KR20160077182A - Adhesion promoting adducts containing metal ligands, compositions thereof, and uses thereof - Google Patents

Abstract

Disclosed are compositions, such as sealant compositions, useful in aerospace applications where the adhesion promoting additive comprises an adhesion promoter and a metal ligand and the adhesion promoting additive. The adhesion promoting adducts are useful as adhesion promoting additives in polymer compositions or as copolymerizable reactants.

Description

FIELD OF THE INVENTION [0001] The present invention relates to metal ligand-containing adhesion promoting adducts, compositions thereof, and uses thereof. ≪ Desc / Clms Page number 1 >

The invention relates to an adhesion promoting additive containing an adhesion promoter and a metal ligand. The adhesion promoting adduct may be used as an additive in the polymer composition or may be copolymerized with the sulfur-containing polymer backbone to provide improved surface adhesion to the metal surface. Compositions comprising a sulfur-containing prepolymer and an adhesion promoting additive useful in aerospace sealant applications are also disclosed.

Related Applications and Cross References

This application is a continuation-in-part of U.S. Patent Application No. 13 / 529,183, filed June 21, 2012, U.S. Patent Application No. 13 / 923,941, filed June 21, 2013, and U.S. Patent Application, filed June 21, 13 / 923,903, each of which is incorporated herein by reference in its entirety.

Sealants useful in aerospace and other applications must meet the required mechanical, chemical and environmental conditions. The sealant can be applied to a variety of surfaces including metal surfaces, primer coatings, intermediate coatings, finish coatings and aged coatings. Typically, an adhesion promoter is added to the sealant formulation to improve adhesion of the various components to each other and also to the surface to which the sealant is applied. There is a continuing need for a method that provides improved surface adhesion while maintaining other favorable properties of the sealant.

Sulfur-containing polymers such as polythioethers and polysulfides are useful in aerospace applications. Examples of suitable polythioethers and polysulfides are described, for example, in U.S. Patent Nos. 2005/0010003, 2006/0270796, 2007/0287810, 2009/0326167, and 2010/036063 Each of which is incorporated herein by reference in its entirety.

Polymeric sulfur-containing adhesion promoters containing a terminal adhesion promoter and used in sulfur-containing polymer compositions are disclosed in U.S. Patent Application No. 13 / 529,183. Sulfur-containing polymers having a bis (sulfonyl) alkanol metal ligand incorporated into the backbone of the sulfur-containing polymer and / or as a terminal group of the sulfur-containing polymer are disclosed in U.S. Patent Application No. 13 / 923,903 and U.S. Patent Application No. 13 / 923,941.

Disclosed is an adhesion promoting adduct useful for improving adhesion to a metal surface.

In a first aspect, there is provided an adhesion promoting adduct comprising an adhesion promoter and a metal ligand.

In a second aspect, there is provided a composition comprising an adhesion promoter and an adhesion promoting additive comprising a metal ligand.

In a third aspect, there is provided a cured sealant formed from a sealant composition comprising an adhesion promoter and an adhesion promoting additive comprising a metal ligand.

Fig. 1 shows the reaction described in Example 1. Fig.
Fig. 2 shows the reaction described in Example 2. Fig.
3 is a table showing the calculated energies for the interaction of the ligand with the aluminum (III) surface described in Example 4. Fig.
Reference will now be made to specific embodiments of compositions and methods. The disclosed embodiments are not intended to limit the scope of the claims. On the contrary, the appended claims are intended to cover all alternatives, modifications and equivalents.

Justice

In the following detailed description, it is to be understood that the embodiments provided herein may represent various other variations and step sequences, except where otherwise explicitly specified. Furthermore, it is to be understood that all values expressing the amounts of constituents used in the specification and claims are to be understood as being modified in all instances by the term "about" Accordingly, unless indicated otherwise, the numerical parameters set forth in the following description and the appended claims are approximations that may vary depending upon the desired properties to be obtained. At the very least, and without intending to limit the application of the principles corresponding to the scope of the claims, each numerical parameter should be inferred by applying a conventional approximation technique in light of at least the number of significant numbers reported.

The numerical values set forth in the specific examples are reported as precisely as possible, even though the numerical ranges and parameters that are indicative of the broad scope of the embodiments provided by the present application are approximations. However, any numerical value implicitly has a certain error inevitably arising from the standard deviation found in the individual test measurements.

It is also to be understood that any numerical range recited herein is intended to include all subsets encompassed therein. For example, a range of "1 to 10" includes a range between a quoted minimum value of about 1 and a quoted maximum value of about 10 (including these minimum and maximum values), i.e., a minimum value of about 1 and a maximum value of about 10 We want to include all subsets with values. Also, even though "and / or" may be expressly used in certain instances, the use of "or" herein means "and / or" unless specifically stated otherwise.

A "-" that is not between two letters or symbols is used to indicate the point of attachment of the substituent or between two atoms. For example, -CONH ₂ is bonded to another chemical moiety through a carbon atom.

"Alkane die work", for example, 1 to 18 carbon atoms (C _{1 -18), 1} to 14 carbon atoms (C _{1 -14), 1} to 6 carbon atom (C _{1 -6), 1} to 4 carbon atom (C _{1 -4)} or from one to three carbon atoms (C _{1 -3)} refers to a divalent radical of a saturated branched or straight chain acyclic hydrocarbon group having from. It can be seen that the branched alkanediyl has at least three carbon atoms. In certain embodiments, the alkanes do die C _{2 -14} alkane die work, C _{2 -10} alkane die yl, C _2-8 alkane die work, C _{2 -6} alkanoic die work, C _{2 -4} alkane die and one specific embodiment In an embodiment, it is C _{2 -3} alkanediyl. Examples of alkane di diary methane-di one (-CH ₂ -), ethane-1,2-di one (-CH ₂ CH ₂ -), propane-1,3-yl and iso-propane-1,2 -di (e. g., -CH ₂ CH ₂ CH ₂ - and _{-CH (CH 3) CH 2 -} ), butane-1,4-di one _{(-CH 2 CH 2 CH 2 CH} 2 -), pentane 1,5-yl _{(-CH 2 CH 2 CH 2 CH} 2 CH 2 -), hexane-1,6-yl _{(-CH 2 CH 2 CH 2 CH} 2 CH 2 CH 2 -), heptane -1 , 7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, dodecane-1,12-diyl and the like.

Refers to a saturated hydrocarbon group having one or more cycloalkyl and / or cycloalkanediyl groups and one or more alkyl and / or alkanediyl groups, wherein the cycloalkyl, cycloalkanediyl, alkyl, Lt; / RTI > In certain embodiments, each cycloalkyl and / or cycloalkanediyl group (s) is C _{3 -6} , C _{5 -6} , and in certain embodiments is cyclohexyl or cyclohexanediyl. In certain embodiments, each of the alkyl and / or alkane die group (s), C _{1 -6,} C _{1 -4,} is a C _1-3, in certain embodiments, methyl, methane di one, ethyl or ethane-1, 2-yl. In certain embodiments, alkane alkane cycloalkyl group is C ₄ alkane _-18 cyclo alkane, C ₄ alkane _-16 cyclo alkane, C ₄ alkane _-12 cyclo alkane, C ₄ alkane _-8 cyclo alkanes, C _{6 -12} alkane alkane cycloalkyl, C the _6-10 alkanes and cyclo alkanes certain embodiments is a C ₆ cycloalkyl _-9 alkane alkane. Examples of alkane cycloalkane groups include 1,1,3,3-tetramethylcyclohexane and cyclohexylmethane.

"Alkanecycloalkanediyl" refers to a divalent radical of an alkane cycloalkane group. In certain embodiments, the alkane cycloalkane diyl group is selected from the group consisting of C _{4 -18} alkane cycloalkanediyl, C _{4 -16} alkane cycloalkanediyl, C _{4 -12} alkane cycloalkanediyl, C _{4 -8} alkane cycloalkanediyl a C _{6 -12} alkane bicyclo alkane die yl, C _{6 -10} in the alkane bicyclo alkane die work and certain embodiments _-9 C ₆ alkane, bicyclo alkane di one. Examples of alkane cycloalkanediyl groups include 1,1,3,3-tetramethylcyclohexane-1,5-diyl and cyclohexylmethane-4,4'-diyl.

An "alkenyl" group refers to a group (R) ₂ C = C (R) ₂ or -RC = C (R) ₂ , where the alkenyl group is an end group and is bonded to a larger molecule. In such embodiments, each R is, for example, be selected from hydrogen and C _{1 -3} alkyl. In certain embodiments, each R is an alkenyl group having a structure of hydrogen and -CH = CH ₂ .

"Alkoxy" refers to the -OR group wherein R is alkyl as defined herein. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy. In certain embodiments, the alkoxy group is a C _1-3 alkoxy group in C _{1 -8} alkoxy, C _{1 -6} alkoxy, C _{1 -4} alkoxy and certain embodiments.

"Alkyl" means, for example, a saturated branched or straight-chain non-cyclic hydrocarbon having from 1 to 20 carbon atoms, from 1 to 10 carbon atoms, from 1 to 6 carbon atoms, from 1 to 4 carbon atoms or from 1 to 3 carbon atoms Means a monovalent radical of a hydrocarbon group. In certain embodiments, the alkyl group is C _{2 -6} alkyl, C _{2 -4} alkyl, and in certain embodiments, C _{2 -3} alkyl. Examples of the alkyl group include methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-hexyl, n-decyl and tetradecyl. In certain embodiments, the alkyl group is a C _{2 -3} alkyl in the C _2-6 alkyl, C _{2 -4} alkyl and certain embodiments. It can be seen that the branched alkyl group has at least three carbon atoms.

"Cycloalkanediyl" refers to a divalent radical of a saturated monocyclic or polycyclic hydrocarbon group. In certain embodiments, the cycloalkyl group is C ₃ alkane die _-12 cyclo alkane die yl, C _{3 -8} cycloalkyl alkane die yl, C _{3 -6} cycloalkyl alkane and a die work in certain embodiments cycloalkyl C _5-6 alkane die days . Examples of cycloalkanediyl groups include cyclohexane-1,4-diyl, cyclohexane-1,3-diyl and cyclohexane-1,2-diyl.

"Cycloalkyl" refers to a monovalent or polycyclic hydrocarbon monovalent radical. In certain embodiments, the cycloalkyl group is a C _{5 -6} cycloalkyl in the C _{3 -12} cycloalkyl, C _{3 -8} cycloalkyl, C _{3 -6} cycloalkyl, and certain embodiments.

"Bis (sulfonyl) alkanol group" refers to a group having the formula (1)

-S (O) _2- R ¹⁰ -CH (-OH) -R ¹⁰ -S (O) ₂ -

In this formula,

Each R < ¹⁰ > is independently selected from C1-3 alkanediyl and substituted C1-3 alkanediyl, wherein at least one of the substituents is -OH.

In certain embodiments, bis (sulfonyl) alkanol group formula _{-CH 2 -CH 2 -S (O)} 2 -R 10 -CH (-OH) -R 10 -S (O) 2 -CH 2 -CH 2 - to have, in certain embodiments, the structural formula _{^{-R 9 -S (O) 2 -R}} 10 -CH (-OH) -R 10 -S (O) 2 -R 9 - having a, wherein each R ⁹ is is an organic residue, each R ¹⁰ is independently C _{1 -3} alkane and die work, and substituted C _{1 -3} days alkane die, wherein at least one substituent is -OH.

In certain embodiments, the "bis (sulfonyl) alkanol group" may be a monovalent bis (sulfonyl) alkanol group or a divalent bis (sulfonyl) alkanol group. In certain embodiments, the monovalent bis (sulfonyl) alkanol can be a terminal bis (sulfonyl) alkanol group, e.g., a "1- (ethylene sulfonyl) -n- (vinylsulfonyl) . The terminal bis (sulfonyl) alkanol group can be derived from the reaction of a bis (sulfonyl) alkanol and can be derived from a compound of the structure -R ⁹ -S (O) ₂ -R ¹⁰ -CH (-OH) -R ¹⁰ -S ₂ -R ⁸ , wherein R ⁹ is a residue derived from the reaction of a bis (sulfonyl) alkanol with a compound having a group reactive with the bis (sulfonyl) alkanol; Each R ¹⁰ is independently C _{1 -3} doedoe alkane selected from one die, and substituted C _{1 -3} days alkane die, wherein at least one substituent is -OH. In certain embodiments, R ⁸ is -CH = CH ₂ . In certain embodiments, the terminal bis (sulfonyl) alkanol group is a 1- (ethylene sulfonyl) -n- (vinylsulfonyl) alkanol group such as 1- (ethylene sulfonyl) -3- is propan-2-ol, that _{is, -CH 2 -CH 2 -S (O} ) 2 -CH 2 -CH (-OH) -CH 2 -S (O) 2 -CH = CH 2. In certain embodiments, the end-bis (sulfonyl) alkanol group formula _{-CH 2 -CH 2 -S (O)} 2 -R 15 -CH (-OH) -R 15 -S (O) 2 -CH = CH 2 .

In certain embodiments, the bis (sulfonyl) alkanol groups may also be bivalent, for example when the group is incorporated into the backbone of a prepolymer such as the polythioether disclosed in U.S. Patent Application No. 13 / 923,903. In certain embodiments, the divalent bis (sulfonyl) alkanol group may have the structure -R ⁹ -S (O) ₂ -R ¹⁵ -CH (-OH) -R ¹⁵ -S (O) ₂ -R ^{9 -} Have; In certain embodiments, it may have -CH ₂ -CH ₂ -S (O) ₂ -R ¹⁵ -CH (-OH) -R ¹⁵ -S (O) ₂ -CH ₂ -CH ₂ - _{^{in, -R 9 -S (O) 2}} -CH 2 -CH (-OH) -CH 2 -S (O) 2 -R 9 - may have, in certain embodiments, -CH ₂ -CH ₂ - _{S (O) 2 -CH 2 -CH} (-OH) -CH 2 -S (O) 2 -CH 2 -CH 2 - may have a, in which R ⁹ and R ¹⁵ are as defined herein. In certain embodiments of the bis (sulfonyl) alkanol, each R ⁹ is an ethane-dileyl group and / or each R ¹⁵ is methane-diyl.

Refers to a compound of the formula R ⁸ -S (O) ₂ -R ¹⁵ -CH (-OH) -R ¹⁵ -S (O) ₂ -R ⁸ wherein each R ⁸ Is a residue having a terminal reactive group; Each R ¹⁰ is independently selected from C _{1 -3} days and alkane di-substituted C _{1 -3} days alkane die, wherein the one or more substituents are -OH. In certain embodiments, each R ⁸ is a leaving group that is reactive with a thiol group, such as an alkenyl group, an epoxy group, a Michael acceptor group, or a nucleophilic substitution group that is highly compatible with nucleophilic substitution, such as -Cl, -Br, - I, -OSO ₂ CH ₃ (mesylate), -OSO ₂ -C ₆ H ₄ -CH ₃ (tosylate), and the like. In certain embodiments, the bis (sulfonyl) alkanol may be a non (vinylsulfonyl) alkanol comprising a terminal alkenyl group. In certain embodiments, the bis (sulfonyl) alkanol may be a bis (vinylsulfonyl) alkanol, wherein R ⁸ is a terminal group such as the formula CH ₂ = CH-S (O) ₂ -R ¹⁵ -CH -OH) -R ¹⁵ -S (O) ₂ -CH = CH ₂ . In certain embodiments, the bis (vinylsulfonyl) alkanol is 1,3-bis (vinylsulfonyl) -2-propanol. In certain embodiments, the bis (sulfonyl) alkanol containing compound is a compound wherein the bis (vinylsulfonyl) alkanol is reacted with a terminal group reactive with the terminal alkenyl group of the reactive terminal functional group and the bis (vinylsulfonyl) alkanol, Or a compound having an epoxy group. In such embodiments, the bis (sulfonyl) alkanol formula _{^{R 9 -CH 2 -CH 2 -S (}} O) 2 -R 15 -CH (-OH) -R 15 -S (O) 2 -CH 2 - CH ₂ -R ⁹ , wherein each R ⁹ is a residue derived from the reaction of the compound with a terminal alkenyl group of a bis (vinylsulfonyl) alkanol.

A "bis (sulfonyl) alkanol-containing" polymer, prepolymer or adduct refers to a polymer, prepolymer or adduct in which one or more bis (sulfonyl) alkanol groups are incorporated into the backbone of the polymer, prepolymer or adduct .

The divalent bis (sulfonyl) alkanol group can be introduced into the prepolymer by reacting, for example, a polythiol monomer or prepolymer of the following formula (2) with a bis (sulfonyl) alkanol of the formula (3) Can:

R (-SH) _w (2)

R ⁸ -S (O) ₂ -R ¹⁰ -CH (-OH) -R ¹⁰ -S (O) ₂ -R ⁸ (3)

In this formula,

R is an organic residue, w is an integer of 2 or more, each R ⁸ is an end group such as an alkenyl group and an epoxy group which are reactive with a thiol group, or a leaving group which is very suitable for nucleophilic substitution, Br, -I, -OSO ₂ CH ₃ (mesylate), -OSO ₂ -C ₆ H ₄ -CH ₃ (tosylate), and the like. In certain embodiments, the bis (sulfonyl) alkanol of formula (3) can be a bis (vinylsulfonyl) alkanol having the structure of formula (4)

_{CH 2 = CH-S (O} ) 2 -R 10 -CH (-OH) -R 10 -S (O) 2 -CH = CH 2 (4)

In this formula,

Each R ¹⁰ is independently selected from C _{1 -3} days and alkane di-substituted C _{1 -3} days alkane die, wherein the one or more substituents are -OH. In certain embodiments, the bis (sulfonyl) alkanol may be 1,3-bis (vinylsulfonyl) -2-propanol. Alternatively, the bis (sulfonyl) alkanol group can be incorporated into the prepolymer backbone by reacting the thiol-capped bis (sulfonyl) alkanol of formula (5) with a reactant of formula (6) :

HS-RS (O) ₂ -R ¹⁰ -CH (-OH) -R ¹⁰ -S (O) ₂ -R-

R ²¹ -R ²⁰ -R ²¹ (6)

In this formula,

Each R ²⁰ is a divalent residue, each R ¹⁰ are as defined herein, and each R ²¹ is

Thiol group reactive end groups, for example alkenyl group, an epoxy group, or, for example, a preferred leaving group for nucleophilic substitution _{-Cl, -Br, -I, -OSO 2} CH 3 ( mesylate), -OSO ₂ -C ₆ H ₄ -CH ₃ (tosylate), and the like.

