis of the spectra of all the candidate polyols shows a series of similar peaks containing 102 repeating units of propylene carbonate (m/z 102) which is Mw of (CH(CH₃)CH₂OC0₂)n. The candidate polyols also have a much narrower molecular weight distribution that the control polycarbonate polyols.

Once the PUDs were prepared, they were allowed to sit in the shelf overnight so that the froth is settled. The average particle size was measured with water-diluted samples of PUD using Submicron Particle Sizer, NICOMP™ 380, which uses the method of dynamic light scattering (photocorrelation spectroscopy). Both Gaussian and Nicomp methods for calculating particle size averages were used. The particle size obtained for all the PUDs are given in Table 7. The particle sizes obtained for all the PUDs are less than 500 nm in most cases indicating that a stable dispersion is formed. One can notice that the particle size is very broad in the case of NOV 7E21-1 and NOV 94B0-1 in the first attempt of synthesis. Percent resin solids of the PUDs (theoretical and experimental) and pH values are presented in Table 7. Viscosity measurements were done using Brookfield DV-II+ Pro viscometer. The viscosity was measured at room temperature around 23 °C with spindle 06 at 100 rpm and the results are included in Table 7. Tab e 7. Particle size, pH, % resins and viscosity of the PUDs

PUD coating films were prepared by drawdown over TEFLON sheets glued to aluminum panels. PUD coating films were also prepared by drawdown over microscope glass slides and aluminum Q panels. Curing was achieved by allowing the coatings to lie horizontally for overnight at ambient conditions and is referred as room temperature cured coatings. Another set of coatings were cured for overnight at ambient conditions followed by an overnight heat treatment at 70 °C. Free films were obtained by releasing the coatings from the TEFLON^® sheet using a spatula at one edge of the coating. PUDs were

characterized by DSC to get the Tg after they were cured on microscope slides. Temperature was ramped from -100 °C to 100 °C at 10 °C mnf¹ in nitrogen for PUD films and the results are shown in Figure 11. Control PUDs have Tg- below zero degrees and most of the candidate PUD have Tgs close to zero or above zero degrees.

An automated surface energy measurement unit manufactured by Symyx Discovery Tools, Inc and First Ten Angstroms was used to measure the surface energy of PUD coatings. Droplets of water and methylene iodide (MI) were deposited on the PUD coating separately and a CCD camera imaged the droplets and then automated image analysis was used to determine the contact angles. Three droplets of water and MI were used for each measurement. Surface energy was calculated from the contact angle data using the Owens- Wendt equation. PUD coating films prepared on microscope glass slides were used for measuring the contact angles and surface energies. The water and MI contact angles and surface energies for PUD coatings cured at room temperature are given in Figure 12. Similarly Water and MI contact angles and surface energies for PUD coatings cured at room temperature followed by 70 °C overnight are given in Figure 13.

Quasistatic Nanoindentation was performed using Hysitron Triboindenter (Hysitron Incorporated) mounted with a Berkovich tip. The indenting was done in load control mode with the following operating parameters: a 5 second loading, a hold time of 5 seconds at the maximum load to allow visco-elastic dissipation, and a 5 second unloading. Maximum load was 300 μΝ and pre-load was set to 2 μΝ. Moduli of the samples were obtained from the unloading segment of a resulting force-depth curve using the Oliver and Pharr method. PUD coating films prepared on microscope glass slides were used to obtain reduced modulus and hardness using Nanoindentation. The reduced modulus and hardness for PUD coatings cured at room temperature as well as coating cured at RT followed by 70 °C are given in Figure 14. The room temperature cured PUDs seem to be soft and once they are cured at 70 °C they seem to become much harder. This is in particular applicable to all candidate PUDs. The control PUDs does not seems to change much after curing at 70 °C. Room temperature cured samples are expected to contain residual NMP, which can act as a plasticizer. Curing at 70 °C can drive off residual NMP and yield a film that is not plasticized. Thus the modulus and hardness of the coating is increased.

