HUT74320A - Carbonyl containing compounds - Google Patents

Abstract

The present invention relates to novel compounds produced from acyclic compounds containing carbonyl groups and unsaturated hydrocarbons which can be used to increase the viscosity of solutions. The compounds of the invention in the formula (I): Ra, Rfc, Εθ, E E and Εθ are each independently hydrogen, C1-CΙΟθ alkyl, or ΙΟθenenen alkenyl, which may be substituted with alkoxy, halogen, cyano, hydroxyl , ΗΟζΟΗ, ^ ΟΙ ^ Ο), acyl, acyloxy and / or aryl; and - X and Y are hydroxy, -OH is -OE- (C 1 -C 18) -alkyl, R 1 is C 1-18 -alkyl and R 2 is -NR- (C 1 -C 18 -alkyl); C1-8 alkyl, E2, hydrogen or C1-C18 alkyl, E1 and R6 are C1-C18 alkyl; , R 1 is -OR 1 or -C 1-8 alkyl;

Description

CARBONYLIC COMPOUNDS

Exxon Research and Engineering Company, Florham Park,

USA

Inventor:

BROIS Stanley, Westfield, USA

Date of filing: 03.12.1993

Priority: -

International Application Number: PCT / US93 / 12707

International Publication Number: WO 95/15303

Our file number is 83789-3102-tm

Our agent: dr. Palágyi T.

This invention relates to novel compounds prepared from acyclic compounds containing carbonyl groups and unsaturated hydrocarbons.

Various unsaturated hydrocarbon polymers have already been reacted with maleic anhydride to produce the maleic anhydride addition reaction products of those unsaturated hydrocarbon polymers, but there are many unsaturated hydrocarbon polymers for which maleic anhydride has only a low reactivity. An example of such a polymer is EPDM rubber, with which maleic anhydride does not react even when significant amounts of heat are supplied. Unlimited increases in thermal energy remain ineffective. Alternative solutions have so far been provided by free radical reactions that can be used to inoculate maleic acid onto unsaturated hydrocarbon polymers. In the case of free radical inoculation, chain breakage, crosslinking and, if the solvent used is sufficiently reactive, solvent inoculation occur. All of these disadvantages can be avoided by reacting acyclic compounds containing carbonyl groups with unsaturated hydrocarbon polymers. These acyclic monomers containing carbonyl groups can be reacted in bulk or in solution with unsaturated hydrocarbon polymers at moderate temperatures without the use of free radical initiators. As a reaction product, new polymers are formed which can be used to increase the viscosity of solutions.

In the novel compounds of formula I of the present invention, " ^E a ' ^R b' ^E c ' ^R d ^{and R} e' are independently hydrogen, C 1 -C 6 alkyl, C 3 -C 10 alkenyl, or a group of about 1 to about 10 carbon atoms. C 10 -C 10 substituted alkyl or about C 1 -C 6 substituted alkenyl substituted with alkoxy, halogen, cyano, hydroxy, HO (CH 8 CH 8 O) - x = 1-10, acyl, acyl. oxy and aryl groups; furthermore

X and I are hydroxy, -OR ^ is a radical of R 1 where R 1 is C 1 -C 18 alkyl, R 1 is C 1 -C 18 alkyl, and R 8 is hydrogen or

-NR 1 R 8 containing C 1 -C 18 alkyl, C 1 -C 18 alkyl, R 8 being hydrogen, or C 1 -C 18 alkyl having R 1 and R 6 being about 1 to 18 carbon atoms -NR ^ R ^ containing alkyl, R ^ is hydrogen or C 1-18 alkyl having -OR ^, Rg is hydrogen or C 1-18 alkyl, -GOOR g, cyano or R ? -SR ?? a group of the general formula.

The compounds of formula (I) are prepared by contacting the hydrocarbons of formula (II) for sufficient time and temperature to form one another - in formula (II), R _< 1 _& gt ;, R _< _c > ··· ······················································································· (··· és· és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és és ) X and Y are as defined above, Q is HOH, MeOH, EtOH or n-BuOH, and n is an integer greater than 0, 1 or 1.

Typical monomers include ketomalonic acid, esters of ketomalonic acid, including alkyl and aryl esters, other suitable two-carboxylic acids, such as alpha-ketobutyric acid, diketobuccinic acid, alpha-ketomonocarboxylic acids and alpha, beta-dicetocarboxylic acids, and esters and amides of acids having molecular weights of about 130-500. Suitable ketones are, for example, dimethyl, diphenyl and ditolyl triketones, as well as dimethyl, diphenyl and ditolyl tetraketones.

The compounds of the present invention may be used as agents for increasing the viscosity of solutions.