By selecting an appropriate ratio of the reactants of the formulas (2) and (3) or the reactants of the formulas (5) and (6), one or more bis (sulfonyl) alkanol groups can be used as chain fragments, ≪ / RTI > or both as prepolymers. For example, a bis (vinylsulfonyl) alkanol may be prepared by reacting one or more 1, n-bis (ethylene sulfonyl) alkanol groups with a prepolymer chain, one or more terminal 1- (ethylene sulfonyl) Alkanol groups or both into the backbone.

In certain embodiments, bis (vinylsulfonyl) -2-propanol can be reacted with a thiol-capped monomer / polymer to incorporate a 1,3-bis (ethylene sulfonyl) -2-propanol group into the polymer chain.

In certain embodiments, bis (vinylsulfonyl) -2-propanol may be reacted with a thiol-capped monomer / polymer to provide the 1- (ethylene sulfonyl) -3- (vinylsulfonyl) Wherein the terminal alkenyl group is a well-known Michael acceptor.

The residue derived from the reaction of a bis (sulfonyl) alkanol with a thiol group refers to a residue containing a terminal group that is reactive with the thiol and thiol groups of the reaction product. Examples of the thiol group and the reactive terminal group is an epoxy group, an alkenyl group, Michael acceptor group, and a nucleophilic leaving group, for example, in a preferred substitution _{-Cl, -Br, -I, -OSO 2} CH 3 ( mesylate) , -OSO ₂ -C ₆ H ₄ -CH ₃ (tosylate), and the like. In certain embodiments, bis (sulfonyl) moiety derived from the reaction of an alkanol with a thiol group has the structural formula _{-CH 2 -CH 2 -R-, -CH (} -OH) -CH 2 -R-, -CH 2 - CH (-OH) having a -R-, or -CH ₂ -CH ₂ -SO ₂ -R-, where R represents an organic residue bonded to a covalent bond or a sulfonyl.

The residue derived from the reaction of the bis (sulfonyl) alkanol with the thiol group also represents the residue R ⁹ , which is derived from the reaction of the group R ⁸ , where R ⁸ is a reactive group with a thiol group, .

In certain embodiments, R ⁹ is derived from the reaction of a bis (sulfonyl) alkanol with a compound having a reactive group with a terminal group and a bis (sulfonyl) alkanol that is reactive with a thiol group. In certain embodiments, R ⁹ is derived from the reaction of a bis (vinylsulfonyl) alkanol with a compound having a reactive group with a thiol group and a reactive group with an alkenyl group. In such embodiments, R ⁹ can have the structure: -CH ₂ -CH ₂ -R'-CH ₂ -CH ₂ -, -CH (-OH) -CH ₂ -R'-CH _{2 -CH 2 -, -CH 2 -CH (} -OH) -R'-CH 2 -CH 2 -, or _{-CH 2 -CH 2 -SO 2 -R'-} CH 2 -CH 2 - ( wherein, R ' is bis (ethylene sulfonyl) alkanol for example, an alkenyl group, an epoxy group, or a Michael acceptor group, or, for example, a preferred leaving group for nucleophilic substitution _{-Cl, -Br, -I, -OSO 2} CH ₃ (mesylate), -OSO ₂ -C ₆ H ₄ -CH ₃ (tosylate), and the like.

In certain embodiments, R ⁹ is C _{2 -10} alkane di one, substituted C _{2 -10} alkane die days, _-10 C ₂ hetero alkanoic die yl, substituted C _{2 -10} hetero alkanoic die yl, C _{4 -14} alkane, bicyclo alkane di one, substituted C ₄ alkane _-14 cyclo alkane di one, C _{4 -14} hetero alkanoic bicyclo alkane di one, substituted C _{4 -14} hetero alkanoic bicyclo alkane di one, C ₄ alkane, arene die _-14 days is selected from substituted C ₄ alkane, arene die _-14 days, _-14 C ₄ alkane hetero arene one die, and substituted C _{4 -14} hetero alkanoic arene one die. In certain embodiments, R < ⁹ > is ethane-diyl.

In certain embodiments, R ⁹ is C _{2 -10} alkyl, substituted C _{2 -10} alkyl, C _{2 -10} heteroaryl alkyl, substituted C _{2 -10} heteroalkyl, C ₄ alkane _-14 cycloalkyl, substituted C _{4 -14} alkane cycloalkyl, C ₄ alkane _-14 hetero-cycloalkyl, substituted C _{4 -14} hetero alkanoic cycloalkyl, C ₄ alkane _-14 aryl, substituted C ₄ alkane _-14 aryl, C _{4 -14} hetero aryl alkanoic, and it is selected from substituted C _{4 -14} hetero aryl alkane. In certain embodiments, R ⁸ is ethylene, i.e., -CH = CH ₂ .

"Acetylacetonate group" means a group having the structure of the formula (1)

.

.

In certain embodiments, the acetylacetonate refers to a metal chelator comprising an acetylacetonate group and at least one reactive functional group.

The "hydroxypyridinone group" includes, for example, groups such as 3-hydroxy-4-pyridinone and 3-hydroxy-2-pyridinone each having the structure of the following formula (8a) or :

In this formula,

R is an organic group such as an alkyl group.

The hydroxypyridinone metal chelator comprises a hydroxypyridinone group and at least one reactive functional group such as a terminal thiol group.

Quot; refers to a compound having a fully conjugated cyclic polyionic structure derived from an aromatic compound by converting an even number of -CH = groups into a -C (= O) - group by any rearrangement of the double bonds. Examples of quinones include 1,2-benzoquinone, 1,4-benzoquinone, 1,4-naphthaloquinone and 9,10-anthraquinone. The quinone group may be a metal ligand.

"Metal ligand" means an ion or molecule that combines with metal atoms and potentially other atoms to form a coordination complex. The bond between the metal and / or the atom generally comprises the donation of one or more electron pairs to the metal, and the nature of the bond can be for example covalent, ionic or hydrogen bonding. The metal ligands provided by the present invention can form coordination complexes on aerospace surfaces such as aluminum and titanium surfaces that can be oxidized. In the case of an oxidized surface, the metal ligand may form a coordination complex with a metal such as, for example, Al (III) and an oxygen atom. The coordination complex can improve the adhesion to the metal or oxidized metal surface.

The metal ligand can be incorporated into the backbone of the prepolymer provided herein. For incorporation into the prepolymer backbone, as well as the moiety capable of forming a coordination complex, the metal ligand may comprise or be comprised of two or more groups that are reactive with the group of sub-units of the prepolymer. Such reactive metal ligands are either commercially available or can be derivatized to include appropriate reactive substituents using methods known to those skilled in the art.

"Heteroalkanediyl" refers to an alkanediyl group in which one or more carbon atoms is replaced by a heteroatom such as N, O, S, or P. In certain embodiments of heteroalkanediyl, the heteroatom is selected from N and O.

"Heterocycloalkanediyl" refers to a cycloalkanediyl group in which one or more carbon atoms is replaced by a heteroatom such as N, O, S, or P. In certain embodiments of the heterocycloalkanediyl, the heteroatom is selected from N and O.

"Michael acceptor" refers to an activated alkene such as an alkenyl group adjacent to an electron-withdrawing group such as a ketone, nitro, halo, nitrile, carbonyl or nitro group. Michael acceptors are well known in the art. "Michael acceptor group" refers to an activated alkenyl group and an electron-withdrawing group. In certain embodiments, the Michael acceptor group is selected from vinyl ketone, vinyl sulfone, quinone, enamine, ketimine, aldimine, oxazolidine, and acrylates. Other examples of Michael acceptors are described by Mather et al ., Proc . Polym. Sci . , 2006, 31, 487-531], and includes acrylate esters, acrylonitrile, acrylamide, maleimide, alkyl methacrylate, and cyanoacrylate. Other Michael acceptors include vinyl ketones, alpha, beta -unsaturated aldehydes, vinylphosphonates, acrylonitriles, vinyl pyridines, specific azo compounds, beta -ketoacetylene, and acetylene esters. In certain embodiments, the Michael acceptor group is derived from vinyl ketone and has the structure of the formula -S (O) ₂ -C (R) ₂ = CH ₂ wherein each R is hydrogen, fluorine, and C _{1 -3} alkyl Lt; / RTI > In certain embodiments, each R is hydrogen. In certain embodiments, the Michael acceptor or Michael acceptor group does not include acrylate. A "Michael receptor compound" refers to a compound comprising at least one Michael acceptor. In certain embodiments, the Michael acceptor compound is divinylsulfone and the Michael acceptor group is vinylsulfonyl, for example, -S (O) ₂ -CH = CH ₂ .

"Heteroalkanediyl" refers to an alkanediyl group in which one or more carbon atoms is replaced by a heteroatom such as N, O, S, or P. In certain embodiments of heteroalkanediyl, the heteroatom is selected from N and O.

"Heterocycloalkanediyl" refers to a cycloalkanediyl group in which one or more carbon atoms is replaced by a heteroatom such as N, O, S, or P. In certain embodiments of the heterocycloalkanediyl, the heteroatom is selected from N and O.

"Michael acceptor" refers to an activated alkene, such as an alkenyl group adjacent to an electron-withdrawing group such as a ketone, nitro, halo, nitrile, carbonyl or nitro group. Michael acceptors are well known in the art. "Michael acceptor group" refers to an activated alkenyl group and an electron-withdrawing group. In certain embodiments, the Michael acceptor group is selected from vinyl ketone, vinyl sulfone, quinone, enamine, ketimine, aldimine, oxazolidine, and acrylates. Other examples of Michael acceptors are described in Mather et al., Prog . Polym . Sci ., 2006, 31, 487-531) and include acrylate esters, acrylonitrile, acrylamide, maleimide, alkyl methacrylate, cyanoacrylate. Other Michael acceptors include vinyl ketones, alpha, beta -unsaturated aldehydes, vinylphosphonates, acrylonitrile, vinyl pyridine, certain azo compounds, beta -ketoacetylene, and acetylene esters. In certain embodiments, the Michael acceptor group is derived from a vinyl ketone formula _{-S (O) 2 -C (R} ) 2 = CH 2 ( wherein each R is independently selected from hydrogen, fluoro and C _{1 -3} alkyl In certain embodiments, each R is hydrogen. In certain embodiments, the Michael acceptor or Michael acceptor group does not comprise acrylate. "Michael acceptor compound" refers to a compound comprising at least one Michael acceptor. in the embodiment, the Michael acceptor compound is a divinyl sulfone, a Michael acceptor group is a vinyl sulfonyl e.g. _{-S (O) 2 -CH 2 =} CH 2.

"Michael acceptor" means that at least one alkene / alkyne group is substituted with one or more electron-withdrawing groups such as carbonyl (-CO), nitro (-NO ₂ ), nitrile (-CN), alkoxycarbonyl phosphonate (-PO (OR) _2), trifluoromethyl (-CF _3), sulfonyl (-SO ₂ -), methanesulfonyl trifluoromethyl (-SO ₂ CF _3), p- toluenesulfonyl ( -CF ₃ ) and the like. Compounds of the type that act as Michael acceptors are vinyl ketone, quinone, nitroalkene, acrylonitrile, acrylate, methacrylate, cyanoacrylate, acrylamide, maleimide, dialkyl vinyl phosphate and vinyl sulfone. Other examples of Michael acceptors are described in Mather et al., Prog . Polym . Sci . 2006, 31, 487-531. Michael acceptor compounds having at least one Michael acceptor group are also well known. Examples thereof include diacrylates such as ethylene glycol diacrylate and diethylene glycol diacrylate, dimethacrylates such as ethylene glycol methacrylate and diethylene glycol methacrylate, bismaleimides such as N, N '- ( 1,3-phenylene) dimaleimide and 1,1 '- (methylenedi-4,1-phenylene) bismaleimide, vinyl sulfone such as divinylsulfone and 1,3-bis (vinylsulfonyl) -2 -Propanol and the like. In certain embodiments, the Michael acceptor group has the structure of formula (9a) or (9b): < EMI ID =

_{-CH 2 -CH 2 -S (0)} 2 -R 15 -CH (-OH) -R 15 -S (0) 2 -CH = CH 2 (9a)

_{-CH 2 -CH 2 -S (0)} 2 -CH 2 -CH (-OH) -CH 2 -S (0) 2 -CH = CH 2 (9b)

In this formula,

Each R ¹⁵ is independently C _{1 -3} alkane and die work, and substituted C _{1 -3} days alkane die, wherein at least one substituent is -OH.

A "Michael acceptor compound" refers to a compound comprising at least one terminal Michael acceptor group. In certain embodiments, the Michael acceptor compound is divinylsulfone and the Michael acceptor group is vinylsulfonyl, i.e., -S (O) _2- CH = CH ₂ . In certain embodiments, the Michael acceptor compound is a bis (vinyl sulfonyl) alkanol, a Michael acceptor groups of 1- (ethylene sulfonyl) -n- (vinyl sulfonyl) alkanol, i.e., -CH ₂ -CH ₂ -S ( O) ₂ -R ¹⁰ -CH (-OH) -R ¹⁰ -S (O) ₂ -CH = CH ₂ and in certain embodiments 1- (ethylene sulfonyl) -3- (vinylsulfonyl) -O- (-CH ₂ -CH ₂ -S (O) ₂ -CH ₂ -CH (-OH) -CH ₂ -S (O) ₂ -CH = CH ₂ ).

"Polyalkoxysilyl group" refers to a group having the structure of formula (10)

-Si (-R ⁷ ) _p (-OR ⁷ ) _3-p (10)

In this formula,

p is selected from 0, 1 and 2, each R ⁷ is independently is selected from C _{1 -4} alkyl.

In certain embodiments of the polyalkoxysilyl group, p is 0 or 1, and in certain embodiments, p is 2. In certain embodiments of the polyalkoxysilyl group, each R < ⁷ > is independently selected from ethyl and methyl. In certain embodiments of the polyalkoxysilyl group, each R ⁷ is ethyl, and in certain embodiments, each R ⁷ is methyl. In certain embodiments of the polyalkoxysilyl group, the group is selected from the group consisting of -Si (-OCH ₂ CH ₃ ) ₃ , -Si (-OCH ₃ ) ₃ , -Si (-CH ₃ ) (-OCH ₃ ) ₂ , _{CH 3) 2 (-OCH 3)} , -Si (-CH 3) (- OCH 2 CH 3) 2, -Si (-CH 3) 2 (-OCH 2 CH 3), -Si (-CH 2 CH 3 ) (- it is selected from OCH _3), and _{-Si (-CH 2 CH 3) 2} (-OCH 3).

"Polyalkoxysilane" refers to a compound comprising a polyalkoxysilyl group. The polyalkoxysilyl group is an adhesion promoter, and thus the polyalkoxysilane is an adhesion promoter. In certain embodiments, the polyalkoxysilane has the formula R ¹¹ -PR ¹² wherein P is the core of the polyalkoxysilane, R ¹¹ comprises a polyalkoxysilyl group, and R ¹² comprises a reactive functional group.

As used herein, "polymer" refers to oligomers, homopolymers and copolymers. Unless otherwise indicated, the molecular weight is the number average molecular weight of the polymeric material, designated "Mn ", as determined, for example, by gel permeation chromatography using a polystyrene standard sample in a manner known in the art. The term "prepolymer" is also used when referring to a polymeric component of a composition that forms a cured polymer upon curing.

"Substituted" refers to a group in which one or more hydrogen atoms are each independently replaced with the same or different substituent (s). In certain embodiments, the substituent is selected from the group consisting of halogen, -S (O) ₂ OH, -S (O) ₂ , -SH, -SR wherein R is C _{1 -6} alkyl, -COOH, -NO ₂ , -NR ₂ (wherein each R is independently, from hydrogen and C _{1 -3} alkyl selected), -CN, -C = O, C 1 -6 alkyl, -CF _3, -OH, phenyl, C _{2 - 6} (wherein, R is C _{1 -6} alkyl) heteroalkyl, C _{5 -6-heteroaryl,} C _{1 -6} alkoxy and -COR is selected from. In certain embodiments, substituents are selected from -OH, -NH _2, and C _{1 -3} alkyl.

Specific embodiments of adhesion promoting adducts, prepolymers, compositions and methods will be discussed. The disclosed embodiments are not intended to limit the scope of the claims. On the contrary, the appended claims are intended to cover all alternatives, modifications and equivalents.

Adhesion promoting adjunct

Adhesion promoting adjuncts provided herein include adhesion promoters and metal ligands.

Groups that promote adhesion to metal surfaces are well known in the art. Examples of groups promoting adhesion include polyalkoxysilyl groups, phosphonate groups, amine groups including primary and secondary amines, carboxylic acid groups and phosphonic acid groups.

In certain embodiments, the adhesion promoter has the structure -Si (R ⁴ ) _{y 1} (OR ⁵ ) _y 2

Wherein y1 is selected from 0, 1 and 2; y2 is selected from 1, 2 and 3; the sum of y1 and y2 is 3; Each R ⁴ is independently selected from C _{1 -4} alkyl; Each R ⁵ is independently C _{1 -4} alkyl) may be poly alkoxysilyl group which may have a date.

In certain embodiments, the adhesion promoting groups are structural formula ^{-P (= O) (OR 6} ) 2 may be an optionally having (wherein each R ⁶ is independently C _{1 -4} are selected from alkyl) phosphonate. In certain embodiments, the adhesion promoting groups may be a phosphonic acid group having the formula ^{-P (= O) (OR 6} ) 2 ( wherein each R ⁶ is hydrogen).

In certain embodiments, the adhesion promoter can be a primary amine, and in certain embodiments can be a secondary amine.

In certain embodiments, the adhesion promoter may be a carboxylic acid group.

Typical aerospace vehicle surfaces include, for example, aluminum, anodized aluminum, Al (III), Alodine (R) and titanium. Thus, for aerospace sealant applications, the metal chelating agent is preferably coordinated with aluminum, aluminum oxide, alloys, titanium, and titanium oxides. Thus, in certain embodiments, the metal ligand comprises a moiety capable of forming a coordination complex on one or more of these aerospace surfaces. In addition to forming a coordination complex with the metal, other transition metals or elements such as oxygen may be included in the coordination complex through covalent, ionic or hydrogen bonding interactions. For applications on other surfaces, suitable metal ligands can be selected.