Mechanical properties of the coatings were measured using an MTS Insight Tensile Tester following the procedures outlined in ASTM D 882-02. Test specimens were produced by removing cured films from TEFLON^® covered aluminum substrate. The gauge length of the specimens was 80 mm and the width was 5 mm. The thickness of each specimen was measured in three different positions along the gauge area and averaged. For testing, a 50-N load cell was used in conjunction with a cross-head speed of 40 mm/min. A minimum of three specimens were tested for each composition and average values for Young's modulus, elongation at break (% EB), toughness, and tensile strength were reported. Table 8 gives the mechanical properties of all the PUD free films cured at room temperature for about a week. Since NOV 7E21-1 and NOV 7E21-2 become paste in two weeks, they were not evaluated. Table 8. Tensile strength of the RT cured PUD free films

Another two sets of PUDs films were immersed in the humidity chamber with ~ 95 % humidity and at 70 °C (the humidity was not checked). But within 20 minutes the candidate PUD films collapsed into the water and crumbled. Hence another set of PUD free films were made, cured at RT followed by 70 °C curing overnight. Surprisingly these PUD free films are very brittle and hence further characterization was not done.

Dynamic mechanical analysis (DMA) was performed using a TA Instruments Q800 DMA in rectangular tension/compression geometry. Free films of the cured materials were obtained by removing the material from TEFLON^® covered aluminum substrate using a spatula. Sample size was 21 mm x 5 mm and film thickness was measured using a

MICROMASTER^® micrometer. The analysis was carried out from -75 °C to 100 °C at a frequency of 1 Hz and a ramp rate of 5 °C min^_I. Tg was obtained from the maximum peak in the tan δ curves. Storage Modulus and Tg data are presented in Figure 15 and 16, respectively. NOV 7E21-1 and NOV 7E21-2 become paste in two weeks hence they were not evaluated.

Hardness testing was performed with a BYK Gardener pendulum hardness tester in Konig mode. Test results are reported as the time in seconds for the swing to be damped from a higher to a lower angle i.e. from 6 to 3 degrees. Usually harder coatings give longer times. PUD coatings were made on aluminum panels and they were cured at RT as well as at 70 °C. The results are presented in Figure 17. From the results it is clear that the hardness values of the control coatings do not change upon curing at 70 °C. On the other hand, all the candidate PUDs show a large increase in the hardness values after curing at RT followed by 70 °C curing overnight. Cross-hatch adhesion was done using the ASTM procedure (D3359-97) and the results are given in Table 9. The most widely used specification test is the cross-hatch adhesion test. Usually using a device with 6 or 11 sharp blades, a scratch mark pattern is made across the sample, followed by a 2nd set cut perpendicular to the first. In our case since the device was not enough sharp, 11 cuts were made using a sharp blade and also in perpendicular direction. A strip of pressure-sensitive adhesive tape is pressed over the pattern of squares and pulled off. Adhesion is accessed qualitatively on a 5B-0B scale (5B=best) by comparing to a set of photographs provided in the ASTM method, ranging from trace removal along the incisions to remove of most of the area. From the results it is clear that all the RT cured coatings have 5B values and the RT followed by 70 °C cured coatings have variable values.

Table 9. Cross hatch adhesion test for the PUD coatings

PUD coatings were subjected to four different chemical solutions such as 10 %

NaOH, H₂S0₄, HC1 and H₃P0₄ solutions. In addition, seven solvents namely ethanol, isopropyl alcohol, toluene, xylene, MIBK, MEK, and butanol were tested against the PUD coatings. Each PUD was tested under 66 conditions, making a total of 594 measurements using pencil hardness. For measuring the pencil hardness 2B pencil was used. PUD films were made as given in the earlier section and cured at RT; the RT cured coatings were divided into two and one was used as such for chemical and solvent resistance. Another set was cured at 70 °C overnight and then tested for chemical and solvent resistance. Each of the PUD was tested using the list of solvent given above at 4, 24 and 48 h. Approximately, 2-3 drops were dispensed onto the PUD coatings and covered with a cap. After the said time is over the coatings were rinsed with water, dried off the water and tested using 2B pencil. For the test (ASTM D3363), the pencil is held at a 45 degree angle to the panel and pushed forward with a constant pressure (300 g) and was repeated three times. A general scheme was made to rate the coatings, Pass - No scratch; Intermediate - Scratch and slight scratches; Fail - Scratch with film dissolved, cut and swollen. The list of assessment of all the PUDs are in the attached appendix and it is presented in two forms: 1) one PUD with different conditions and 2) one condition in comparison with other PUDs. Some of the observations made are 1) the caps get stuck to the coating due to spreading of the solvents in particular; 2) coating with HCl had corroded caps; and 3) with 10 % solutions, the droplet remained after 4 and 24 h.