As mentioned above, compounds of formula I are prepared by contacting olefins and carbonyl-containing acyclic compounds at suitable temperatures for a sufficient period of time. A typical reaction for the preparation of new carbonyl-containing compounds is illustrated in Scheme 1, wherein

- E _& E ^, Εθ, E ^ and Εθ is - independently selected from hydrogen, about 1-10 ^ alkyl, alkenyl, or about 3-10θ is about l ΙΟθ carbon atoms substituted alkyl, or about 3 to 10 ⁶ C alk alk alk alkenyl substituted with alkoxy, halogen, cyano, hydroxy, HO (CH ^C ^O)

groups x-1-10 acyl groups, acyloxy groups and commodity groups;

- Q is HOH, MeOH, EtOH or n-BuOH;

- n is an integer equal to 0, 1 or more; furthermore

X and Y are hydroxy, R 1 is -OR- ^, wherein R 1 is C 1 -C 18 alkyl, R ₁ is C 1 -C 18 alkyl, and R ₂ is hydrogen, or

-NR 1 -R ₂ containing C 1 -C 18 alkyl, C 1 -C 18 alkyl, R _{2 being} hydrogen, or C 1 -C 18 alkyl having R 1 and R 1 being about 1 -NR ^ R ^ containing -C 18 alkyl, -OR ^ being optionally hydrogen or C 1 -C 18 alkyl, -COR ^ wherein R ^ is hydrogen or C 1 -C 18 alkyl, cyano or R? -SR containing from about 1 to about 18 carbon atoms in the alkyl group; a group of the general formula

Typical monomers include ketomalonic acid, esters of ketomalonic acid, including alkyl and aryl esters, other suitable two-carboxylic acids, such as alpha-succinic acid, diketobuccinic acid, alpha-ketomonocarboxylic acids and alpha, beta-diketocarboxylic acids, and their esters and amides of acids having a molecular weight of from about 50 to about 50,000. Suitable ketones are, for example, dimethyl, diphenyl and ditolyl triketones, as well as dimethyl, diphenyl and ditolyl tetraketones.

• · · ·

As olefin hydrocarbons, it is particularly preferred to use C 8 -C 5 alkenes and olefinic polymers having about 500 to 10,000,000 molecular weight allyl-type hydrogen atoms. The olefinic hydrocarbons may, of course, be substituted with functional groups and atoms such as cyano, hydroxy, ΟΒΟ ^ ΟΒΟ, Ο) - (x = 1-10), alkoxy, halogen, formula (c). a group of formula (d) containing a group W or CH or a nitrogen atom, a group of the formula (e) containing V, an oxygen atom, a sulfur atom or a SO2 group, a group of the formula (g) and X in the formula (f) R 1 is -OR ^ containing from about 1 to about 18 carbon atoms in the alkyl group, -NR ^ R ^ containing from 1 to about 18 carbon atoms, and from the radical R ^ in the case of hydrogen or from about 1 to about 18 carbon atoms; -C18 alkyl, hydrogen or about A radical of formula (a) having from 1 to 18 carbon atoms, a radical of formula -NR ^ R ^ having from about 1 to 18 carbon atoms in R ^ and R ^, containing a hydrogen atom or a alkyl group of from 1 to 18 carbon atoms in R R8 is -COORg, R3 is hydrogen or C1-C18 alkyl, cyano or R6 is hydrogen; -SR containing from about 1 to about 18 carbon atoms in the alkyl group; a group of the general formula.

Typical examples of substituted alkenes include oleic acid, oleyl alcohol, methyl oleate, 2-octadec

nyl succinic anhydride, octadecenylbenzene, octadecenylmethyl ketone, octadecenylphenylsulfide, octadecenylphenylsulfone, octadecenyl chloride, octadecenylphenol, butyl chloride, polyisobutenylsuccinic acid and the like, containing olefins and polyolefins.

Preferred polymers include EPDM polymers as well as butyl rubber. The term "butyl rubber" is used herein to refer to copolymers obtained by polymerization of reaction mixtures containing from 70 to 99.5% by weight of isobutylene and from about 0.5 to about 50 ng of C4-C14 conjugated multiolefin such as isoprene. The resulting copolymer contains from 85 to 98.8% by weight of isoolefin and 0.2 to 15 multiolefin.

The butyl rubbers usually have a molecular weight determined by Staudinger gel permeation chromatography of about 20,000-500,000, preferably about 25,000-400,000, and most preferably about 100,000-400,000, and a Wijs iodine number of about 0.5-50, preferably 1-15 · Butyl rubbers are disclosed in U.S. Patent No. 2,556,128. can be prepared as described in U.S. Pat. The material of this patent application is to be construed as reference text to supplement the description of the invention.