Metal ligands, especially aluminum (III) metal ligands, include hard Lewis acids such as -OH, -PO ₄ , -SO ₄ , -COOH, -C = O, and -NH ₂ groups, For example, aluminum (III). The basic donors effective for forming the multidentate coordination complex with aluminum (III) include aliphatic monohydroxy acid anions, catecholates, aromatic hydroxycarboxylic acid anions, 3-hydroxy-4-pyridinones, hydroxamates, Hydroxy-2-pyridinone. The stable aluminum (III) complex is due to a multidentate ligand with a negative oxygen electron donor. The metal ligand may form a multidentate ligand complex with the metal, for example a bidentate or bidentate complex.

In certain embodiments, the metal ligand functional group is derived from a metal chelating agent selected from bis (sulfonyl) alkanol, benzoquinone, hydroxypyridinone, and acetylacetonate.

Examples of aluminum, aluminum oxide and / or Al (III) ligands include 2,3-dihydroxybenzoic acid, 5-nitrosalicylate, 3-hydroxy-4-pyridinone, 3-hydroxy- N, N'-diacetic acid (EDTA), N, N'-dihydroxyacetophenone, N, N'-diacetic acid - (2-hydroxy) ethylenediaminetriacetic acid (HEDTA), ethylenediamine-N, N'-bis (2-hydroxyphenylacetic acid) (EDDHA) and N, N'- Diamine-N, N'-diacetic acid (HBED), acetoacetate and quinone. Other aluminum and aluminum oxide chelators are described, for example, in Yokel, Coordination Chemistry Reviews 2002, 228, 97-113 and Martell et al., Coordination Chemistry Reviews 1996, 149, 311-328.

Examples of titanium or titanium oxide ligands include H ₂ O ₂ , acetoacetonate (CH ₂ (COCH ₃ ) ₂ ), EDTA, trans-1,2-cyclohexanediaminetetraacetic acid, glycol ethanediamine tetraacetic acid (GEDTA, _{(CH 2 OCH 2 CH 2 N} (CH 2 COOH) 2) 2)), diethylene tri-amine penta acetic acid _{(DTPA, HOOCH 2 N (CH} 2 CH 2 N (CH 2 COOH) 2) 2), nitrile tri-acetic acid (NTA, N (CH ₂ COOH) ₃ ), salicylic acid, lactic acid, acetylacetonate, triethanolamine, and any combination thereof.

In certain embodiments, the metal ligand comprises two or more hetero atomic groups capable of coordinating to aluminum (III). In certain embodiments, the metal ligands include _{-OH, -PO 4, -P (O} ) 2 -, -SO 4, -S (O) 2 -, -COOH, -C = O, -NH 2, -NH- , And combinations of any two or more of these.

U.S. Patent Applications Nos. 13 / 923,903 and 13 / 923,941 to Cai et al. Disclose a method for improving the surface adhesion of a cured composition to an aerospace surface using a bis (sulfonyl) alkanol group combined with a sulfur- . The bis (sulfonyl) alkanol group may have the structure of the formula (11a) or the formula (11b)

-S (O) _2- R ¹⁵ -CH (-OH) -R ¹⁵ -S (O) _2- (11a)

_{-S (O) 2 -CH 2 -CH} (-OH) -CH 2 -S (O) 2 - (11b)

In this formula,

Each R ¹⁵ is independently C _{1 -3} alkane die work and is selected from substituted C _{1 -3} days alkane die, wherein the at least one substituent is -OH.

In certain embodiments, the metal ligand comprises a compound of formula (12a), (12b), (12c), (12d), (12e) and any combination thereof:

_{-X- (CH 2) n -CH (} -OH) - (12a)

_{- X- (CH 2) n -CH} (-OH) - (CH 2) n -X- (12b)

-CH (-OH) - (CH ₂ ) _n -X- (CH ₂ ) _n -CH (-OH) - (12c)

-CH (-OH) -R < ⁵ > -CH (-OH) - (12d)

-C (O) -R < ⁵ > -C (O) - (12e)

In this formula,

Each X is independently selected from -C (O) - and -S (O) ₂ - is selected from, n is an integer from 1 to 3, R ⁵ is a C _{1 -4} days alkane die.

In certain embodiments, the metal ligand comprises a bis (sulfonyl) alkanol, a hydrosipyridine, a quinone, an acetylacetonate, or any combination thereof.

The adhesion promoting adducts provided herein may also contain functional groups that are reactive with the polyfunctionalizing agent or functional groups of the prepolymer. For example, the reactive groups may be reactive with the end groups of the polyfunctionalizing agent and may be used to prepare polyfunctional adhesion promoting adducts, copolymerizable adhesion promoting adducts, or copolymerizable sulfur-containing adhesion promoting adducts as disclosed herein . In another embodiment, the reactive group may be reactive with the functional groups of the polyfunctional sulfur-containing prepolymer, e.g., polythioether or polysulfide, and / or may be reactive with the curing agent. In any case, the reactive groups may be useful for grafting adhesion promoting adducts to the backbone of the cured polymer useful for improving the adhesive strength of the composition.

In certain embodiments, the adhesion promoting adduct comprises a reaction product comprising a reactant comprising an adhesion promoter and an adhesion promoter that VHG bonds the functional group, and a metal chelating agent comprising a metal ligand and a functional group that is reactive with the functional group of the adhesion promoter do. For example, in certain embodiments, the adhesion promoting adduct comprises a reaction product of a reactant comprising an adhesion promoter of the formula R ¹¹ -PR ¹² with a metal chelating agent of the formula R ¹³ -MR ¹⁴ wherein R ¹¹ is Wherein P comprises a core of an adhesion promoter, M comprises a metal ligand, R ¹² and R ¹³ comprise a mutually reactive functional group and R ¹⁴ is selected from a non-reactive group, a reactive functional group Or absent.

In certain embodiments, the adhesion promoting adduct has the structure of formula (13)

R ¹¹ -PR ^{12 '} -R ^13' -MR ¹⁴ (13)

In this formula,

R ¹¹ comprises an adhesion promoter;

P comprises a core of an adhesion promoter;

M comprises a metal ligand;

R ^{12 '} and R ^13' represent residues derived from the reaction of R ¹² and R ¹³ of the adhesion promoter R ¹¹ -PR ¹² and the metal chelating agent R ¹³ -MR ¹⁴ , wherein R ¹² and R ¹³ are mutually reactive functional groups And R < ¹⁴ > is selected or absent from non-reactive groups and reactive functional groups.

Suitable reaction conditions for reacting the adhesion promoter with the metal chelating agent to provide an adhesion promoting adduct can be determined by those skilled in the art.

In certain embodiments, the adhesion promoter comprises an alkenyl, thiol, or amine group that is reactive with the group of said metal chelating agent. In certain embodiments, the adhesion promoter comprises a thiol-terminated polyalkoxysilane.

In certain embodiments, the adhesion promoter comprises a mercaptosilane, and in certain embodiments, an aminosilane. Examples of polyalkoxysilyl-containing adhesion promoters having a reactive amine or thiol group include amine-functional adhesion promoters such as N- (β-aminoethyl) γ-aminopropyltrimethoxysilane (Silquest® A- 1120) and thiol-functional adhesion promoters such as gamma-mercaptopropyl trimethoxysilane (Silquest A-189).

In certain embodiments, the adhesion promoter has the structure of formula (14a), the structure of formula (14b), the structure of formula (14c), or any combination thereof:

In this formula,

Each R ¹⁶ is independently selected from C _{1 -3} alkyl, each R ¹⁷ is selected from hydrogen and C _{1 -3} alkyl.

In certain embodiments, the metal chelating agent comprises an aluminum or an aluminum oxide chelating agent and is selected from a bis (sulfonyl) alkanol, quinone, acetylacetonate, hydroxypyridinone, and any combination thereof. Specific examples of aluminum chelating agents include acetylacetonates such as 2- (methyl acryloyloxy) ethylacetoacetate (2-MEAA), hydroxypyridines such as 3-hydroxy-4-pyridinone and 3- Hydroxy-2-pyridinone and bis (sulfonyl) alkanols such as bis (vinylsulfonyl) -2-propanol.

In certain embodiments, the thiol-terminated adhesion promoter such as gamma -mercaptopropyltrimethoxysilane is reacted with a bis (sulfonyl) alkanol such as 1,3-bis (vinylsulfonyl) -2-propanol May provide an adhesion promoting adduct of formula (15): < EMI ID =

In this formula,

Each R < ¹⁶ > is independently selected from methyl and ethyl.

As another example, an amine-functional adhesion promoting adduct, for example N- (β-aminoethyl) γ-aminopropyltrimethoxy-silane, may be prepared by reacting an acrylate- or benzoquinone- (16a) to (16d) by reacting the resulting compound with (methacryloyloxy) ethylacetoacetate (2-MEAA) or benzoquinone You can provide:

In this formula,

Each R < ¹⁶ > is independently selected from methyl and ethyl.

As can be seen from these examples, the interacting functional groups of the adhesion promoter and the metal chelating agent may be terminal functional groups or may comprise a core of an adhesion promoter or metal chelating agent. Thus, in certain embodiments, the moieties -P- and -M- may comprise one or more reactive functional groups.

The extended adhesion promoting adduct

In certain embodiments, the adhesion promoting adduct comprises at least one reactive functional group. This reactive functional group can react with another compound to form an extended adhesion promoting adduct. For example, in certain embodiments, the adhesion promoting adduct comprises a reaction product comprising an adhesion promoting adduct and a first reactive functional group such as an adhesion promoting adduct of formula (13) and a second reactive functional group reactive with the first reactive functional group A reaction product of a compound having a reactive functional group.

In certain embodiments, the adhesion promoting adduct may be reacted with a polyamine such as a diamine, or a polythiol such as a dithiol.

In certain embodiments, a compound having a functional group that is reactive with the adhesion promoting adduct may have the structure of formula (17): < EMI ID =

R ³¹ -R ³⁰ -R ³¹ (17)

In this formula,

Each R ³¹ is selected from a functional group which is reactive with the adhesion promoting adduct, for example -NH ₂ , -SH or -CH = CH ₂ ;

Each R ³⁰ is independently C _{2 -6} alkanoic die yl, _-8 C ₆ cycloalkyl alkane die days, _-10 C ₆ alkane bicyclo alkane die yl, C _{5 -8} heterocycloalkyl alkane die work, and - [- (CHR _{^{6) s -X-] q - (}} CHR 6) r - is selected from;

Each R < ⁶ > is independently selected from hydrogen and methyl;

Each X is independently selected from -O-, -S-, and -NR-, wherein R is selected from hydrogen and methyl;

s is an integer from 2 to 6;

q is an integer from 1 to 5;

r is an integer of 2 to 10;

Examples of extended adhesion promoting adducts include the reaction product of the adhesion promoting adduct of formula (13) and the compound of formula (17) is 3,3 '- ((oxybis (ethane- ) Bis (oxy)) bis (propane-1 -amine), 2,2'-thiol diethanethiol or 2,2'-oxydaiethanethiol.

In another embodiment, the adhesion promoting adduct may react with the reactive functional groups of the prepolymer to provide an adhesion promoting adduct-functional or terminated prepolymer. In certain embodiments, the prepolymer may be any of those disclosed herein, including a sulfur-containing prepolymer, e.g., a polythioether prepolymer.

The polyfunctional adhesion promoting adduct

In certain embodiments, the adhesion promoting adduct is one or more adhesion promoting adducts that are bonded to a common core.

The multiple adhesion promoting adduct may be formed by reacting an adhesion promoting adduct having reactive groups with a reactive group of the polyfunctionalizing agent.

Thus, in certain embodiments, the polyfunctional adhesion promoting adduct comprises a z-polyfunctionalizing agent comprising an end functional group that is reactive with the functional group of the adhesion promoting adduct and an adhesion promoting adduct comprising an adhesion promoter, a metal ligand and a functional group Lt; / RTI > reactants.

Adhesion promoting adducts with reactive groups useful for reaction with the polyfunctionalizing agents include, for example, bis (sulfonyl) alkanols such as adducts of formula (13) having a terminal alkenyl group capable of reacting with the thiol group of the polyfunctionalizing agent Derived adhesion promoting adducts.

Examples of polyfunctionalizing agents suitable for use in the preparation of such polyfunctional adhesion promoting adducts include trifunctionalizing agents, i. E. Compounds with z = 3. Suitable trifunctionalizing agents include, for example, triallyl cyanurate (TAC), 1,2,3-propanetriethiol, isocyanurate-containing trithiol as disclosed in U.S. Patent Application Publication No. 2010/0010133 Quot ;, which is incorporated herein by reference in its entirety. Other useful polyfunctionalizing agents include those described in U.S. Patent Nos. 4,366,307; 4,609,762; And trimethylolpropane tribinyl ether and polythiol as described in US 5,225,472. Mixtures of polyfunctionalizing agents may also be used.

In certain embodiments, the polyfunctionalizing agent comprises a structural formula B (-V) z wherein B represents the core of the polyfunctionalizing agent, z is an integer from 3 to 6, Is a residue comprising a terminal group that is reactive with the functional group of the adduct. In certain embodiments, z is 3, z is 4, z is 5, and in certain embodiments, z is 6. In certain embodiments, the polyfunctional compound is trifunctional. In certain embodiments, the multifunctional compound is triallyl cyanurate (TAC), wherein B has the structure:

;

;

Each -V have the formula _{-O-CH 2 -CH = CH 2} .

In certain embodiments, the multifunctional compound B (-V) _z has a molecular weight of less than 800 daltons, less than 600 daltons, less than 400 daltons, and in certain embodiments less than 200 daltons. The multifunctional compound B (-V) _z , where _z is greater than or equal to 3, can be any polyfunctionalizing agent useful in polymer chemistry. Preparations comprising a multifunctional agent with mixed functional groups, i. E., A moiety that reacts with both a thiol group and a vinyl group (typically a separate moiety), may also be used. Other useful polyfunctionalizing agents include trimethylolpropane tribinylether, and the polythiol described in U.S. Patent No. 4,366,307, U.S. Patent No. 4,609,762, and U.S. Patent No. 5,225,472, each of which is incorporated herein by reference. Combinations of polyfunctionalizing agents having the same terminal groups such as thiol groups or allyl groups may also be used.

In certain embodiments, the polyaddition promoting adduct has the structure of formula (18)

B (-V'-R ^{14 '} -MR ^13' -R ^{12 '} -PR ¹¹ ) _z (18)

In this formula,

R ¹¹ comprises an adhesion promoter;

P comprises a core of an adhesion promoter;

M comprises a metal ligand;

R ^{12 '} and R ^13' represent residues derived from the reaction of R ¹² and R ¹³ of the adhesion promoter R ¹¹ -PR ¹² and the metal chelating agent R ¹³ -MR ¹⁴ wherein R ¹² and R ¹³ are mutually reactive functional groups R ¹⁴ comprises a reactive functional group;

R ^{14 '} represents a residue derived from the reaction of R ¹⁴ and V;

B represents the core of z- the polyfunctionalizing agent B (-V) _z ,

z is an integer from 3 to 6;

Each -V is a group containing a group reactive with R < ¹⁴ >;

Each -V'- is derived from the reaction of -V with R < ^{14 &} gt ;.

In certain embodiments, the polyadhesion promoting adduct may be formed by reacting an adhesion promoting adduct of formula (13) with a polyfunctionalizing agent B (-V) _z , wherein the adhesion promoting adduct is a functional group of -V It includes a functional group such as reactive R ^4.

In certain embodiments, the polyadhesion promoting adduct is a compound of the formula B (-V) _z , wherein B represents the core of the polyfunctionalizing agent, z is an integer from 3 to 6, A group containing a reactive functional group); And reaction products of reactants comprising an adhesion promoter, a metal ligand, and an adhesion promoting adduct comprising a second reactive functional group reactive with the first reactive functional group of the polyfunctionalizing agent.

The ratio of adhesion promoting adduct to polyfunctionalizing agent can be adjusted to provide a range of functionality.

The multivalent sulfur-containing adhesion promoting adduct

In certain embodiments, the adhesion promoting adduct is a polyvalent sulfur-containing adhesion promoting adduct having the structure of formula (19)

B (-V'-S-R^One-S- R^{14 '}-M-R^{13 '}-R^{12 '}-P-R¹¹)_z (19)

In this formula,

z is an integer from 1 to 6;

Each R ¹ is independently C _{2 -6} alkanoic die yl, C _{6 -8} cycloalkyl alkane die yl, C _{6 -10} alkane bicyclo alkane die yl, C _{5 -8} heterocycloalkyl alkane die work and - [- (CHR ³ ) _s- X-] _q- (CHR < ³ >) _r -

Each R < ³ > is independently selected from hydrogen and methyl;

Each X is independently selected from -O-, -S-, and -NR-, wherein R is selected from hydrogen and methyl;

s is an integer from 2 to 6;

q is an integer from 1 to 5;

r is an integer from 2 to 10;

R ¹¹ comprises an adhesion promoter;

P comprises a core of an adhesion promoter;

M comprises a metal ligand;

R ^{12 '} and R ^13' represent residues derived from the reaction of R ¹² and R ¹³ of the adhesion promoter R ¹¹ -PR ¹² and the metal chelating agent R ¹³ -MR ¹⁴ wherein R ¹² and R ¹³ are mutually reactive functional groups , And R ¹⁴ includes a reactive functional group.

R ^{14 '} represents a residue derived from the reaction of R ¹⁴ with a thiol group;

B represents the core of z- the polyfunctionalizing agent B (-V) _z ,

z is an integer from 3 to 6;

Each -V is a group comprising a group reactive with a thiol group;

Each -V'- is derived from the reaction of -V with a thiol group.

In certain embodiments, the polyvalent sulfur-containing adhesion promoting adducts comprise (a) a polyfunctionalizing agent having a terminal group reactive with a thiol group, (b) a dithiol, and (c) an adhesion promoting additive having a functional group reactive with a thiol group ≪ / RTI > In certain embodiments of the reaction, the reaction product comprises at least one compound of formula (19). In the multivalent sulfur-containing adhesion promoting adduct, each or some of the arms of the polyfunctionalizing agent may be terminated in the adhesion promoting adduct. In the copolymerizable adhesion promoting adduct, the one or more arms are reactive with the copolymer and / or the curing agent.

In certain embodiments, a multifunctional compound having a terminal group that is reactive with a thiol group has the structural formula B (-V) _z , where z is an integer from 3 to 6, and B and -V are as defined herein.

In certain embodiments of B (-V) _z , each -V comprises a terminal alkenyl group.