Conclusions

It was demonstrated that aqueous PUDs can be successfully synthesized using polycarbonate diols supplied by Novomer. Two of the three PUDs are stable with most of the desired properties of a PUD. It is likely that adjustments to the PUD recipe (increasing neutralization, acid content) can improve the stability of the PUD with the lowest MW candidate resin.

Overall, the film properties indicate that the PUDs made with the candidate polyols are harder and more brittle than the control polyols after the NMP is driven off. It is also interesting that there seemed to be little variation in the hardness and Tg of the PUDs made from the candidate polyols considering that the starting polyols had a wide range of Tgs. The candidate polyol-based PUDs also were not able to withstand high humidity. Introducing a slight amount of crosslinking into the PUD might help overcome some of these property limitations.

The complete disclosures of all patents, patent applications including provisional patent applications, and publications, and electronically available material cited herein are incorporated by reference. The foregoing detailed description and examples have been provided for clarity of understanding only. No unnecessary limitations are to be understood therefrom. The invention is not limited to the exact details shown and described; many variations will be apparent to one skilled in the art and are intended to be included within the invention defined by the claims.

Claims

What is claimed is:

1. An isocyanate-terminated prepolymer, comprising a plurality of segments derived from one or more polyols derived from epoxide-C0₂ copolymerization, wherein the polyol segments are connected via urethane linkages.

2. A higher polymer derived from an isocyanate-terminated prepolymer of claim 1, by

reaction of the prepolymer with one or more reagents having a plurality of functional groups reactive toward isocyanates.

3. An aqueous polyurethane dispersion comprising a composition of claim 1.

4. An aqueous polyurethane dispersion comprising a composition of claim 2.

5. A coating composition comprising an aqueous polyurethane dispersion of claim 4.

6. An adhesive composition comprising an aqueous polyurethane dispersion of claim 4.

7. A composition of matter comprising an isocyanate-functionalized prepolymer of fomiula:

wherein,

R¹, R², R³, and R⁴ are, at each occurrence in the polymer chain, independently selected from the group consisting of -H, fluorine, an optionally substituted C_1-30 aliphatic group, and an optionally substituted C_1-20 heteroaliphatic group, and an optionally substituted C_6-10 aryl group, where any two or more of R¹, R², R³, and R⁴ may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms;

n and n' are, independently at each occurrence, an integer from about 3 to about 1,000 and may be the same or different;

substistuted C_1-12 aliphatic group;

f^ is a multivalent moiety;

represents the carbon skeleton of a diisocyanate;

ZZI represents a segment comprising the carbon skeleton of a coreactant having any combination of hydroxyl-, amino-, carboxyl-, or tbio-groups; m is an integer greater than zero;

p is zero or greater; and

y" is, independently at each occurrence, 0 or 1.

8. The composition of matter of claim 7, wherein f) comprises the carbon skeleton of a molecule selected from the group consisting of: a polyhydric alcohol, a polyacid, a hydroxyacid, and a mixture of any two or more of these.

9. The composition of matter of claim 8, wherein ( ) comprises the carbon skeleton of a commercially available diol.

10. The composition of matter of claim 7, wherein each

in the prepolymer is independently selected from the group consisting of:

where each R^x is independently an optionally substituted group selected from the group consisting of C_2-20 aliphatic, C2_-2o heteroaliphatic, 3- to 14-membered carbocyclic, 6- to 10-membered aryl, 5- to 10-membered heteroaryl, and 3- to 12- membered heterocyclic.