In certain embodiments, the dithiol has the structure of formula (20)

HS-R ¹ -SH (20)

Wherein R ¹ is selected from the group consisting of C _{2 -6} alkanediyl, C _{6 -8} cycloalkanediyl, C _{6 -10} alkane cycloalkanediyl, C _{5 -8} heterocycloalkanediyl and - [- (CHR ³ ) _s- X-] _q- (CHR < ³ >)_r-; Wherein each R < ³ > is independently selected from hydrogen and methyl; Each X is independently selected from -O-, -S-, and -NR-; R is selected from hydrogen and methyl; s is an integer from 2 to 6; q is an integer from 1 to 5; r is an integer of 2 to 10;

In certain embodiments, R ¹ is - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r -.

In certain embodiments of compounds of formula (20), X is a selected from -O- and -S-, thus the general formula (20) - [- (CHR 3) s -X-] q - (CHR 3) r - - - - (- CH ₂ -) _p --O--] _q - (CH ₂ ) _r - or - [- CH ₂ -) _p --S--] _q - (CH ₂ ) _r -. In certain embodiments, p and r are the same as when both are two.

In certain embodiments, R ¹ is C _{2 -6} alkanoic one die and _{^{- [- (CHR 3) s}} -X-] q - (CHR 3) r - a.

In certain embodiments, R ¹ is - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r -, and in certain embodiments X is -O- and in certain embodiments X is -S .

R ¹ is _{^{- [- (CHR 3) s}} -X-] q - (CHR 3) r - in which certain embodiments, p is 2, and r is 2, q is 1, X is -S- and ; In certain embodiments, p is 2, q is 2, r is 2, and X is -O-; In certain embodiments, p is 2, r is 2, q is 1, and X is -O-.

In certain embodiments in which R ¹ is - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r -, each R ³ is hydrogen and in certain embodiments at least one R ³ is methyl.

In certain embodiments of the compounds of formula (20), each R ¹ is the same and, in certain embodiments, at least one R ¹ is different.

Examples of suitable dithiols are, for example, 1,2-ethanedithiol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, -Butane dithiol, 1,3-pentane dithiol, 1,5-pentane dithiol, 1,6-hexane dithiol, 1,3-dimercapto-3-methyl butane, dipentene dimercaptan, ethylcyclohexyl di Thiols (ECHDT), dimercaptodiethylsulfide, methyl-substituted dimercaptodiethylsulfide, dimethyl-substituted dimercaptodiethylsulfide, dimercaptodioxaoctane, 1,5-dimercapto-3-oxapentane and And any combination of these. The polythiol may have at least one pendant group selected from a lower (for example, C _{1 -6} ) alkyl group, a lower alkoxy group and a hydroxyl group. Suitable alkyl pendant groups include, for example, C _{1 -6} linear alkyl, C _{3 -6} branched alkyl, cyclopentyl and cyclohexyl.

Other examples of suitable dithiol are Dimer in Cobb Todai ethyl sulfide (DMDS) {the formula (20), R ¹ is _{- [(- CH 2 -)} p -X-] q - (CH 2) r - , and, p is 2, r is 2, q is 1, and X is -S-; Dimercaptodioxaoctane (DMDO) wherein, in the formula (20), R ¹ is - [(CH ₂ -) _p -X-] _q - (CH ₂ ) _r -, p is 2, q is 2 , r is 2, and X is -O-; Dimercapto-3-oxapentane wherein R ¹ is - [(CH ₂ -) _p -X-] _q - (CH ₂ ) _r -, p is 2, r is 2, q is 1, and X is -O-. It is also possible to use dithiols containing heteroatoms in both the carbon skeleton and pendant alkyl groups (e.g., methyl groups). Such compounds for example, _{HS-CH 2 CH (CH 3} ) -S-CH 2 CH 2 -SH, HS-CH (CH 3) methyl such as _{CH 2 -S-CH 2 CH 2} -SH - substituted DMDS, And dimethyl-substituted DMDS such as HS-CH ₂ CH (CH ₃ ) -S-CHCH ₃ CH ₂ -SH and HS-CH (CH ₃ ) CH ₂ -S-CH ₂ CH (CH ₃ ) -SH .

The multivalent sulfur-containing adhesion promoting adduct can impart additional flexibility to the polyfunctional adhesion promoter resulting in improved surface adhesion. In certain embodiments, the polyvalent sulfur-containing adhesion promoting adduct may be prepared by first reacting the polyfunctionalizing agent with a sulfur-containing compound to provide a polyfunctionalizing agent having a sulfur-containing group. This intermediate can then be reacted with an adhesion promoter such as an adduct of formula (13) having a functional group reactive with the sulfur-containing group. The fire-containing polyfunctionalizing agent and the adhesion promoting adduct may react at a rate such that all or some of the mercury is terminated with the adhesion promoting adduct.

Copolymerizable  Adhesion promoting adjunct

Adhesion promoting adducts that can be directly polymerized with the sulfur-containing polymer backbone can improve the adhesion of compositions such as sealant compositions. The copolymerizable adhesion promoting adduct

Surface adhesion and adhesion promoters and metal ligands that provide reactive groups that are reactive with the end groups of the copolymer and / or the curing agent. During the curing reaction, at least a portion of the reactive end groups of the adhesion promoting adduct copolymerizable with the end groups of the copolymer react with the copolymer and / or the curing agent, thereby directly bonding the copolymerizable adhesion promoting adduct to the polymer network . In another embodiment, the copolymerizable adhesion promoting adduct may comprise a group that is reactive with the copolymer.

Thus, in certain embodiments, the copolymerizable adhesion promoting adduct is an adhesion promoting adduct comprising an adhesion promoter, a metal ligand and a reactive functional group; And a z-polyfunctionalizing agent comprising a functional group wherein the adhesion promoting moiety is reactive with the functional group of the water, wherein the copolymerizable adhesion promoting adduct comprises 1 to z-1 terminal adhesion promoting moieties It contains water.

In certain embodiments, the copolymerizable adhesion promoting adduct has the structure of formula (21): < EMI ID =

B (-V^One'-R^{14 '}-M-R^{13 '}-R^{12 '}-P-R¹¹)_z1(-V²)_{z- z1} (21)

In this formula,

R ¹¹ comprises an adhesion promoter;

P comprises a core of an adhesion promoter;

M comprises a metal ligand;

R ^{12 '} and R ^13' represent residues derived from the reaction of R ¹² and R ¹³ of the adhesion promoter R ¹¹ -PR ¹² and the metal chelating agent R ¹³ -MR ¹⁴ wherein R ¹² and R ¹³ are mutually reactive functional groups R ¹⁴ comprises a reactive functional group;

B represents the core of the z-polyfunctionalizing agent of the formula (22)

_{^{B (-V 1) z1 (-V}} 2) z- z1 (22)

In this formula,

z is an integer from 3 to 6;

z1 is an integer from 1 to z-1;

Each -V ¹ is a group containing a first reactive functional group;

At least one -V ² is a second reactive functional group, and;

Each R ^{14 '} represents a residue derived from the reaction of R ¹⁴ and -V ¹ ;

Each -V ^{1 '} - represents a residue derived from the reaction of -V ¹ and R ¹⁴ .

In certain embodiments, the copolymerizable adhesion promoting adduct comprises a reaction product of reactants comprising:

A polyfunctionalizing agent of the formula (22)

_{^{B (-V 1) z1 (-V}} 2) z- z1 (22)

[In the above formula,

B represents the core of z- the polyfunctionalizing agent B (-V) _z ,

z is an integer from 3 to 6;

z1 is an integer from 1 to z-1;

Each -V ¹ is a group containing a first reactive functional group;

And at least one -V ² comprises a second reactive functional group; And

An adhesion promoter, a metal ligand, and a third functional group reactive with said first reactive functional group.

In certain embodiments, V ¹ and V ² are the same and, in certain embodiments, V ¹ and V ² are different. In certain embodiments, V ¹ and V ² comprise the same reactive functional group, and in certain embodiments, V ¹ and V ² comprise different reactive functional groups. In certain embodiments, each V ² is selected to be reactive with a curing agent, a prepolymer, or combinations thereof. In certain embodiments, each V < ² > comprises the same reactive group as the prepolymer forming the composition.

The copolymerizable adhesion promoting adduct comprises at least some groups that are reactive with the curing agent and / or the curing agent or copolymer such as 2 to 5 groups that are reactive with the copolymer.

Copolymerizable  The sulfur-containing adhesion promoting adduct

In certain embodiments, the copolymerizable adhesion promoting adduct may be a copolymerizable sulfur-containing adhesion promoting adduct. Copolizable sulfur-containing adhesion promoters are disclosed in U.S. Patent Application No. 13 / 529,183. Such copolymerizable sulfur-containing adhesion promoting adducts contain sulfur-containing groups bonded to the polyfunctional core, wherein at least a portion of the sulfur-containing groups terminate with groups that are reactive with the curing agent or prepolymer, Terminated with adducts.

Embodiments herein include a copolymerizable adhesion promoter similar to that disclosed in U.S. Patent Application No. 13 / 529,183, wherein the adhesion promoting adduct herein replaces at least some or all of the adhesion promoting adducts disclosed herein .

Thus, in certain embodiments, the copolymerizable sulfur-containing adhesion promoting adduct is selected from the group consisting of dithiol; A multifunctional agent comprising a functional group that is reactive with a thiol group; And reaction products of reactants comprising an adhesion promoter, an adhesion promoting adduct comprising a metal ligand and a group reactive with the thiol group. In certain embodiments, compounds other than dithiol may be used to introduce sulfur-containing groups into the adduct.

In certain embodiments, the copolymerizable sulfur-containing adhesion promoting adduct has the structure of formula (23)

^{B (-V'-SR 1 -S- R} 14 '-MR 13' -R 12 '-PR 11) z1 (-V'-SR 1 -SH) z- z1 (23)

In this formula,

Each R ¹ is independently C _{2 -6} alkanoic die yl, C _{6 -8} cycloalkyl alkane die yl, C _{6 -10} alkane bicyclo alkane die yl, C _{5 -8} heterocycloalkyl alkane die work and - [- (CHR ³ ) _s- X-] _q- (CHR < ³ >) _r -

Each R < ³ > is independently selected from hydrogen and methyl;

Each X is independently selected from -O-, -S-, and -NR-, wherein R is selected from hydrogen and methyl;

s is an integer from 2 to 6;

q is an integer from 1 to 5;

r is an integer from 2 to 10;

R ¹¹ comprises an adhesion promoter;

P comprises a core of an adhesion promoter;

M comprises a metal ligand;

R ^{12 '} and R ^13' represent residues derived from the reaction of R ¹² and R ¹³ of the adhesion promoter R ¹¹ -PR ¹² and the metal chelating agent R ¹³ -MR ¹⁴ wherein R ¹² and R ¹³ are mutually reactive functional groups , And R ¹⁴ includes a reactive functional group.

R ^{14 '} represents a residue derived from the reaction of R ¹⁴ with a thiol group;

B represents the core of z- the polyfunctionalizing agent B (-V) _z ,

z is an integer from 3 to 6;

z1 is an integer from 1 to z-1;

Each -V is a group comprising a group reactive with a thiol group;

Each -V'- is derived from the reaction of -V with a thiol group.

In certain embodiments, the copolymerizable sulfur-containing adhesion promoting adduct is selected from the group consisting of dithiol; A multifunctional agent comprising a functional group that is reactive with a thiol group; And a reaction product of reactants comprising an adhesion promoting adduct of claim 1 comprising a functional group that is reactive with the thiol group.

In certain embodiments, the copolymerizable adhesion promoting adducts provided by the present invention include, for example, sulfur-containing polymers such as thiol-terminated sulfur-containing polymers including thiol-terminated polythioethers and thiol- Lt; / RTI > backbone.

In certain embodiments, the adhesion promoting adduct may be copolymerized with a thiol-terminated polythioether polymer. Examples of thiol-functional polythioethers are disclosed, for example, in U.S. Patent No. 6,172,179. In certain embodiments, the thiol-functional polythioether includes Permapol (R) P3.1E, available from PRC-DeSoto International Inc., Shilo, Calif. do.

In certain embodiments, the adhesion promoting adduct may be copolymerized with the polysulfide polymer. In certain embodiments, the polysulfide polymer may be any of the polymers disclosed, for example, in U.S. Patent No. 4,623,711.

The compounds of formulas (21) and (23) comprise at least one terminal adhesion promoting adduct and at least two terminal thiol groups. The one or more adhesion promoting adducts provide adhesion to the surface and / or other components of the formulation that are part of the formulation, and the terminal thiol-groups react with the curing agent to form a polymer network. Thus, in the compounds of formulas (21) and (23), z2 is greater than or equal to 2, and in certain embodiments, z2 is 2, 3, 4 and, in certain embodiments, z2 is 5. In certain embodiments of formulas (21) and (23), z 1 is 1, 2, 3, and in certain embodiments, z 1 is 4. In certain embodiments, the compounds of formulas (21) and (17) are trivalent such that z is 3. In certain embodiments, the compounds of formulas (21) and (23) are tetravalent wherein z is 4, and in certain embodiments, compound z of formulas (21) and (17) is 5, z is a trivalent such that it is six.

In formula (21), and certain embodiments of (23), R ¹ is C ₂ - ₆ alkanoic die and one - is selected from _{^{- [- (CHR 3) s}} -X-] q - (CHR 3) r.

In certain embodiments of formulas (21) and (23), R ¹ is - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r -, in certain embodiments X is- In certain embodiments, X is -S-.

In certain embodiments of formula (21) and (23) wherein R ¹ is - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r -, p is 2, r is 2, 1, and X is -S-; In certain embodiments, p is 2, q is 2, r is 2, and X is -O-; In certain embodiments, p is 2, r is 2, q is 1, and X is -O-.

In certain embodiments of formula (21) and (23) wherein R ¹ is - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r -, each R ³ is hydrogen and in certain embodiments , And at least one R < ³ > is methyl.

In certain embodiments of the compounds of formulas (21) and (23), each R ¹ is the same and, in certain embodiments, at least one R ¹ is different.

In certain embodiments of the compounds of formulas (21) and (23), the terminal group that is reactive with the thiol group of compound A includes an alkenyl group, an isocyanate group, an epoxy group, a Michael acceptor group, g is selected from a group comprising a saturated carbon with _{-Cl, -Br, -I, -OSO 2} CH 3 ( _{mesylate), -OSO 2 -C 6 H 4} -CH 3 ( tosylate) or the like. In certain embodiments of compounds of formulas (21) and (23), the terminal group that is reactive with the thiol group of compound A is an alkenyl group, an isocyanate group, an epoxy group, a Michael acceptor group and, in certain embodiments, Is a group comprising saturated carbons having suitable leaving groups such as -Cl, -Br, -I, -OSO ₂ CH ₃ (mesylate), -OSO ₂ -C ₆ H ₄ -CH ₃ (tosylate) .

In certain embodiments of the compounds of formulas (21) and (23), the terminal groups that promote adhesion are selected from polyalkoxysilyl, phosphonates, amines, carboxylic acids and phosphonic acids. In certain embodiments of the compounds of formulas (21) and (23), the end-group promoting adhesion is a polyalkoxysilyl group, a phosphonate group, an amine group, a carboxylic acid group, and in certain embodiments, a phosphonic acid group.

In certain embodiments of the compounds of formulas (21) and (23), the metal ligand is selected from any of those disclosed herein.

In certain embodiments, -V is a residue comprising a terminal group that is reactive with a thiol group. For example, in certain embodiments, is -V and -R ¹⁰ -CH = CH _2, wherein R ¹⁰ is C ₁ - ₆ alkane di one, substituted C ₁ - ₆ alkane die yl, C ₁ - ₆ heteroaryl alkane It is selected from ₆ hetero alkane di-yl-di one and substituted C _1. However, the structure of -V is not limited. In certain embodiments, each -V may be the same and, in certain embodiments, one or more -V may be different.

In certain embodiments of compounds of formulas (21) and (23), each adhesion promoting moiety is the same and is selected from the following formulas (24a), (24b), (24c) and (24d)

In this formula,

Each R ¹⁰ is C _{2 -8} alkanediyl, y 1 is selected from 0, 1 and 2, y 2 is selected from 1, 2 and 3, the sum of y 1 and y 2 is 3, each R ⁵ and R ⁶ is independently selected from C _{1 -4} alkyl, R ⁸ is selected from hydrogen and C _{1 -4} alkyl.

In certain embodiments of the compounds of formulas (21) and (23), each -A 'is the same and is a residue of formula (24a), a residue of formula (24b) Is the residue of formula (24d).

In the copolymerizable sulfur-containing adhesion promoting adducts of formulas (21) and (23), B represents z- the polyfunctional compound B (-V) _z , wherein z is an integer from 3 to 6. In certain embodiments, z is 3, z is 4, z is 5, and in certain embodiments, z is 6. In certain embodiments, the polyfunctional compound is trifunctional. In certain embodiments, the multifunctional compound is triallyl cyanurate (TAC), wherein B has the structure:

;

;

Each -V has a structural formula _{-O-CH 2 -CH = CH 2} .

In certain embodiments, the multifunctional compound B (-V) _z has a molecular weight of less than 800 daltons, less than 600 daltons, less than 400 daltons, and in certain embodiments less than 200 daltons. The multifunctional compound B (-V) _z , where _z is greater than or equal to 3, can be any polyfunctionalizing agent useful in polymer chemistry. It is also possible to use formulations comprising multifunctional agents with mixed functionality, i. E., Residues (typically separate residues) that react with both thiol and vinyl groups. Other useful polyfunctionalizing agents include trimethylolpropane tribinylether, and the polythiol described in U.S. Patent No. 4,366,307, U.S. Patent No. 4,609,762, and U.S. Patent No. 5,225,472, each of which is incorporated herein by reference. Combinations of polyfunctionalizing agents having the same terminal groups such as thiol groups or allyl groups may also be used.

In certain embodiments, each of the -V, for example, alkenyl groups, epoxy groups, Michael acceptor groups, or nucleophilic substitution in a preferred leaving group, for example _{-Cl, -Br, -I, -OSO 2} CH 3 ( mesylate a residue comprising _{rate), -OSO 2 -C 6 H 4} -CH 3 ( tosylate) group and a group reactive with the terminal thiol group, such as containing a saturated carbon with like. In certain embodiments, each -V is the same and, in certain embodiments, one or more -V is different. In certain embodiments, -V is a C ₃ - ₈ alkene-1-yl, and C ₃ - _8, and a heteroatom-alkene-1-yl, wherein the one or more heteroaryl group is selected from -O- and -S-.