11. The composition of matter of claim 10, wherein each

in the prepolymer is independently selected from the group consisting of:

12. The co l2:

13. The composition of matter of claim 12, wherein the polyol segments of formula cl2, are derived from poly(propylene carbonate) polyol having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol.

14. The composition of matter of claim 12, wherein the polyol segments of formula cl2, are derived from poly(propylene carbonate) polyol having a polydisperisty index less than about 1.25.

15. The composition of matter of claim 12, wherein the polyol segments of formula cl2, are derived from poly(propylene carbonate) polyol having at least 95% carbonate linkages.

16. The composition of matter of claim 12, wherein the polyol segments of formula cl2, are derived from poly(propylene carbonate) polyol having at least 98% -OH end groups.

17. The composition of matter of claim 12, wherein the polyol segments of formula cl2, are derived from poly(propylene carbonate) polyol having an average molecular weight number of about 500 to about 1,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups.

18. The composition of matter of claim 12, wherein the polyol segments of formula cl2, are derived from poly(propylene carbonate) polyol having an average molecular weight number of about 2,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups.

19. The composition of matter of claim 12, wherein the polyol segments of formula cl2, are derived from poly(propylene carbonate) polyol having an average molecular weight number of about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups.

20. The

21. The composition of matter of claim 12, wherein the polyol segments of formula cl3, are derived from poly(ethylene carbonate) polyol having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol.

22. The composition of matter of claim 12, wherein the polyol segments of formula cl3, are derived from poly(ethylene carbonate) polyol having a polydisperisty index less than about 1.25.

23. The composition of matter of claim 12, wherein the polyol segments of formula cl3, are derived from poly(ethylene carbonate) polyol having at least 85%) carbonate linkages.

24. The composition of matter of claim 12, wherein the polyol segments of formula cl3, are derived from poly(ethylene carbonate) polyol having at least 98%> -OH end groups.

25. The composition of matter of claim 12, wherein the polyol segments of formula cl3, are derived from poly(ethylene carbonate) polyol having an average molecular weight number of about 1,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups.

26. The composition of matter of claim 12, wherein the polyol segments of formula cl3, are derived from poly(ethylene carbonate) polyol having an average molecular weight number of about 2,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups.

27. The composition of matter of claim 12, wherein the polyol segments of formula cl3, are derived from poly(ethylene carbonate) polyol having an average molecular weight number of about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups.

28. The composition of matter of any of claims 7 through 27, wherein ΗΙ^β represents the carbon skeleton of a commercially-available aliphatic diisocyanate.

29. The composition of matter of claim 28, wherein aliphatic diisocyanate is selected from the group consisting of: HDI, IPDI, H₁₂MDI, H6-XDI, TMDI, 1,4-cyclohexyl diisocyanate, 1,4-tetramethylene diisocyanate, trimethylhexane diisocyanate, and mixtures of any two or more of these.

30. The composition of matter of any of claims 7 through 27, wherein™ represents the carbon skeleton of a commercially available aromatic diisocyanate.

31. The composition of matter of claim 30, wherein aromatic diisocyanate is selected from the group consisting of: 2,4-TDI, 2,6-TDI, MDI, XDI, TMXDI, and mixtures of any two or more of these.

32. The composition of matter of any of claims 7 through 27, wherein the prepolymer

comprises segments derived from one or more coreactants.

33. The composition of matter of claim 32, wherein a coreactant segment is derived from a polyhydric alcohol.

34. The composition of matter of claim 33, wherein coreactant segments comprise one or more hydrophilic functional groups.

35. The composition of matter of claim 34, wherein hydrophilic functional groups comprise precursors to ionic functional groups.

36. The composition of matter of claim 35, wherein hydrophilic functional groups comprise carboxylic acids.

37. The composition of matter of claim 36, wherein coreactant segments are derived from one or more bis(hydroxylalkyl) alkanoic acids.

38. The composition of matter of claim 37, wherein the bis(hydroxylalkyl) alkanoic acids are selected from the group consisting of DMPA; DMBA, tartaric acid, and 4,4'- bis(hydroxyphenyl) valeric acid.

39. The composition of matter of claim 32, comprising coreactant segments derived from DMPA.

40. The composition of matter of claim 32, comprising coreactant segments derived from DMBA.

41. The composition of matter of claim 37, comprising one or more structures selected fromt the group consisting of:

01-M2 = -CH₃, or -C₂H₅ ]

42. The composition of matter of claim 37, comprising one or more structures selected from

01-b4 [ RS = -CH₃, or -C₂H₅ ]

01-b6 [ RS = -CH₃, or -C₂H₅ ]

Ql-b8 [ RB = -CH₃, or -C₂H₅ ]

43. The composition of matter of claim 36, comprising carboxylate salts of the carboxylic acid groups on the coreactant segments.

44. The composition of matter of claim 43, wherein the carboxylate salts comprise

ammonium salts.

45. The composition of matter of claim 43, wherein the carboxylate salts are metal salts.

46. The composition of matter of claim 35, wherein hydrophilic functional groups comprise amino groups.

47. The composition of matter of claim 46, comprising coreactant segments derived from one or more amino diols.

48. The composition of matter of claim 47, wherein amino diols are selected from the group consisting of: diethanolamine (DEA), N-methyldiethanolamine (MDEA), N- ethyldiethanolamine (EDEA), N-butyldiethanolamine (BDEA), N,N-bis(hydroxyethyl)-a- amino pyridine, dipropanolamine, diisopropanolamine (DIP A), N- methyldiisopropanolamine, Diisopropanol-p-toluidine, N, N-Bis(hydroxyethyl)-3 - chloroaniline, 3-diethylaminopropane-l,2-diol, 3-dimethylaminopropane-l,2-diol and iV- hydroxyethylpiperidine.

49. The composition of matter of claim 46, comprising ammonium salts of the amine groups present on the coreactant segments.

50. The composition of matter of claim 32, wherem the molar ratio of aliphatic

polycarbonate polyol segments to coreactant segments in the prepolymer composition is from about 1,000:1 to about 10:1.

51. The composition of matter of claim 32, wherein the molar ratio of aliphatic

polycarbonate polyol segments to coreactant segments in the prepolymer composition is from about 200:1 to about 50:1.

52. A composition of matter comprising a higher polymer formed by the reaction of a

prepolymer composition of any one of claims 7 through 27 with a chain extending reagent having a plurality of functional groups reactive toward isocyanates.

53. The composition of matter of claim 53, wherein the chain extending reagent comprises an amine.

54. The composition of matter of claim 53, wherein the amine is selected from the group consisting of: mono-, bis- or polyalkoxylated aliphatic, cycloaliphatic, aromatic or heterocyclic primary amines, N-methyl diethanolamine, N-ethyl diethanolamine, N- propyl diethanolamine, N-isopropyl diethanolamine, N-butyl diethanolamine, N-isobutyl diethanolamine, N-oleyl diethanolamine, N-stearyl diethanolamine, ethoxylated coconut oil fatty amine, N-allyl diethanolamine, N-methyl diisopropanolamine, N-ethyl diisopropanolamine, N-propyl diisopropanolamine, N-butyl diisopropanolamine, cyclohexyl diisopropanolamine, N,N-diethoxylaniline, Ν,Ν-diethoxyl toluidine, N,N- diethoxyl-l-aminopyridine, Ν,Ν'-diethoxyl piperazine, dimethyl-bis-ethoxyl hydrazine, N,N'-bis-(2-hydroxyethyl)-N,N'-diethylhexahydr op-phenylenediamine, N- 12- hydroxyethyl piperazine, polyalkoxylated amines, propoxylated methyl diethanolamine, N-methyl-N,N-bis-3 -aminopropylamine, N-(3 -aminopropyl)-N,N'-dimethyl