Each -V'- represents a residue formed by the reaction of a residue -V with a thiol group. In certain embodiments, -V is C _{3 -8} alkene-1-yl, and C _{3 -8} hetero alkene contains a terminal alkenyl selected from 1-yl, V 'is a C _{3 -8} alkane die yl and C _{3 -8heteroalkanediyl} . &_{Lt; /} RTI >

In certain embodiments, the polyfunctionalizing agent having a terminal group that is reactive with a thiol group has the structural formula B (-V) _z , wherein z is an integer from 3 to 6, and B and V are as defined herein.

In certain embodiments of B (-V) _z , each -V comprises a terminal alkenyl group.

In certain embodiments, the copolymerizable sulfur-containing adhesion promoter of Formula (23) comprises: (a) a polyfunctionalizing agent having a terminal group that is reactive with a thiol group; (b) dithiol; And (c) an adhesion promoting adduct having a functional group reactive with the thiol group. In certain embodiments of the reaction, the reaction product comprises at least one compound of formula (23). The polyfunctionalizing agent and adhesion promoting adduct may be, for example, any of those disclosed herein, and the dithiol may be a dithiol of formula (20).

In certain embodiments, the dithiol has the structure of formula (20)

HS-R ¹ -SH (20)

In this formula,

R ¹ is C ₂ - ₆ alkanoic die yl, C ₆ - ₈ cycloalkyl alkane die yl, C ₆ - ₁₀ cycloalkyl alkane alkane die yl, C ₅ - ₈ heterocycloalkyl alkane die work and _{^{- [- (CHR 3) s}} -X -] _q - (CHR < ³ >) _r -, wherein

Each R < ³ > is independently selected from hydrogen and methyl;

Each X is independently selected from -O-, -S-, and -NR-, wherein R is selected from hydrogen and methyl;

s is an integer from 2 to 6;

q is an integer from 1 to 5;

r is an integer of 2 to 10;

In certain embodiments, R ¹ is - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r -.

In certain embodiments of compounds of formula (20), X is a selected from -O- and -S-, thus the general formula (20) - [- (CHR 3) s -X-] q - (CHR 3) r - is - (- CH ₂ -) _p --O--] _q - (CH ₂ ) _r - or - [- CH ₂ -) _p --S--] _q - (CH ₂ ) _r -. In certain embodiments, p and r are the same, e.g., p and r are both 2.

In certain embodiments, R ¹ is C ₂ - ₆ alkanoic die and one - is selected from _{^{- [- (CHR 3) s}} -X-] q - (CHR 3) r.

In certain embodiments, R ¹ is - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r -, and in certain embodiments X is -O-, in certain embodiments X is -S- .

R ¹ is _{^{- [- (CHR 3) s}} -X-] q - (CHR 3) r - in which certain embodiments, p is 2, r is 2, q is 1, X is -S- and ; In certain embodiments, p is 2, q is 2, r is 2, and X is -O-; In certain embodiments, p is 2, r is 2, q is 1, and X is -O-.

In certain embodiments, each R ³ is hydrogen and, in certain embodiments, at least one R ³ is methyl. In certain embodiments, R ¹ is - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r -.

In certain embodiments of the compounds of formula (20), each R ¹ is the same and, in certain embodiments, at least one R ¹ is different.

Examples of suitable dithiols are, for example, 1,2-ethanedithiol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, , 3-butane dithiol, 1,3-pentane dithiol, 1,5-pentane dithiol, 1,6-hexane dithiol, 1,3-dimercapto-3-methyl butane, dipentene dimercaptan, (ECHDT), dimercaptodiethylsulfide, methyl-substituted dimercaptodiethylsulfide, dimethyl-substituted dimercaptodiethylsulfide, dimercaptodioxaoctane, 1,5-dimercapto-3-oxa Pentane, and any combination thereof. The polythiol may have at least one pendant group selected from a lower (e.g., C _{1 -6} ) alkyl group, a lower alkoxy group, and a hydroxyl group. Suitable alkyl pendant groups include, for example, C _{1 -6} linear alkyl, C _{1 -6} branched alkyl, cyclopentyl and cyclohexyl.

Another example of a suitable dithiol is dimercaptodiethylsulfide (DMDS) wherein R ¹ is - [(- CH ₂ -) _p --X -] _q - (CH ₂ ) _r -, where p Is 2, r is 2, q is 1, and X is -S-); In the dimer Cobb Todai-oxa-octane (DMDO) (formula (20), R ¹ is _{- [(- CH 2 -)} p -X-] q - (CH 2) r - , and wherein p is 2, q is 2, r is 2, and X is -O-; (20), R ¹ is - [(- CH ₂ -) _p -X-] _q - (CH ₂ ) _r - wherein p is 2 and , r is 2, q is 1, and X is -O-. Dithiols containing both a heteroatom in the carbon skeleton and a pendant alkyl group such as a methyl group may be used. Such compounds are for example methyl-substituted DMDS e.g., _{HS-CH 2 CH (CH 3} ) -S-CH 2 CH 2 -SH, HS-CH (CH 3) CH 2 -S-CH 2 CH 2 -SH and dimethyl substituted DMDS include, for example, _{HS-CH 2 CH (CH 3} ) -S-CHCH 3 CH 2 -SH and _{HS-CH (CH 3) CH} 2 -S-CH 2 CH (CH 3) -SH .

In certain embodiments of the reaction for preparing a copolymerizable sulfur-containing adhesion promoting adduct, the polyfunctionalizing agent can be reacted with a dithiol to form a thiol-terminated intermediate. The molar ratio of the reactants is appropriately selected. For example, one mole of a trifunctional compound such as TAC can be reacted with 3 moles of dithiol, such as DMDO, to provide a trifunctional thiol-terminated intermediate. A trifunctional thiol-terminated intermediate may be subsequently reacted with a compound comprising a group reactive with a thiol group and a group promoting adhesion. The molar ratio of the compound comprising a group reactive with the thiol group and the group promoting adhesion to the intermediate may be selected to provide a multifunctional compound having the desired average sulfur-containing adhesion promoting adduct functionalization degree. For example, to obtain an average degree of adhesion promoter activation of about 1, about 1 mole of the polyfunctional intermediate is reacted with about 1 mole of a compound comprising a terminal group reactive with a thiol group and an end-capping group promoting adhesion.

In the copolymerizable sulfur-containing adhesion promoting adducts provided by the present application, the compounds include at least one terminal group that promotes adhesion and at least two terminal groups that can react with the curing agent, for example, two or more terminal thiol groups, For example, to be incorporated into the framework. In certain embodiments, the sulfur-containing compound comprises, on average, one adhesion promoter per molecule, and in certain embodiments, an average of two adhesion promoters per molecule.

In certain embodiments, the copolymerizable sulfur-containing adhesion promoting adduct comprises the reaction product of reactants comprising triallyl cyanurate, DMDO and the adhesion promoting adduct provided herein.

Composition

The sulfur-containing adhesion promoting adducts provided by the present application can be used in polymer compositions such as compositions formulated as sealants useful in the aerospace industry.

Adhesion promoting adducts such as those represented by Formula (13), Formula (18), Formula (19), Formula (21), Formula (23), or any combination thereof may be used as adhesion promoting additives in the composition . In certain embodiments, the adhesion promoting adduct comprises, for example, from 1 wt% to 50 wt%, from 5 wt% to 30 wt%, or from 1 wt% to 10 wt% of the composition.

In another embodiment wherein the adhesion promoting adduct is copolymerizable with those represented by the chemical formulas (21) and (23), the copolymerizable adhesion promoting adduct may be incorporated with a copolymer having suitable chemistry and / or a curing agent, A possible adhesion promoting adduct is incorporated into the cured polymer.

The composition may also contain a combination of one or more adhesion promoting adducts and / or copolymerizable adhesion promoting adducts provided herein.

In aerospace sealant applications, the composition may comprise a sulfur-containing polymer. In certain embodiments, the sulfur-containing prepolymer is selected from a thiol-terminated polythioether prepolymer, a thiol-terminated polysulfide prepolymer, a thiol-terminated sulfur-containing polyfoam prepolymer, and any combination thereof. Containing thiol-terminated sulfur-containing prepolymer. In certain embodiments, the sulfur-containing prepolymer comprises a thiol-terminated polythioether prepolymer.

In certain embodiments, the thiol-terminated sulfur-containing polymer comprises a thiol-terminated polythioether. The thiol-terminated polythioether may comprise a mixture of different polythioethers, and the polythioether may have the same or different functional groups of thiol groups. In certain embodiments, the thiol-terminated polythioether has an average degree of functionalization of from 2 to 6, from 2 to 4, from 2 to 3, and in certain embodiments from 2.05 to 2.8. For example, thiol-terminated polythioethers may be selected from bifunctional sulfur-containing polymers, trifunctional sulfur-containing polymers, and combinations thereof.

Examples of thiol-functional polythioethers are disclosed, for example, in U.S. Patent No. 6,172,179. In certain embodiments, the thiol-functional polythioether includes Permapol® P3.1E, commercially available from Piali-Desoto International, Inc. (Sylma, Calif.).

In certain embodiments, the thiol-terminated polythioether comprises (a) a backbone comprising the structure of formula (25): < EMI ID =

^{-R 1 - [- S- (CH} 2) 2 -O - [- R 2 -O-] m - (CH 2) 2 -SR 1] n - (25)

Wherein each R ¹ is independently selected from the group consisting of a C _{2 -10} n-alkanediyl group, a C _{3 -6} branched alkanediyl group, a C _{6 -8} cycloalkanediyl group, a C _{6 -10} alkane cycloalkanediyl group, heterocyclic _{group, - [(- CH 2 -} ) p -X-] q - (CH 2) r - group, and at least one -CH ₂ - unit is substituted with a group _{- [(- CH 2 -)} p - _{X-] q - (CH 2)} r - is independently selected from the group; (ii) each R ² is selected from the group consisting of a C _{2 -10} n-alkanediyl group, a C _{3 -6} branched alkanediyl group, a C _{6 -8} cycloalkanediyl group, a C _{6 -14} alkane cycloalkanediyl group, , And - [(- CH ₂ -) _p -X-] _q - (CH ₂ ) _r - groups; (iii) each X is independently selected from O, S, and -NR- groups, wherein R is selected from hydrogen and a methyl group; (iv) m is from 0 to 50; (v) n is an integer from 1 to 60; (vi) p is an integer from 2 to 6; (vii) q is an integer from 1 to 5; (viii) r is an integer of 2 to 10;

In certain embodiments, the thiol-terminated polythioether is selected from thiol-terminated polythioethers of formula (26a), thiol-terminated polythioethers of formula (26b), and combinations thereof:

HS-R ¹ - [-S- (CH ₂ ) _p -O- (R ² -O) _m - (CH ₂ ) ₂ -SR ¹ -] _n-

^{{HS-R 1 - [-} S- (CH 2) p -O- (R 2 -O) m - (CH 2) 2 -SR 1 -] n -S-V'-} z B (26b)

In this formula,

Each R ¹ is C _{2 -6} alkanoic die yl, C _{6 -8} cycloalkyl alkane die yl, C _{6 -10} alkane bicyclo alkane die yl, C _{5 -8} heterocycloalkyl alkane die and one - [(- CHR ³ -) _{s -X-] q - (- CHR} 3 -) r - is independently selected from; At this time

s is an integer from 2 to 6;

q is an integer from 1 to 5;

r is an integer from 2 to 10;

Each R < ³ > is independently selected from hydrogen and methyl;

Each X is independently selected from O, S and -NR-, wherein R is selected from hydrogen and methyl;

Each R ² is C _{1 -10} alkane die yl, _-8 C ₆ cycloalkyl alkane die days, _-14 C ₆ alkane bicyclo alkane die work, and ^{- [(- CHR 3 -)} s -X-] q - (- CHR ³ -) _r -; Wherein s, q, r, R ³ and X are as defined above;

m is an integer from 0 to 50;

n is an integer from 1 to 60;

p is an integer from 2 to 6;

B represents the core of the z-valent polyfunctional compound B (-V) _z ; At this time

z is an integer from 3 to 6; Each -V is a residue comprising a terminal group which is reactive with a thiol group;

Each -V'- represents a residue formed by the reaction of each -V with a thiol group.

In certain embodiments, R ¹ in formulas (26a) and (26b) is - [(- CH ₂ -) _p -X-] _q - (CH ₂ ) _r -, p is 2, X is -O -, q is 2, r is 2, R ² is ethanediyl, m is 2, and n is 9.

In certain embodiments of formula (26a) and formula (26b), R ¹ is C _{2 -6} alkanoic die and one - is selected from _{^{- [- (CHR 3) s}} -X-] q - (CHR 3) r.

In certain embodiments of formulas (26a) and (26b), R ¹ is - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r -, and in certain embodiments X is -O- In certain embodiments, X is -S-.

In certain embodiments of formulas (26a) and (26b) wherein R ¹ is - [- (CHR ³ ) _s -X-] _q - (CHR ³ ) _r -, p is 2, r is 2, q Is 1, and X is -S-; In certain embodiments, p is 2, q is 2, r is 2, and X is -O-; In certain embodiments, p is 2, r is 2, q is 1, and X is -O-.

R ¹ is _{^{- [- (CHR 3) s}} -X-] q - (CHR 3) r - and the formula (26a) and is In certain embodiments, each R ³ in the formula (26b) hydrogen, certain embodiments Lt; ³ > is methyl.

In certain embodiments of formulas (26a) and (26b), each R ¹ is the same and, in certain embodiments, at least one R ¹ is different.

These polythioethers can be prepared by various methods. Examples of suitable thiol-functional polythioethers for use in the compositions disclosed herein and methods of making them are described in U.S. Patent No. 6,172,179 (2nd column, line 29 to fourth column, line 22, Column 39 to column 10, and column 11, line 65 to column 12, line 22). These thiol-functional polythioethers may be bifunctional (i.e., linear polymers having two thiol end groups) or multifunctional (i.e., branched polymers having three or more thiol end groups). Suitable thiol-functional polythioethers are commercially available, for example, as FermaPol ® P3.1E from Piale-Desoto International Inc. (Sillma, Canada).

A suitable thiol-functional polythioether can be produced by reacting a mixture of divinyl ether or divinyl ether with an excess of dithiol or a mixture of dithiols. For example, suitable dithiols for use in preparing such thiol-functional polythioethers include combinations of dithiols of formula (20), other dithiols disclosed herein, or any of the dithiols disclosed herein.

Suitable divinyl ethers include, for example, divinyl ethers of the formula (27)

CH ₂ CH - O - (- R ² --O--) _m --CHCH ₂ (27)

Wherein R ² in formula (27) is a C _{2 -6} n-alkanediyl group, a C _{3 -6} branched alkanediyl group, a C _{6 -8} cycloalkanediyl group, a C _{6 -10} alkane cycloalkanediyl group, And - [(- CH ₂ -) _p -O-] _q - (- CH ₂ -) _r -; p is an integer from 2 to 6; q is an integer from 1 to 5; r is an integer of 2 to 10;

In certain embodiments of a divinyl ether of formula (27), R ² is C _{2 -6} n- alkanes die group, C _3-6 branched alkane di group, C _{6 -8} cycloalkyl die alkane group, C _{6 -10} Alkane-cycloalkanediyl group, and in certain embodiments - - (- CH ₂ -) _p --O--] _q - (- CH ₂ -) _r -.

Suitable divinyl ethers include compounds having one or more oxyalkanediyl groups such as, for example, 1 to 4 oxyalkanediyl groups, i.e., compounds wherein m in formula (27) is an integer from 1 to 4. In certain embodiments, m in formula (27) is an integer from 2 to 4. It is also possible to use a commercially available divinyl ether mixture characterized by non-integer mean values of the number of oxyalkane dile units per molecule. Thus, m in formula (27) can take a rational number value of 0 to 10.0, such as 1.0 to 10.0, 1.0 to 4.0, or 2.0 to 4.0.

Examples of suitable divinyl ethers include, for example, divinyl ether, ethylene glycol divinyl ether (EG-DVE) wherein R ² is ethanediyl and m is 1 in formula (27), butane diol di divinyl ether (BD-DVE) (and R ² is butane die one of the formula 27, m is 1 Im), hexane diol divinyl ether the R ² of the (HD-DVE) (formula 27 hexane die days And m is 1), diethylene glycol divinyl ether (DEG-DVE) (R ² of formula (4) is ethanediyl and m is 2), triethylene glycol divinyl ether (formula 27) wherein R ² is ethanediyl and m is 3, tetraethylene glycol divinyl ether (R ² of formula (27) is ethanediyl and m is 4), cyclohexanedimethanol di Vinyl ether, polytetrahydrofuryl divinyl ether; Tribinyl ether monomers such as trimethylolpropane tribinyl ether; Tetrafunctional ether monomers such as pentaerythritol tetravinyl ether; And combinations of two or more of such polyvinyl ether monomers. The polyvinyl ether may have at least one pendant group selected from an alkyl group, a hydroxyl group, an alkoxy group and an amine group.

In certain embodiments, divinyl ethers wherein R ² in formula (27) is C _{3 -6} branched alkanediyl can be prepared by reacting a polyhydroxy compound with acetylene. An example of this type of divinyl ether is a compound in which R ² in formula (27) is an alkyl-substituted methanediyl group such as -CH (CH ₃ ) - [for example, Pluriol E-200 die (In this case R ² in formula (27) is ethanediyl and m is 3.8) or alkyl-substituted ethanediyl (for example, - CH ₂ CH (CH ₃ ) -), such as DPE polymer blends including DPE-2 and DPE-3 (International Specialty Products, Wayne, NJ).

Other useful divinyl ethers include polytetrahydrofuryl (poly-THF) or polyoxyalkanediyl such that R ² in formula (27) has an average of about three monomer units.

More than one type of polyvinyl ether monomer of formula (27) may be used. Thus, in a particular embodiment, two dithiols of formula (20), one polyvinyl ether monomer of formula (27), one dithiol of formula (20) and two polyvinyl ether monomers of formula (27) A variety of thiol-functional polythioethers can be produced using two dithiol of formula (20), two divinyl ether monomers of formula (27), and compounds of one or both of the two more than two.

In certain embodiments, the polyvinyl ether monomer comprises from 20 to 50 mole percent, and in certain embodiments from 30 to 50 mole percent, of the reactants used to prepare the thiol-functional polythioether.

In certain embodiments provided by the present application, the relative amount of dithiol and divinyl ether is selected to produce a terminal thiol group. Thus, a mixture of a dithiol of formula (20) or a mixture of two or more different dithiols of formula (20) with a divinyl ether of formula (27) or a mixture of two or more different divinyl ethers of formula (27) Vinyl group is greater than 1: 1 (for example, 1.1 to 2.0: 1.0).

The reaction between the dithiol compound and the divinyl ether compound can be promoted by a free radical catalyst. Suitable free radical catalysts include, for example, azo compounds such as azobisnitrile [e.g., azo (bis) isobutyronitrile (AIBN)]; Organic peroxides such as benzoyl peroxide and tert-butyl peroxide; And inorganic peroxides such as hydrogen peroxide. The catalyst may be a free-radical catalyst, an ionic catalyst or ultraviolet. In certain embodiments, the catalyst does not comprise an acidic or basic compound and does not produce an acidic or basic compound upon decomposition. Examples of free-radical catalysts include Vazo®-57 (Du Pont), Vazo®-64 (DuPont), Vazo®-67 (DuPont), V-70® (Wako Specialty Chemicals Specialty Chemicals) and V-65B (Wako Specialty Chemicals). Examples of other free-radical catalysts are alkyl peroxides such as tertiary-butyl peroxide. The reaction can also be carried out by irradiation with ultraviolet light in the presence or absence of a cationic photoinitiator.

The thiol-functional polythioether provided herein is prepared by combining one or more compounds of formula (20) with one or more compounds of formula (27), followed by addition of a suitable catalyst and heating at from 30 ° C to 120 ° C, At 90 < 0 > C for 2 to 24 hours, for example 2 to 6 hours.

As disclosed herein, thiol-terminated polythioethers may include multifunctional polythioethers. That is, an average degree of functionalization of greater than 2.0. Suitable multifunctional thiol-terminated polythioethers include, for example, those having the structure of formula (28): < EMI ID =

B (-A-SH) _z (28)

(Ii) B is the z residue of the polyfunctionalizing agent; (iii) z is an average value greater than 2.0, in certain embodiments from 2 to 3, A value of 2 to 4, a value of 3 to 6, and in certain embodiments an integer of 3 to 6.

Suitable polyfunctionalizing agents for preparing such multifunctional thiol-functional polymers include triblocking agents, i. E. Compounds with z = 3. Suitable trifunctionalizing agents include, for example, triallyl cyanurate (TAC), 1,2,3, 4-triazacyanilate (TAC) as disclosed in paragraphs [0102] to [0105] of U.S. Patent Publication No. 2010/0010133, -Propanetriethiol, isocyanurate-containing trithiol, and combinations thereof. Other useful polyfunctionalizing agents include trimethylolpropane tribinylether, and the polythiol described in U.S. Patent Nos. 4,366,307, 4,609,762 and 5,225,472. Mixtures of polyfunctionalizing agents may also be used.

As a result, thiol-functional polythioethers suitable for use in the embodiments provided herein can have a broad average degree of functionalization. For example, the trifunctionalizing agent may provide an average degree of functionalization of from 2.05 to 3.0, such as from 2.1 to 2.6. A wider average degree of functionalization can be obtained by using a multifunctional agent or a higher functional multifunctional agent. The degree of functionalization may also be influenced by factors such as stoichiometry, as will be appreciated by those skilled in the art.

Thiol-functional polythioethers having degrees of functionalization greater than 2.0 can be prepared in a manner analogous to the bifunctional thiol-functional polythioethers described in U.S. Patent Publication No. 2010/0010133. In certain embodiments, the polythioether can be prepared by combining (i) one or more dithiols described herein with (ii) one or more of the divinyl ethers described herein and (iii) one or more polyfunctionalizing agents. The mixture can then optionally be reacted in the presence of a suitable catalyst to provide a thiol-functional polythioether having a degree of functionalization of greater than 2.0.

Thus, in certain embodiments, the thiol-terminated polythioether comprises the reaction product of a reactant comprising: (a) a dithiol of formula (20) and (b) a divinyl ether of formula (27)

HS-R ¹ -SH (20)

CH ₂ = CH-O - [- R ² --O -] _m --CH = CH ₂ (27)

Wherein R ¹ is selected from the group consisting of C _{2 -6} alkanediyl, C _{6 -8} cycloalkanediyl, C _{6 -10} alkane cycloalkanediyl, C _{5 -8} heterocycloalkanediyl and - [- (CHR ³ ) _s- X-] _q- (CHR < ³ >)_r-; Wherein each R < ³ > is independently selected from hydrogen and methyl; Each X is independently selected from -O-, -S-, -NH-, and -NR-; R is selected from hydrogen and methyl; s is an integer from 2 to 6; q is an integer from 1 to 5; r is an integer from 2 to 10; Each R ² is C _{1 -10} alkane die yl, _-8 C ₆ cycloalkyl alkane die days, _-14 C ₆ alkane bicyclo alkane die work, and ^{- [(- CHR 3 -)} s -O-] q - (- CHR ³ -) _r -; Wherein s, q, r, R ³ and X are as defined above; m is an integer from 0 to 50; n is an integer from 1 to 60; p is an integer of 2 to 6;

Also, in certain embodiments, the reactants comprise multifunctional compounds such as (c) a multifunctional compound B (-V) _z wherein B, -V and z are as defined herein.

The thiol-terminated polythioethers provided by the present application represent thiol-terminated polythioethers having a molecular weight distribution. In certain embodiments, the thiol-terminated polythioether useful in the composition may exhibit a number average molecular weight of from 500 daltons to 20,000 daltons, in certain embodiments from 2,000 daltons to 5,000 daltons, and in certain embodiments from 3,000 daltons to 4,000 daltons. In certain embodiments, useful thiol in the compositions provided by the present - in the terminated polythioether emitter 1 to 20, certain embodiments a polydispersity of 1 to 5 degrees (M _w / M _n; weight-average molecular weight / number average molecular weight ). The molecular weight distribution of thiol-terminated polythioethers can be characterized by gel permeation chromatography.

The curable composition may further comprise a curing agent. The composition may further comprise additives, catalysts, fillers and / or other sulfur-containing prepolymers such as polythioether, sulfur-containing polyfoam and / or polysulfide.

Suitable curing agents are selected to be reactive with the bis (sulfonyl) alkanol-containing polythioether and the optional end groups of the sulfur-containing prepolymer.

In certain embodiments wherein the bis (sulfonyl) alkanol-containing polythioether or prepolymer thereof is terminated with a thiol group, a suitable curing agent is a polyepoxide. Examples of suitable polyepoxides include, for example, polyepoxide resins such as hydantine diepoxide, diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, Novolac ) Type epoxides such as DEN (TM) 438 (Dow Chemical Company), certain epoxidized unsaturated resins, and any combination thereof. A polyepoxide refers to a compound having two or more reactive epoxy groups. In certain embodiments, the epoxy curing agent is selected from EPON (TM) 828 (Momentive Specialty Chemicals, Inc.), DEN (TM) 431 (Dow Chemical Company), and combinations thereof. An example of a useful curing agent that is reactive with a thiol group includes a diepoxide.

Other examples of useful curing agents that are reactive with the terminal epoxy groups include amines such as diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), diethylaminopropylamine (DEAPA) Aminoethylpiperazine (N-AEP), isophoronediamine (IPDA), m-xylenediamine, diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS); Aromatic amine, ketimine; Polyamines; Polyamide; Phenolic resin; Anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endo Methylene tetrahydrophthalic anhydride; Polymercaptans; Polysulfide; And other curing agents known to those skilled in the art.

In certain embodiments, the polyepoxy curing agent comprises an epoxy-functional polymer. Examples of suitable epoxy-functional polymers include the epoxy-functional sulfur-containing polyfoam polymers disclosed in U.S. Patent Application No. 13 / 050,988 and the epoxy-functional polythioether polymers disclosed in U.S. Patent No. 7,671,145. Generally, when used as a curing agent, the epoxy-functional polymer has a molecular weight of less than about 2,000 daltons, less than about 1,500 daltons, less than about 1,000 daltons, and in certain embodiments less than about 500 daltons.

In certain embodiments, the polyepoxy comprises from about 0.5% to about 20%, from about 1% to about 10%, from about 2% to about 8%, from about 2% to about 6% In certain embodiments, it may comprise from about 3% to about 5% by weight, wherein the% by weight is based on the total solids weight of the composition.

In certain embodiments in which the bis (sulfonyl) alkanol-containing polythioether or prepolymer is terminated with a thiol group, suitable curing agents include unsaturated compounds such as acrylic or methacrylic esters of unsaturated compounds such as polyols, unsaturated synthetic or natural resin compounds, Triallyl cyanurate, and sulfur-containing compounds such as olefin-terminated derivatives of polythioether.

In certain embodiments where, for example, amines and / or hydroxyl-terminated bis (sulfonyl) alkanol-containing polythioethers or prepolymers thereof are used, the compositions provided herein can be prepared by reacting an isocyanate curing agent, An isocyanate and / or a triisocyanate curing agent. Examples of suitable isocyanate curing agents include toluene diisocyanate and any combination thereof. Isocyanate hardeners are commercially available and are commercially available under the trade names Baydur® (Bayer MaterialScience), Desmodur® (Bayer MaterialScience), Solubond® (DSM), ECCO (ECCO), Vestanat® (Evonik), Irodur® (Huntsman), Rhodocoat® (Perstorp) and Vanchem® (VT Vanderbilt). In certain embodiments, the polyisocyanate curing agent comprises an isocyanate group that is reactive with the thiol group and less reactive with the Michael acceptor group. Examples of useful curing agents that are reactive with amine groups include polymeric polyisocyanates, non-limiting examples of which include urethane linkages (-NH-C (O) -O-), thiourethane linkages (-NH-C (-NH-C (S) -S-), a thiocarbamate linking group (-NH-C (S) -O-), a dithiourethane linking group Based on the total weight of the polyisocyanate.

In certain embodiments, the isocyanate curing agent comprises an isocyanate-functional polymer. Examples of suitable isocyanate-functional polymers include the isocyanate-functional sulfur-containing polyfoam polymers disclosed in U.S. Patent Application No. 13 / 051,002. Generally, when used as a curing agent, the isocyanate-functional polymer has a molecular weight of less than about 2,000 daltons, less than about 1,500 daltons, less than about 1,000 daltons, and in certain embodiments, less than about 500 daltons.

In such a composition, the isocyanate curing agent may be present in an amount of from about 0.5% to about 20%, from about 1% to about 10%, from about 2% to about 8%, from about 2% to about 6% In certain embodiments, it may comprise from about 3% to about 5% by weight, wherein the% by weight is based on the total solids weight of the composition.

In certain embodiments, such as where an isocyanate-terminated bis (sulfonyl) alkanol-containing polythioether or prepolymer thereof is used, the compositions provided herein comprise an amine curing agent. Examples of useful curing agents that are reactive with isocyanate groups include diamines, polyamines, polythiols, and polyols, including those disclosed herein.

In certain embodiments, such as where a Michael acceptor-terminated bis (sulfonyl) alkanol-containing polythioether or a prepolymer thereof is used, the compositions provided herein may be formulated with monomeric thiols, polythiols, polyamines, ≪ / RTI > polyamines.

Curing agents useful in the compositions provided herein include compounds that are reactive with the terminal groups of bis (sulfonyl) alkanol-containing polythioethers such as hydroxyl, alkenyl, epoxy, thiol, amine or isocyanate groups Reactive < / RTI >

Examples of useful curing agents that are reactive with hydroxyl groups include diisocyanates and polyisocyanates, examples of which are disclosed herein.

Examples of useful curing agents that are reactive with alkenyl groups include dithiol and polythiol, examples of which are disclosed herein.

The polyalkoxysilyl-terminated bis (sulfonyl) alkanol-containing polythioethers provided herein can be hydrolyzed in the presence of water to induce self-polymerization through condensation. Catalysts for use with polyalkoxysilyl-terminated bis (sulfonyl) alkanol-containing polythioethers include organotitanium compounds such as tetraisopropoxytitanium, tetra-tert-butoxytitanium, titanium di Isopropoxy) bis (ethylacetoacetate) and titanium di (isopropoxy) bis (acetylacetoacetate); Organotin compounds such as dibutyl tin dilaurate, dibutyl tin bis acetylacetoacetate and tin octylate; Metal dicarboxylates such as lead dioctylate; Organo-zirconium compounds such as zirconium tetraacetylacetonate; And organoaluminum compounds such as aluminum triacetyl-acetonate. Other examples of catalysts suitable for moisture curing include diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetonate) titanium and dibutoxy titanium (methyl acetoacetonate) titanium. Since the curing agent for the polyalkoxysilyl-terminated bis (sulfonyl) alkanol-containing polythioether may be atmospheric moisture, the polyalkoxysilyl-terminated bis (sulfonyl) alkanol-containing polythioether- It can be seen that it is not necessary to include a curing agent in the curable composition. Thus, a composition comprising a polyalkoxysilyl-terminated bis (sulfonyl) alkanol-containing polythioether and a curing agent for a polyalkoxysilyl group refers to atmospheric moisture.

The compositions provided herein contain a stoichiometric amount of a predetermined curing agent in a stoichiometric amount of from about 90% to about 150%, from about 95% to about 125%, in certain embodiments from about 95% to about 105% can do.

Additional sulfur-containing polymers

In certain embodiments, the compositions provided herein comprise a reaction product of a bis (sulfonyl) alkanol-containing polythioether or prepolymer thereof, or any of the reactants disclosed herein, or any combination thereof, At least one additional sulfur-containing polymer. The sulfur-containing polymer may be any polymer having at least one sulfur atom in the repeat unit and may be, for example, a polymeric thiol, a polythiol, a thioether, a polythioether, a sulfur-containing polyfoam and a polysulfide But are not limited to these. As used herein, "thiol" refers to a compound comprising a thiol or mercaptan group, i.e., a "SH" group, with or without other functional groups such as hydroxyl groups as in the case of thioglycerols. The polythiol refers to a compound having at least one SH group such as a dithiol or higher functional thiol. These groups are typically terminals and / or pendants that have active hydrogens that are reactive with other functional groups. The polythiol may comprise both terminal and / or pendant sulfur (-SH) and non-reactive sulfur atoms (-S- or -S-S-). Thus, the term polythiol generally includes polythioethers and polysulfides.

Examples of additional sulfur-containing polymers useful in the compositions provided herein include those disclosed, for example, in U.S. Patent Nos. 6,172,179, 6,509,418 and 7,009,032. In certain embodiments, the composition provided herein comprises a polythioether having the structure of formula (29): < EMI ID =

- R ¹ - [- S - (CH ₂ ) ₂ --O - [- R ² --O--] _m - (CH ₂ ) ₂ --SR ¹ -] _n -

In this formula,

R ¹ is C _{2 -6} alkanoic die yl, C _{6 -8} cycloalkyl alkane die yl, C _{6 -10} cyclo alkane alkane di _{one, - [(- CH 2 -} ) s -X-] q - (- CH 2 - ) _r - and - (- CH ₂ -) _s - X -] _q - (- CH ₂ -) _r -, wherein one or more --CH ₂ - units are substituted with methyl groups; R ² is C _{2 -6} alkanoic die yl, _-8 C ₆ cycloalkyl alkane die yl, C _{6 -10} cyclo alkane alkane die work, and _{- [(- CH 2 -)} s -X-] q - (- CH 2 -) _r -; X is O, S, -NR ⁵ - is selected from (wherein R ⁵ is selected from hydrogen and methyl); m is an integer from 0 to 10; n is an integer from 1 to 60; p is an integer from 2 to 6; q is an integer from 1 to 5; r is an integer of 2 to 10;

Such polythioethers are described in U.S. Patent No. 6,172,179, column 2, line 29 to column 4, line 34.

The one or more additional sulfur-containing polymers may be bifunctional or multifunctional, for example with 3 to 6 terminal groups or mixtures thereof.

In certain embodiments, the compositions provided herein comprise from about 10% to about 90% by weight of the sulfur-containing polymer provided herein, from about 20% to about 80%, from about 30% to about 70% In certain embodiments, the composition comprises from about 40 wt% to about 60 wt% sulfur-containing polymer, wherein the wt% is based on the total weight (i.e., dry weight) of all non-volatile components of the composition.

As used herein, the term polysulfide refers to a polymer containing at least one sulfide linkage at the polymer backbone and / or pendant positions on the polymer chain, i.e., -Sx- (where x is 2 to 4) linking groups. In certain embodiments, the polysulfide polymer has two or more sulfur-sulfur linkages. Suitable polysulfides are commercially available, for example, under the trade names Thiokol-LP and Thioplast® from Akzo Nobel and Toray Fine Chemicals. Thioplast products are available in a wide range of molecular weights, for example from less than 1,100 to more than 8,000, wherein the molecular weight is the average molecular weight (g / mole). In some cases, the polysulfide has a number average molecular weight of from 1,000 daltons to 4,000 daltons. The crosslinking density of these products also depends on the amount of crosslinking agent used. The -SH content, i. E. The thiol or mercaptan content, of these products may also vary. The mercaptan content and molecular weight of the polysulfide can affect the curing rate of the polymer, which increases as the molecular weight increases.

Sulfur-containing polyfoam prepolymers useful in aerospace sealant applications are disclosed, for example, in U.S. Patent Application Publication No. 2012/0234205 and U.S. Patent Application Publication No. 2012/0238707.

In certain embodiments, the sulfur-containing polymer is selected from polythioethers and polysulfides, and the like. In certain embodiments, the sulfur-containing polymer comprises a polythioether, and in certain embodiments, the sulfur-containing polymer comprises a polysulfide. The sulfur-containing polymer may comprise a mixture of different polythioethers and / or polysulfides, and the polythioether and / or polysulfide may have the same or different functionality. In certain embodiments, the sulfur-containing polymer has an average functionality of from 2 to 6, from 2 to 4, from 2 to 3, and in certain embodiments, from 2.05 to 2.5. For example, the sulfur-containing polymer may be selected from bifunctional sulfur-containing polymers, trifunctional sulfur-containing polymers, and combinations thereof.

A curing agent which is reactive with the end groups of the sulfur-containing polymer and the sulfur-containing compound can be selected. In certain embodiments, the sulfur-containing polymer and the sulfur-containing compound provided herein comprise the same group that is reactive with the curing agent. For example, in certain embodiments, both the sulfur-containing polymer and the sulfur-containing compound provided by the invention comprise a reactive thiol group and the curing agent is a reactive alkenyl group, an epoxy group, an isocyanate group, a Michael acceptor group, Include groups containing saturated carbons having a suitable leaving group such as -Cl, -Br, -I, -OSO ₂ CH ₃ (mesylate), -OSO ₂ -C ₆ H ₄ -CH ₃ (tosylate) do.