ethylenediamine, N-(3-aminopropyl)-N-methyl ethanolamine, N,N'-bis-(3-aminopropyl)- Ν,Ν'-dimethyl ethylenediamine, N,N'-bis-(3-aminopropyl)-piperazine, N-(2-aminoethyl)- piperazine, N, N'-bisoxyethyl propylenediamine, 2,6-diaminopyridine,

diethanolaminoacetamide, diethanolamidopropionamide, N,N-bisoxyethylphenyl thiosemicarbazide, Ν,Ν-bis-oxyethylmethyl semicarbazide, p,p'-bis-aminomethyl dibenzyl methylamine, 2,6-diaminopyridine, and 2-dimethylammomethyl-2- methylpropanel.

55. The composition of matter of claim 53, wherein the amine is selected from the group consisting of: ethylene diamine, 1,6-hexamethylene diamine, and 1,5-diamino-l -methyl - pentane.

56. The composition of matter of claim 53, wherein the amine comprises ethylene diamine.

57. An aqueous polyurethane dispersion comprising a higher polymer from any one of claims 52 through 55.

58. The aqueous polyurethane dispersion of claim 57 comprising from about 10 to about 70 weight percent solids.

59. The aqueous polyurethane dispersion of claim 57 comprising from about 20 to about 60 weight percent solids.

60. The aqueous polyurethane dispersion of claim 57 comprising from about 40 to about 60 weight percent solids.

61. The aqueous polyurethane dispersion of claim 57 further comprising one or more

additives selected from the group consisting of: pigments, dyes, fillers, stabilizers, curing agents, surfactants, defoamers, antimicrobial agents, antioxidants, UV absorbing compounds, glossing agents, and viscosity modifiers.

62. A coating formed from the aqueous polyurethane dispersion of claim 57.

63. An adhesive formed from the aqueous polyurethane dispersion of claim 57.

64. A method comprising the steps of:

a)

b) contacting the aliphatic polycarbonate polyol with one or more reagents having a plurality of isocyanate groups, optionally in the presence of one or more coreactants capable of reacting with isocyanate groups, where the coreactants are selected from any of those disclosed hereinabove; and

c) allowing the polyol to react with the reagent having a plurality of isocyanate groups to form a prepolymer,

wherein,

R¹, R², R³, and R⁴ are, at each occurrence in the polymer chain, independently

selected from the group consisting of -H, fluorine, an optionally substituted C_1-30 aliphatic group, and an optionally substituted C_1-20 heteroaliphatic group, and an optionally substituted C_6-i₀ aryl gi'oup, where any two or more of R¹, R², R³, and R⁴ may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms;

Y is, at each occurrence, independently -H or the site of attachment to any of the chain-extending moieties described in the classes and subclasses herein; n is an integer from about 3 to about 1,000; -/ is a multivalent moiety; and

x and y are each independently an integer from 0 to 6, where the sum of x and y is between 2 and 6.

65. The method of claim 64, wherein the aliphatic polycarbonate polyol provided in step (a) is selected from the group consisting of: P2, P3, P4, P5, P6, P7, P8 and mixtures of two or more of these.

66. The method of claim 64, wherein the aliphatic polycarbonate polyol provided in step (a) is selected from the group consisting of compounds P2a through P2r-a.

67. The method of claim 64, wherein the aliphatic polycarbonate polyol provided in step (a) is selected from the group consisting of: Ql, Q2, Q3, Q4, and mixtures of any of these

68. The method of claim 64, wherein the aliphatic polycarbonate polyol provided in step (a) is selected from the group consisting of:

Poly(propylene carbonate) of formula Ql having an average molecular weight number of between about 1,000 g/mol and about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

Poly (propylene carbonate) of formula Ql having an average molecular weight number of about 1,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98%) -OH end groups;

Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 2,000 g/mol, a polydisperisty index less than about 1.25, at least 95%) carbonate linkages, and at least 98%) -OH end groups;

Poly(propylene carbonate) of formula Ql having an average molecular weight number of about 3,000 g/, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups; Poly(propylene carbonate) of formula Q2 having an average molecular weight number of between about 1,000 g/mol and about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 1,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

Poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 2,000 g/mol, a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of between about 1,000 g/mol and about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98%» -OH end groups;

Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 1,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 2,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98%) -OH end groups;

Poly(ethylene carbonate) of formula Q3 having an average molecular weight number of about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 85%) carbonate linkages, and at least 98%) -OH end groups;

Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of between about 1,000 g/mol and about 3,000 g/mol (e.g. each n is between about 4 and about 16), a polydisperisty index less than about 1.25, at least 95% carbonate linkages, and at least 98%) -OH end groups; Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 1 ,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups;

Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 2,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups; and

Poly(ethylene carbonate) of formula Q4 having an average molecular weight number of about 3,000 g/mol, a polydisperisty index less than about 1.25, at least 85% carbonate linkages, and at least 98% -OH end groups.

69. The method of claim 64, wherein the reagent having a plurality of isocyanate groups utilized in step (b) is selected from the group consisting of: aliphatic diisocyanates, aromatic diisocyanates, oligomeric diisocyanates, and difunctional isocyanate prepolymers.

70. The method of claim 64, wherein the reagent having a plurality of isocyanate groups utilized in step (b) comprises one or more diisocyanates selected from the group consisting of: HDI, IPDI, H₁₂MDI, H6-XDI, TMDI, 1,4-cyclohexyl diisocyanate, 1,4- tetramethylene diisocyanate, trimethylhexane diisocyanate, and mixtures of any two or more of these.

71. The method of claim 64, wherein the reagent having a plurality of isocyanate groups utilized in step (b) comprises one or more diisocyanates selected from the group consisting of: HDI, IPDI, H₁₂MDI and mixtures of two or more of these.

72. The method of claim 64, wherein the reagent having a plurality of isocyanate groups utilized in step (b) comprises one or more diisocyanates selected from the group consisting of: 2,4-TDI, 2,6-TDI, MDI, XDI, and TMXDI.

73. The method of claim 64, wherein the reagent having a plurality of isocyanate groups utilized in step (b) comprises an oligomer of a diisocyanate.

74. The method of claim 64, wherein the reagent having a plurality of isocyanate groups utilized in step (b) comprises a biuret.

75. The method of claim 64, wherein the reagent having a plurality of isocyanate groups utilized in step (b) comprises any one or more of the materials in Table 1.

76. The method of claim 64, wherein the reagent having a plurality of isocyanate groups utilized in step (b) comprises any one or more of the materials in Table 2.

77. The method of claim 64, wherein the reagent having a plurality of isocyanate groups utilized in step (b) comprises any one or more of the materials in Table 3.

78. The method of claim 64, wherein the reagent having a plurality of isocyanate groups utilized in step (b) comprises one or more diisocyanates selected from the group consisting of: Easaqua™ WAT; Easaqua™ WAT-1; Easaqua™ WT 1000; Easaqua™ WT 2102; Easaqua™ X D 401; Easaqua™ X D 803; Easaqua™ X M 501; Easaqua™ X M 502; Easaqua™ X WAT-3; and Easaqua™ X WAT-4.

79. The method of claim 64, further comprising the step of controlling the ratio of the

aliphatic polycarbonate polyol and, if present, the one or more coreactants, to the reagents having a plurality of isocyanate groups such that there is a molar excess of isocyanate groups.

80. The method of claim 64, wherein the step of contacting aliphatic polycarbonate polyol with the reagent having a plurality of isocyanate groups is performed in the presence of a solvent.

81. The method of claim 80, wherein the solvent is a non-protic polar organic solvent.

82. The method of claim 80, wherein the solvent is acetone.

83. The method of claim 80, wherein the solvent is NMP.

84. The method of claim 64, further comprising the step of providing one or more catalysts at step (b).

85. The method of claim 84, wherein the catalysts provided in step (b) comprise tin

compounds.

85. The method of claim 84, wherein the catalysts provided in step (b) are selected from the group consisting of di-butyl tin dilaurate, dibutylbis(laurylthio)stannate,

dibutyltinbis(isooctylmercapto acetate) and dibutyltinbis(isooctylmaleate), tin octanoate and mixtures of any of these.