In certain embodiments, the copolymerizable adhesion promoting adduct provided by the present invention comprises from 0.1% to 15%, less than 5%, less than 2%, and in certain embodiments less than 1% by weight, based on the total dry weight of the composition, ≪ / RTI >

The compositions provided herein may comprise one or more catalysts. The catalyst may be selected as appropriate for the curing chemistry used. In certain embodiments, for example, in the thiol-terminated bis (sulfonyl) alkanol-containing polythioether or prepolymer and polyepoxide cure, the catalyst is an amine catalyst. The curing catalyst may be present in an amount of from 0.1 to 5% by weight, based on the total weight of the composition. Examples of suitable catalysts include 1,4-diazabicyclo [2.2.2] octane (commercially available from DABCO®, Air Products chemical division, Allentown, PA) and DMP-30 (Accelerator composition comprising 2,4,6-tris (dimethylaminomethyl) phenol).

In certain embodiments, the compositions provided herein comprise one or more adhesion promoters. The one or more additional adhesion promoters may be present in an amount of from 0.1 wt% to 15 wt%, less than 5 wt%, less than 2 wt%, and in certain embodiments less than 1 wt% of the composition, based on the total dry weight of the composition . Examples of adhesion promoters are phenolic based, for example, Methylon (R) phenolic resins and organosilanes such as epoxy, mercapto or amino functional silanes such as Silquest (R) A-187 and Silquest A-1100 < / RTI > Other useful adhesion promoters are known in the art.

In certain embodiments, the composition provided herein comprises an ethylenically unsaturated silane, such as, for example, a sulfur-containing ethylenically unsaturated silane, wherein the ethylenically unsaturated silane improves the adhesion of the cured sealant to the metal substrate can do. As used herein, the term "sulfur-containing ethylenically unsaturated silane" refers to a silane having at least one sulfur (S) atom in the molecule, (ii) at least one, in some cases at least two ethylenically unsaturated carbon- (Iii) at least one silane group -Si (-R) _m (-OR) _3-m , wherein each R is independently selected from the group consisting of hydrogen, Alkyl, cycloalkyl, aryl, and the like, and m is selected from 0, 1, and 2. Examples of ethylenically unsaturated silanes are disclosed in U.S. Patent Publication No. 2012/0040104, the entirety of which is incorporated herein by reference.

In certain embodiments, the compositions provided herein can be cured using actinic radiation. An example of a composition comprising a polythioether composition that can be cured using actinic radiation is disclosed in U.S. Patent Publication No. 2012/0040104. Such compositions include polyenes such as polyvinyl ethers, including, for example, polyvinyl ethers of formula (27), one or more sulfur-containing polymers such as thiol-terminated sulfur-containing polymers in addition to the adhesion promoting adducts provided by the present application.

In certain embodiments, the compositions provided herein comprise one or more curing agents, such as epoxies, isocyanates, and combinations thereof.

The compositions provided herein may comprise one or more catalysts.

The compositions provided herein may comprise one or more different types of fillers. Suitable fillers include carbon black and inorganic fillers such as calcium carbonate (CaCO ₃ ), silica, polymer powders and lightweight fillers, which are conventionally known in the art. Suitable lightweight fillers include those described, for example, in U.S. Patent No. 6,525,168. In certain embodiments, the composition comprises from 5 wt% to 60 wt%, from 10 wt% to 50 wt%, and in certain embodiments from 20 wt% to 40 wt% of a combination of fillers or fillers, based on the total dry weight of the composition do. The compositions provided herein may additionally comprise one or more coloring agents, thixotropic agents, accelerators, flame retardants, adhesion promoters, solvents, masking agents or any combination thereof. As can be appreciated, these fillers and additives can be selected so that the fillers and additives used in the composition are compatible with each other as well as with the polymer components, curing agents and / or catalysts.

In certain embodiments, the compositions provided herein comprise low density filler particles. As used herein, a low density (when used in connection with a particle) means that the particle has a specific gravity of 0.7 or less, in certain embodiments 0.25 or less, and in certain embodiments 0.1 or less. Suitable lightweight filler particles often fall into two categories: microspheres and amorphous particles. Microspheres portion may from 0.1 to 0.7 days, for example polystyrene foam, polyacrylate, and microspheres of a polyolefin, and a sphere 5 to silica smile having a particle size and 0.25 weight of 100μ [Eco Spears (Eccospheres) ^®] . Other examples include alumina / silica microspheres (Fillite < ( ^R ) > having a particle size of 5 to 300 microns and a specific gravity of 0.7, aluminum silicate microspheres with a specific gravity of about 0.45 to about 0.7 ) ^®], the calcium carbonate having a specific gravity of 0.13-coated polyvinylidene copolymer microspheres [dual Light (Dualite) ^® 6001AE], and calcium carbonate having an average particle size and density of 0.135g / cc to approximately 40㎛ obtain the nitrile copolymer smile coated acrylate and a (dual Light ^® E135) [Canada only (Henkel)]. Fillers suitable for reducing the specific gravity of the composition include hollow microspheres such as, for example, Expancel ^占 microspheres (available from AcroNobel) or DualLight ^占 low density polymer microspheres (available from Henkel). In certain embodiments, the composition provided herein is a lightweight composition comprising an outer surface coated with a thin coating, such as those described in paragraphs [0016] to [0052] of U.S. Patent Publication No. 2010/0041839, Filler particles.

In certain embodiments, the low density filler comprises less than 2 wt%, less than 1.5 wt%, less than 1.0 wt%, less than 0.8 wt%, less than 0.75 wt%, less than 0.7 wt%, and in certain embodiments less than 0.5 wt% , Where the wt% is based on the total dry solids weight of the composition.

In certain embodiments, the compositions provided herein comprise one or more fillers effective to reduce the specific gravity of the composition. In certain embodiments, the specific gravity of the composition is 0.8 to 1, 0.7 to 0.9, 0.75 to 0.85, and in certain embodiments 0.8. In certain embodiments, the specific gravity of the composition is less than about 0.9, less than about 0.8, less than about 0.75, less than about 0.7, less than about 0.65, less than about 0.6, in certain embodiments less than about 0.55.

In certain embodiments, the thiol-terminated sulfur-containing polymer comprising a combination of thiol-terminated sulfur-containing polymers comprises from about 50% to about 90%, from about 60% to about 90% From about 70 wt% to about 90 wt%, and in certain embodiments from about 80 wt% to about 90 wt%, wherein the wt% is based on the total dry solids weight of the composition.

In certain embodiments, the thiol-terminated polythioether comprising a combination of thiol-terminated polythioethers comprises from about 50% to about 90%, from about 60% to about 90%, from about 70% Wt% to about 90 wt%, and in certain embodiments, from about 80 wt% to about 90 wt%, wherein the wt% is based on the total dry solids weight of the composition.

The composition may also include any number of additives desired. Examples of suitable additives include plasticizers, pigments, surfactants, adhesion promoters, thixotropic agents, flame retardants, masking agents and accelerators (such as 1,4-diaza-bicyclo [2.2.2] octane, DABCO Amine), and any combination thereof. If used, the additive may be present in the composition in an amount of, for example, from about 0% to 60% by weight. In certain embodiments, the additive may be present in the composition in an amount from about 25% to about 60% by weight.

Usage

The compositions provided herein can be used, for example, in sealants, coatings, encapsulating agents and potting compositions. The sealant comprises a composition capable of withstanding the operating conditions such as moisture and temperature and producing a film having the ability to at least partially block the permeation of water, fuel and other liquid and gaseous materials. The coating composition includes a shell applied to the surface of the substrate to improve the properties of the substrate such as, for example, appearance, adhesion, wettability, corrosion resistance, abrasion resistance, fuel resistance and / or abrasion resistance. Potting compositions include materials useful in electronic assemblies to provide resistance to shock and vibration and to eliminate moisture and corrosive agents. In certain embodiments, the sealant compositions provided herein are useful, for example, as aerospace sealants and as lining for fuel tanks.

In certain embodiments, a composition, such as a sealant, may be provided as a multi-pack composition such as a two-pack composition wherein one package comprises one or more thiol-terminated polythioethers provided by the present application The second package comprises at least one multifunctional sulfur-containing epoxy provided by the present application. Additives and / or other materials may be added to any one package as desired or as required. Both packages can be combined and mixed before use. In certain embodiments, the shelf life of one or more mixed thiol-terminated polythioether and epoxy is greater than 30 minutes, greater than 1 hour, greater than 2 hours, and in certain embodiments greater than 2 hours, Refers to the time that the mixed composition remains in a state suitable for use as a sealant after mixing.

The composition comprising the sealant provided herein can be applied to any of a variety of substrates. Examples of substrates onto which the composition can be applied include metals such as titanium, stainless steel and aluminum, which can be anodized, primed, organic-coated or chromate-coated; Epoxy; urethane; black smoke; Glass fiber composites; Kevlar (Kevlar) ^®; acryl; And polycarbonate. In certain embodiments, the composition provided herein can be applied to a coating on a substrate, such as a polyurethane coating.

By any suitable coating method known to those skilled in the art, the composition provided herein can be applied directly to the surface of the substrate or onto the underlying layer.

Also provided is an opening sealing method using the composition provided by the present application. The method includes, for example, applying the composition provided herein to a surface to seal the opening and cure the composition. In certain embodiments, the method of sealing an opening includes applying the sealant provided by the present application to the defining surface of the opening and curing the sealant to provide a sealed opening.

In certain embodiments, the composition can be cured under ambient conditions, wherein ambient conditions refer to a temperature of 20 ° C to 25 ° C and ambient humidity. In certain embodiments, the composition can be cured under conditions that include a temperature of 0 ° C to 100 ° C and a humidity of 0% relative humidity to 100% relative humidity. In certain embodiments, the composition can be cured at a high temperature above 50 C, in certain embodiments above 30 C, above 40 C. In certain embodiments, the composition may be cured at room temperature, e.g., 25 < 0 > C. In certain embodiments, the composition can be cured upon exposure to actinic radiation, e.g., ultraviolet light. As can be seen, the method can be used to seal openings on aerospace vehicles, including aircraft and aerospace vehicles.

In certain embodiments, the composition is non-sticky at a temperature of less than about 2 hours, less than about 4 hours, less than about 6 hours, less than about 8 hours, in certain embodiments, less than about 10 hours, tack-free curing.

The time for forming an effective seal using the present curable compositions may vary depending on several factors, as will be appreciated by those skilled in the art and as defined by the conditions of applicable standards and specifications. Generally, the curable composition of the present invention exhibits adhesive strength within 24 hours to 30 hours, and 90% of the total adhesive strength is expressed in 2 to 3 days after mixing and applying to the surface. In general, the total adhesive strength and other properties of the cured compositions herein are fully expressed within 7 days of application of the curable composition to the surface.

Cured compositions such as the cured sealants disclosed herein exhibit acceptable properties for use in aerospace applications. In general, it is preferred that the sealants used in aerospace and aerospace applications exhibit the following properties: AMS 3265B, which is immersed in JRF Type I for 7 days, then immersed in 3% NaCl solution, Abrasion strength greater than 20 pounds per linear inch (pli) on Aerospace Material Specification (AMS) 3265B substrate; A tensile strength of 300 pounds per square inch (psi) to 400 psi; Tear strength greater than 50 pounds per linear inch (pli); Elongation of 250% magma 300%; And a durometer greater than 40 durometer A. These and other cured sealant properties suitable for aviation and aerospace applications are disclosed in AMS 3265B, which is incorporated herein by reference. It is also preferred that the cured compositions herein used for aviation and aircraft applications exhibit a% volume swell of less than 25% after being immersed in JRF Type I for one week at 60 캜 (140)) and ambient pressure. Other properties, ranges and / or thresholds may be appropriate for other sealant applications.

Thus, in certain embodiments, the composition provided herein is fuel-resistant. As used herein, the term "fuel resistance" is intended to mean that when the composition is applied to a substrate and then cured, the composition is as described in ASTM D792 (American Society for Testing and Materials) or AMS 3269 Less than 40%, in some cases less than 25%, in some cases less than 20%, after immersion for one week in a Jet Reference Fluid (JRF) Type 1 at 140 ° F (60 ° C) (E. G., A sealant) that otherwise exhibits a percent volume swell of less than or equal to 10%. The jet reference fluid JRF type 1 used to determine the fuel resistance has the following composition: toluene: 28% ± 1% by volume; Cyclohexane (technical grade): 34% ± 1% by volume; Isooctane: 38% ± 1% by volume; And tertiary dibutyl disulfide: 1% ± 0.005% by volume [AMS 2629, available from the Society of Automotive Engineers (SAE), published July 1, 1989, § 3.1.1. Etc].

In certain embodiments, the composition provided herein is a cured product that exhibits a tensile elongation of at least 100% and a tensile strength of at least 400 psi when measured according to the procedure set forth in AMS 3279, § 3.3.17.1, test procedure AS5127 / 1, For example, a sealant).

In certain embodiments, the composition exhibits superimposed shear strength greater than 200 psi, such as greater than 220 psi, greater than 250 psi, and in some cases greater than 400 psi, as measured according to the procedure set forth in paragraph 7.8 of SAE AS5127 / 1 To provide a cured product (e.g., a sealant).

In certain embodiments, the cured sealant comprising the composition provided herein meets or exceeds the requirements for the aerospace sealant described in AMS 3277.

Also disclosed is an aperture comprising an aperture of an aerospace vehicle sealed with the composition provided by the present application.

In certain embodiments, the cured sealant provided herein exhibits the following properties upon curing at room temperature for 2 days, at 140 ° F for 1 day, and at 200 ° F for 1 day: anhydrous hardness of 49, 428 psi Tensile strength and elongation at 266%; And JRF Type I after 7 days, a hardness of 36, a tensile strength of 312 psi and an elongation of 247%.

In certain embodiments, the composition provided herein comprises a Shore A hardness (after 7-day cure) of greater than 10, greater than 20, greater than 30, in certain embodiments greater than 40; Greater than 10 psi, greater than 100 psi, greater than 200 psi, in certain embodiments, greater than 500 psi; Greater than 100%, greater than 200%, greater than 500%, in certain embodiments, greater than 1,000% elongation; And a swelling rate after exposure to JRF type I (7 days) of less than 20%.

Example

Additional embodiments are provided herein by reference to the following examples which describe the synthesis, nature, and use of certain sulfur-compounds and compositions including such adhesion promoting adducts. Those skilled in the art will recognize that many modifications may be made to the materials and methods without departing from the scope of the invention. In the following examples, Permapol P3.1E is a thiol-terminated polymer and Accelerator S-5304 is an epoxy compound, both of which are commercially available from Pialis-Desoto International Inc., Shilma, California Do. The Dacco 33-LV is an amine catalyst commercially available from Air Products and Chemcals, Inc.

Example  One

Thread Quest  A-1120 and 2- ( Methacryloyloxy )ethyl Of acetoacetate (2-MEAA)  Adhesion promoting adjunct

Silquest A-1120 (1 mole, 222.36 g) and ethanol were charged into a 50 mL three-neck round bottom flask. The flask was flushed with nitrogen and attached with an addition funnel and thermometer. 2- (Methacryloyloxy) ethylacetoacetate (2-MEAA, 1 mole, 214.11 g) and ethanol were charged to a 50-mL additional funnel. 1,8-Diazabicycloundec-7-ene (DBU) (0.027 g; one drop from a regular plastic pipette) was added to the silane. 2-MEAA solution was added dropwise over 2.75 hours and the mixture was stirred for 3 days. The product was used as a 50% solution in ethanol. The reactants are outlined in Table 1 below.

A sealant (sealant 1) having the composition shown in Table 1 below was prepared.

Amount (g) Permapol P3.1E Polymer 10.00 The aminosilane adhesion promoting adduct of Example 1 0.20 Calcium carbonate (CaCO ₃₎ 5.00 Accelerator S-5304 2.97 Dukko 33-LV 0.08

Permapor P3.1E and aminosilane adhesion promoting adduct (0.4 g of 50% aqueous solution) were weighed into the mixing cup and mixed in a Hauschild mixer for 30 seconds. Addition of CaC0 _3, and the mixture was mixed for 30 seconds. The contents were hand mixed and then mixed again in a Hauschild mixer for 30 seconds. Accelerator S-5304 was added, mixed by hand and mixed again in a Household mixer for 30 seconds. Catalyst Ack 33-LV (3 drops from a plastic pipette) was added and the contents were mixed. The cured sealant (24 hours at 140)) has a hardness of 35 (Shore A) and percent cohesive failure rates for the test surface are shown in Table 2 below.

Board Example  One
% Cohesive failure rate Chromic acid anodized aluminum 100% Sulfuric acid anodized aluminum 100% Mil-C-27725 100% Alodine® 1200 50% Titanium (according to AMS-4911 specification) 100% Bare aluminum 100% Bear Aluminum (Scotch-Brite®) 100%

Example  2

Thread Quest  A-1120 and Of benzoquinone (BQ)  Adhesion promoting adjunct

Benzoquinone (6.49 g) and ethanol (150 g) were placed in a 250-mL Erlenmeyer flask. While stirring, the contents were heated to dissolve the benzoquinone. After cooling to room temperature, Silkquest A-1120 (13.34 g) and ethanol (20 g) were placed in a 500-mL three-necked round bottom flask, flushed with nitrogen and charged with Polycat® DBU 0.081 g; 3 drops from a narrow pipette). The contents were allowed to react at room temperature for about 4 hours while stirring. The product was obtained in an amount of 13.7% by weight in the ethanol solution. The reactants are schematically shown in Fig.

A first sealant (sealant 1) having the composition of Table 3 below was prepared.

Ingredients - Sealant 1 Amount (g) Permapole 3.1E Polymer 10.00 The amino-hydroquinone adhesion promoting adduct of Example 2 0.20 Calcium carbonate (CaCO ₃₎ 5.00 Accelerator S-5304 3.09 Dukko 33-LV 0.08

The permapole 3.1E prepolymer and the amino-hydroquinone adhesion promoting adduct (1.46 g of about 14% solution) were weighed into a mixing cup and mixed in a Hauschild mixer for 30 seconds. The addition of CaC0 _3, and was mixed by hand in house child mixer. The accelerator S-5304 was added and mixed. The Catalyst Dacco 33-LV (3 drops from a plastic pipette) was added and mixed.

A second sealant (sealant 2) having the composition of Table 4 below was prepared.

Ingredients - Sealant 2 Amount (g) Ferma Paul P3.1E polymer 10.00 The amino-hydroquinone adhesion promoting adduct of Example 2 0.20 The aminosilane adhesion promoting adduct of Example 1 0.20 Calcium carbonate (CaCO ₃₎ 5.00 Accelerator S-5304 3.45 Dukko 33-LV 0.08

A mixture cup of Permapol P3.1E polymer, Example adduct (0.4 g of a 50% solution) and Example 2 adduct (1.46 g of about 14% solution) was weighed and hand mixed in a Household mixer for 30 seconds Respectively. CaC0 _3, S-5304, and catalyst promoter daepko the 33-LV (3 drops from a plastic pipette) was added and mixed in sequence.

The percent cohesive failure rates for the two cured sealant compositions (24 hours at 140 DEG F) on several surfaces are provided in Table 5 below. The hardness (Shore A) of the cured sealant was 39 and 25, respectively.

Board Example  2
(Sealant 1)
% Cohesive failure rate Example  2
(Sealant 2)
% Cohesive failure rate Chromic acid anodized aluminum 100% 100% Sulfuric acid anodized aluminum 100% 100% Mil-C-27725 100% 100% Alodin 1200 100% 100% Titanium (according to AMS-4901 standard, Scotch-Bright) 100% 100% Bare aluminum (cleaned solvent)) 100% 100% Bear Aluminum (Scotch-Bright) 100% 100%

Example  3

Thread Quest  A-189 and 1,3- Bis ( Vinyl sulfonyl )-2- Propanol  Adduct

Silquest A-189 and 1,3-bis (vinylsulfonyl) -2-propanol were reacted in the presence of DBU to provide corresponding adhesion promoting adducts.

A sealant having the composition of Table 6 below was prepared.

ingredient Amount (g) Permapol P3.1E Polymer 6.44 The aminosilane adhesion promoting adduct of Example 3 0.42 Calcium carbonate (CaCO ₃₎ 1.93 Accelerator S-5304 1.33 Dukko 33-LV 0.05

The adhesive specimens were cured at room temperature for 5 days and then cured at 140 ° F for 27 hours. The percent cohesive failure rates of the cured sealant samples are shown in Table 7 below.

surface Coagulation destruction rate (%) Bear aluminum
(Scotch-Bright) 100% Alodin 1200 100%

Comparative Example  One

(10 g, thiol-terminated polymer, commercially available from Phillips-DeSoto International, Inc., Shilma, Calif.) And calcium carbonate (5.0 g) at 2300 rpm for 30 seconds Lt; / RTI > in a Hauschild mixer. The accelerator S-5304 (2.6 g, epoxy paste, commercially available from Palsy-Desoto International Inc., Shilo, Calif.) And the catalyst triethylenediamine (0.08 g) were sequentially added and mixed. The samples were applied to various substrates and cured at room temperature for 24 hours and then cured at 140 ° F for 48 hours. The percent cohesive failure rate was measured by stripping the sample from the substrate. The results are shown in Table 8 below.

Board Comparative Example  One
% Cohesive failure rate Chromic acid anodized aluminum 0 Sulfuric acid anodized aluminum 0 Mil-C-27725 0 Alodin 1200 0 Titanium (according to AMS-4911 specification) 0 Bear aluminum 0 Bear Aluminum (Scotch-Bright) 0

Example  4

Density Functional Theory Calculation

Al ₄ O ₆ clusters representing the aluminum oxide surface of representative aerospace substrates (Li et al., "Structural determination of (Al ₂ O ₃ ) _n (n = 1-7) and Theoretical Chemistry 2012, 996, 125-131) and the Gibbs free energy of the interaction of various functional groups were calculated using the Density Function Theory (DFT) -based method. All structures were optimized using Gaussian 09 / B3LYP / 6-31 g (d) and the vibrational frequencies were calculated at the same level of theory, confirming that the structure was present at the local minimum. The energy in the water environment was calculated using single point energy calculation by the CPCM salvation method. The Gibbs free energy of the interaction was calculated under standard conditions of pressure and temperature (1 atm and 25 ° C) without correction.

Various functional groups were analyzed for these intrinsic properties including HOMO (highest occupied molecular orbital) energy, LUMO (lowest occupied molecular orbital) energy, and energy gap of HOMO and LUMO. Typically, functional groups with higher HOMO energies are more electronegative and those with lower LUMO energy are more electron accepting. Comparing the various functional groups in Table 9 below, 9,3-hydroxy-1,2-dimethylpyridin-4 (1H) -one (HOPO) has the highest HOMO energy, The highest. On the other hand, the functional group bis (sulfonyl) -2-propanol (BSP) has the lowest HOMO energy, indicating that the electron donor is the lowest.

Interactions between various functional groups and aluminum oxide clusters were measured. Vapor (ΔG _g), as well as calculating the Gibbs free energy of interaction of the water (ΔG _w), and the results are shown in Figure 3 with the contributions from the enthalpy (ΔH) of the reaction. In Fig. 3, the more negative value [Delta] G corresponds to a more stable complex or stronger interaction between the functional group and aluminum oxide. BSP and HOPO have stronger interactions with aluminum oxide than acetoacetate in simulated water environments as well as in meteorology. Acetoacetate binds to Al ₄ O ₆ through coordination by electron deficient aluminum (in Al ₄ O ₆ ) of electron rich carbonyl oxygen (in acetoacetate). HOPO interacts with Al ₄ O ₆ as a bidentate ligand. That is, the carbonyl oxygen (in HOPO) bonds with aluminum (in Al ₄ O ₆ ), and the hydroxyl group (in HOPO) is hydrogen bonded with oxygen (in Al ₄ O ₆ ). Three digits combining method of BSP and Al ₄ O ₆ is a hydroxyl group in addition to hydrogen bonding between (BSP medium) and oxygen atom (Al ₄ O ₆ in) 2-sulfonyl group (BSP of) two aluminum atoms (Al ₄ O ₆ ). ≪ / RTI > Although BSP is not a very strong electron donor (as can be seen by the low HOMO energies in Table 9), nevertheless strong binding with Al ₄ O ₆ with three coordination sites is observed.

In conclusion, the BSP functional group was found to cause very strong interactions (adhesion) in combination with aluminum oxide via the three-way method. Unlike other strong binding ligands, for example HOPO, BSP is expected to be difficult to oxidize and have excellent stability. Structures with binding motifs similar to BSP can also result in strong bonding to aluminum oxide.

Similar methods may be used to identify other metal ligands that are suitable for enhancing adhesion to a particular metal surface and which are incorporated into the backbone of the prepolymer as described herein and / or may be provided as the end group of the prepolymer.

Finally, it should be noted that there are other ways of implementing the embodiments disclosed herein. Accordingly, this embodiment is to be considered as illustrative rather than restrictive. Further, the claims are not limited to the detailed description given herein, but encompass the entire scope and equivalents thereof.

Claims (33)

An adhesion promoter adduct comprising an adhesion promoter and a metal ligand. The method according to claim 1,
An adhesion promoting adduct comprising a reactive functional group. The method according to claim 1,
Wherein the adhesion promoter comprises a polyalkoxysilyl, a phosphonate, an amine, a carboxylic acid and / or a phosphonic acid. The method according to claim 1,
An adhesion promoter comprising an adhesion promoter and a first functional group; And
A metal chelating agent comprising a metal ligand, and a second functional group reactive with the first functional group of the adhesion promoter,
≪ / RTI > and a reaction product of the reactants. 5. The method of claim 4,
Wherein the first functional group of the adhesion promoter comprises an alkenyl group, a thiol group and / or an amine group. 5. The method of claim 4,
Wherein the adhesion promoter comprises a thiol-terminated polyalkoxysilane. 5. The method of claim 4,
Wherein the adhesion promoter comprises a structure of formula (14a), a structure of formula (14b), a structure of formula (14c), or any combination thereof:

In this formula,
Each R ¹⁶ is independently selected from C _{1 -3} alkyl, each R ¹⁷ is selected from hydrogen and C _{1 -3} alkyl. 5. The method of claim 4,
Wherein the metal chelating agent comprises a bis (sulfonyl) alkanol, quinone, acetylacetonate, hydroxypyridine or any combination thereof. 5. The method of claim 4,
Wherein the adhesion promoter comprises an amino-terminated polyalkoxysilane and / or a thiol-terminated polyalkoxysilane;
Wherein the metal chelating agent comprises a bis (sulfonyl) alkanol, quinone, acetylacetonate and / or hydroxypyridinone. The method according to claim 1,
Wherein the metal ligand is a coordination complex with aluminum, Al (III), aluminum oxide, titanium, titanium oxide, anodized aluminum, Alodine (R), or any combination thereof. A group capable of forming an adhesion promoting adduct. The method according to claim 1,
Wherein the metal ligand is capable of forming a coordination complex with Al (III). The method according to claim 1,
Wherein the metal ligand comprises an aluminum oxide or Al (III) ligand and is selected from the group consisting of 2,3-dihydroxybenzoic acid, 5-nitrosalicylate, 3-hydroxy-4-pyridinone, N, N'-diacetic acid, pyruvic acid, pyruvic acid, pyruvic acid, pyruvic acid, pyruvic acid, pyruvic acid, (EDTA), N- (2-hydroxy) ethylenediaminetriacetic acid (HEDTA), ethylenediamine-N, N'-bis (2-hydroxyphenylacetic acid) Hydroxybenzyl) ethylenediamine-N, N'-diacetic acid (HBED), acetoacetate, quinone, and any combination thereof. The method according to claim 1,
Wherein the metal ligand comprises a titanium or titanium oxide ligand and is selected from the group consisting of H ₂ O ₂ , acetoacetonate (CH ₂ (COCH ₃ ) ₂ ), EDTA, trans-1, 2- cyclohexanediaminetetraacetic acid, glycol ethanediamine tetraacetic acid _{(GEDTA, (CH 2 OCH 2} CH 2 N (CH 2 COOH) 2) 2)), diethylene tri-amine penta acetic acid _{(DTPA, HOOCH 2 N (CH} 2 CH 2 N (CH 2 COOH) 2) 2 ), Nitrile triacetic acid (NTA, N (CH ₂ COOH) ₃ ), salicylic acid, lactic acid, acetylacetonate, triethanolamine and any combination thereof. The method according to claim 1,
Wherein the metal ligand comprises a structure selected from the following formula (12a), (12b), (12c), (12d), (12e), and any combination thereof:
_{-X- (CH 2) n -CH (} -OH) - (12a)
_{- X- (CH 2) n -CH} (-OH) - (CH 2) n -X- (12b)
-CH (-OH) - (CH ₂ ) _n -X- (CH ₂ ) _n -CH (-OH) - (12c)
-CH (-OH) -R < ⁵ > -CH (-OH) - (12d)
-C (O) -R < ⁵ > -C (O) - (12e)
In this formula,
Each X is independently selected from -C (O) - and -S (O) _2- ,
n is an integer of 1 to 3,
R ⁵ is a C _{1 -4} days alkane die. The method according to claim 1,
An adhesion promoting adduct comprising a structure of the following formula (16a), a structure of the following formula (16b), or a combination thereof:

In this formula,
Each R ¹⁶ is independently chosen from C _{1 -3} alkyl. The method according to claim 1,
An adhesion promoting adduct comprising a structure of formula (15): < EMI ID =

In this formula,
Each R ¹⁶ is independently chosen from C _{1 -3} alkyl. The method according to claim 1,
An adhesion promoting adduct having a structure represented by the following formula (13):
R ¹¹ -PR ^{12 '} -R ^13' -MR ¹⁴ (13)
In this formula,
R ¹¹ comprises an adhesion promoter;
P comprises a core of an adhesion promoter;
M comprises a metal ligand;
R ^{12 '} and R ^13' represent residues derived from the reaction of R ¹² and R ¹³ of the adhesion promoter R ¹¹ -PR ¹² and the metal chelating agent R ¹³ -MR ¹⁴ wherein R ¹² and R ¹³ are mutually reactive functional groups And R < ¹⁴ > is selected or absent from non-reactive groups and reactive functional groups. 18. The method of claim 17,
The adduct
An adhesion promoter of the formula R ¹¹ -PR ¹² ; And
Metal chelating agents of the formula R ¹³ -MR ¹⁴
≪ / RTI > and a reaction product of the reactants. 18. The method of claim 17,
Wherein P comprises a reactive functional group, or R ¹⁴ comprises a reactive functional group, or both P and R ¹⁴ comprise a reactive functional group. The method according to claim 1,
An adhesion promoting adduct of claim 1 comprising a first reactive functional group; And
A compound having a second reactive functional group which is reactive with the first reactive functional group
≪ RTI ID = 0.0 > a < / RTI > reaction product of the reaction product. 21. The method of claim 20,
Wherein the compound comprises a polyamine or a polythiol. The method according to claim 1,
Wherein the adduct comprises a polyaddition promoting adduct having a structure of formula (18): < EMI ID =
B (-V'-R ^{14 '} -MR ^13' -R ^{12 '} -PR ¹¹ ) _z (18)
In this formula,
R ¹¹ comprises an adhesion promoter;
P comprises a core of an adhesion promoter;
M comprises a metal ligand;
R ^{12 '} and R ^13' represent residues derived from the reaction of R ¹² and R ¹³ of the adhesion promoter R ¹¹ -PR ¹² and the metal chelating agent R ¹³ -MR ¹⁴ wherein R ¹² and R ¹³ are mutually reactive functional groups R ¹⁴ comprises a reactive functional group;
R ^{14 '} represents a residue derived from the reaction of R ¹⁴ and V;
B represents the core of z- the polyfunctionalizing agent B (-V) _z , where z is an integer from 3 to 6; Each -V is a group containing a group reactive with R < ¹⁴ >;
Each -V'- is derived from the reaction of -V with R < ^{14 &} gt ;. The method according to claim 1,
The adduct
(-V) _z , wherein B is the core of the polyfunctionalizing agent, z is an integer from 3 to 6, and each -V is a group comprising a first reactive functional group, issue; And
An adhesion promoter, an adhesion promoter comprising a metal ligand, and a second reactive functional group reactive with the first reactive functional group of the polyfunctionalizing agent
Wherein the adhesion promoter is a multi-functional adhesion promoter comprising a reaction product of reactants. The method according to claim 1,
Wherein the adduct is a copolymerizable adhesion promoting additive having a structure of the following formula (21):
B (-V^One'-R^{14 '}-M-R^{13 '}-R^{12 '}-P-R¹¹)_z1(-V²)_{z- z1} (21)
In this formula,
R¹¹Comprises an adhesion promoter;
P comprises a core of an adhesion promoter;
M comprises a metal ligand;
R^{12 '} And R^{13 '}The adhesion promoter R¹¹-P-R¹² And the metal chelating agent R¹³-M-R¹⁴Of R¹²And R¹³, Wherein R < RTI ID = 0.0 >¹² And R¹³Comprises an interacting functional group, and R¹⁴Lt; / RTI > comprises a reactive functional group;
B represents the core of the z- < RTI ID = 0.0 > polyfunctionalizing agent < / RTI &
B (-V^One)_z1(-V²)_{z- z1} (22)
In this formula,
z is an integer from 3 to 6;
z1 is an integer from 1 to z-1;
Each -V^OneIs a group comprising a first reactive functional group;
One or more -V²Comprises a second reactive functional group;
Each R^{14 '}R¹⁴And -V^OneLt; / RTI >;
Each -V^One'- is -V^OneAnd R¹⁴≪ / RTI > The method according to claim 1,
The adduct
A multifunctional agent of formula (22); And
An adhesion promoter, comprising an adhesion promoter, a metal ligand, and a third functional group reactive with the first reactive functional group
An adhesion promoting adduct comprising a reaction product of reactants comprising:
B (-V^One)_z1(-V²)_{z- z1} (22)
In this formula,
B < / RTI > is a polyfunctionalizing agent B (-V)_z≪ / RTI >
z is an integer from 3 to 6;
z1 is an integer from 1 to z-1;
Each -V^OneIs a group comprising a first reactive functional group;
One or more -V²Comprises a second reactive functional group. The method according to claim 1,
Wherein the adduct comprises a copolymerizable sulfur-containing adhesion promoting adduct of Formula (23): < EMI ID =
^{B (-V'-SR 1 -S- R} 14 '-MR 13' -R 12 '-PR 11) z1 (-V'-SR 1 -SH) z- z1 (23)
In this formula,
Each R ¹ is independently C _{2 -6} alkanoic die yl, C _{6 -8} cycloalkyl alkane die yl, C _{6 -10} alkane bicyclo alkane die yl, C _{5 -8} heterocycloalkyl alkane die work and - [- (CHR ³ ) _s- X-] _q- (CHR < ³ >) _r -
Each R < ³ > is independently selected from hydrogen and methyl;
Each X is independently selected from -O-, -S-, and -NR-, wherein R is selected from hydrogen and methyl;
s is an integer from 2 to 6;
q is an integer from 1 to 5;
r is an integer from 2 to 10;
R ¹¹ comprises an adhesion promoter;
P comprises a core of an adhesion promoter;
M comprises a metal ligand;
R ^{12 '} and R ^13' represent residues derived from the reaction of R ¹² and R ¹³ of the adhesion promoter R ¹¹ -PR ¹² and the metal chelating agent R ¹³ -MR ¹⁴ wherein R ¹² and R ¹³ are mutually reactive functional groups R ¹⁴ comprises a reactive functional group;
R ^{14 '} represents a residue derived from the reaction of R ¹⁴ with a thiol group;
B represents the core of z- the polyfunctionalizing agent B (-V) _z ;
z is an integer from 3 to 6;
z1 is an integer from 1 to z-1;
Each -V is a group comprising a group reactive with a thiol group;
Each -V'- is derived from the reaction of -V with a thiol group. The method according to claim 1,
The adduct
Dithiol;
A multifunctional agent comprising a functional group that is reactive with a thiol group; And
The adhesion promoting additive of claim 1 comprising a functional group that is reactive with the thiol group
Wherein the adhesion promoting adduct comprises a copolymerizable sulfur-containing adhesion promoting adduct which comprises the reaction product of reactants comprising a sulfur-containing adduct. A composition comprising the adhesion promoting adduct of claim 1. 29. The method of claim 28,
Wherein the composition comprises a sulfur-containing prepolymer. 30. The method of claim 29,
Wherein the sulfur-containing prepolymer is selected from the group consisting of a thiol-terminated polythioether prepolymer, a thiol-terminated polysulfide prepolymer, a thiol-terminated sulfur-containing polyphosphoric prepolymer, and a thiol- Wherein the composition comprises a terminated sulfur-containing prepolymer. 30. The method of claim 29,
Wherein the sulfur-containing prepolymer comprises a thiol-terminated polythioether prepolymer. 29. The method of claim 28,
A composition formulated as a sealant composition. A cured sealant formed from the sealant composition of claim 32.

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