86. The method of claim 64, further comprising the step of providing one or more

coreactants in step (b).

87. The method of claim 64, wherein the coreactant provided is selected from the group consisting of: other types of polyols (e.g. polyether polyols, polyester polyols, acrylics, or other polycarbonate polyols), and small molecules with functional groups reactive toward isocyanates such as hydroxyl groups, amino groups, and thiol groups, the like.

88. The method of claim 64, wherein the coreactant provided is a dihydric alcohol.

89. The method of claim 88, wherein a provided dihydric alcohol is selected from the group consisting of diethylene glycol, triethylene glycol, tetraethylene glycol, higher poly(ethylene glycol), such as those having number average molecular weights of from 220 to about 2000 g/mol, dipropylene glycol, tripropylene glycol, and higher

poly(propylene glycols) such as those having number average molecular weights of from 234 to about 2000 g/mol.

90. The method of claim 88, wherein the provided dihydric alcohol comprises a diol

containing one or more moieties that can be converted to an ionic functional group.

91. The method of claim 88, wherein a provided dihydric alcohol comprises a moiety

selected from the group consisting of: carboxylic acids, esters, anhydrides, sulfonic acids, sulfamic acids, phosphates, and amino groups.

92. The method of claim 88, wherein a provided dihydric alcohol comprises a diol

carboxylic acid.

93. The method of claim 88, wherein a provided dihydric alcohol is selected from the group consisting of 2,2 bis-(hydroxymethyl)-propanoic acid (dimethylolpropionic acid, DMPA) 2,2-bis(hydroxymethyl) butanoic acid (dimethylolbutanoic acid; DMBA),

dihydroxysuccinic acid (tartaric acid), and 4,4'-bis(hydroxyphenyl) valeric acid.

94. The method of claim 92, further comprising the step of deprotonating the carboxylic acid groups with a base.

95. The method of claim 88, wherein a provided dihydric alcohol comprises an amino diol.

96. The method of claim 88, wherein a provided dihydric alcohol is selected from the group consisting of: diethanolamine (DEA), N-methyldiethanolamine (MDEA), N- ethyldiethanolamine (EDEA), N-butyldiethanolamine (BDEA), N,N-bis(hydroxyethyl)-a- amino pyridine, dipropanolamine, diisopropanolamine (DIP A), N- methyldiisopropanolamine, Diisopropanol-p-toluidine, N, N-Bis(hydroxyethyl)-3 - chloroaniline, 3-diethylaminopropane-l,2-diol, 3-dimethylaminopropane-l,2-diol and N- hy droxy ethylpiperidine .

97. The method of claim 95, further comprising the step of protonating the amino groups with an acid.

98. The method of claim 95, further comprising the step of alkylating the amino groups with an alkylating agent.

99. The method of claim 64, further comprising the step of dispersing the prepolymer from step (c) in water.

100. The method of claim 99, wherein the step of dispersing the prepolymer is performed in the presence of one or more chain-extending reagents wherein the chain extending reagents have a plurality of functional groups reactive toward isocyanates.

101. The method of claim 100, wherein at least one chain extending reagent is dissolved in the aqueous phase prior to or during the step of dispersing the prepolymer.

102. The method of claim 99, wherein the step of dispersing the prepolymer from step (c) into water is performed in the presence of a polyamme compound.

103. The method of claim 102, wherein the polyamine compound is selected from the group consisting of: diethylene triamine (DETA), ethylene diamine (EDA), meta- xylylenediamine (MXDA), aminoethyl ethanolamine (AEEA), 2-methyl pentane diamine, and mixtures thereof.

104. The method of claim 64, further comprismg the step of dispersing the prepolymer from step (c) in water in the presence of a chain extending reagent wherein the chain extending reagent comprises blocked functional groups that are liberated on contact with water and which once liberated will react with isocyanates.

105. The method of claim 104, wherein the blocked functional groups are selected from the group consisting of: hydrazine, substituted hydrazines, hydrazine reaction products, and mixtures thereof.