The butyl rubbers useful in the present invention comprise from about 0.2 to about 10% by weight, preferably from about 0.5 to about 6% by weight, more preferably from about 1 to about 4% by weight, such as 2%, of the multiolefin.

Examples of such butyl rubbers are Exxon butyl 565 (Exxon Chemical Company), which has about 2.0 molar unsaturation and about 40-50 Mooney viscosity (ML). · ···· ·· ····

1 + 3, 100 ° C).

By sulfonating low molecular weight butyl rubbers, for example, based on their viscosity, butyl rubbers having an average molecular weight of about 5,000-85,000 and about 1-5 mol% unsaturation, polymers that can be used in the practice of the invention are obtained. has a molecular weight of about 25,000 to about 60,000.

The terpolymers of SPDM are only slightly unsaturated polymers having ASTM-1418-64. s. The olefinic unsaturation determined according to the standard is about 0.5-10.0% by weight, preferably 2-8% by weight, more preferably 3-7% by weight. These are terpolymers which include a ethylene and propylene backbone and a double bond in the side chain as the multiolefin is incorporated into the backbone. Methods for preparing such terpolymers are described, for example, in U.S. Patent No. 3,280,082. U.S. Patent No. 1,030,289. British Patent Specification No. 1 3θ6,600; French Patent No. 4,268,198. The text of these descriptions is intended to be a reference for supplementing the description of the invention. It is preferred that the terpolymers include about 40-75 ethylene, about 1-10 wt% diene monomer, and propylene in an amount of about 100 wt%. It is preferable to use terpolymers which comprise about 45-70% by weight, for example 50% by weight, of ethylene and about 2.6-8.0% by weight, for example, 5.0% by weight of diene monomer. The diene monomer is preferably non-conjugated diene.

By way of example, some non-conjugated diene monomers which may be used in the preparation of EPDM terpolymers are listed: 1,4-hexadiene, dicyclopentadiene, 4-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-propenyl norbornene methyl tetrahydroindene and 4-methylmethylene-2-norbornene.

A typical EPDM rubber is Vistalon 2504, available from Exxon Chemical Company (Houston, Texas), which has a Mooney viscosity of about 40. (ML, 1 + 8, 100 ° C) terpolymer comprising about 50 ethylene and 5 5-ethylidene-2-norbornene. Vistalon 2504 has a number average molecular weight of about 47,000, gel permeation chromatography, viscosity average molecular weight of about 145,000, and also gel permeation chromatography of about 174,000.

Exxon Chemical Company also markets Vistalon 2504-20, another SPDM terpolymer produced from Vistalon 2504 by controlled extrusion, which results in a product having a Mooney viscosity of about 20 at 100 ° C. Vistalon 2504-20 has a number average molecular weight of about 26,000, gel permeation chromatography, viscosity average molecular weight of about 90,000, and also gel permeation chromatography of about 125,000.

Nordel 1520 is a terpolymer commercially available from Dupont that contains about 55 ethylene, about 5.5% 1,4-hexadiene, and about 45.5 propylene. This terpolymer has a Mooney viscosity of approximately 25 at 100 ° C.

EPDM Terpolymers of the Invention Numerical Mean Molecule by Gene Permeation Chromatography

- 10 - - ^; ···· · ♦ ··· ♦ has a mass (Μ) of about 10,000-200,000, preferably about 15,000-100,000, more preferably about 20,000-60,000. The Money Viscosity (ML) of the SPDM Terpolymer 1 + 8, 100 ° C) about 5-60, preferably about 10-50, more preferably about 15-40. Preferably, the viscosity average molecular weight of the SPDM terpolymer as determined by gel permeation chromatography is below about 550,000, more preferably below about 500,000. The SPDM terpolymer is preferably less than about 500,000, more preferably less than about 550,000, by weight permeation chromatography.

Also suitable are olefinic polymers having a number average molecular weight of about 500 to about 10 θ and having a predominant weight of 2 to 5 carbon atoms, such as ethylene, propylene, butylene, isobutylene and pentene, in the molar fraction. The polymers can be homopolymers such as polyisobutylene and copolymers consisting of two or more olefins such as ethylene / propylene, butylene / isobutylene, propylene / isobutylene and the like.

The carbonyl-containing compounds and the olefin-containing compounds are reacted in solution and melt, as well as in polymer processing equipment such as a rubber roller, Bra'bender, extruder or Banbury mixer.

The addition reactions of the double-bonded compounds can also be carried out in the presence of acidic catalysts such as kaolin, montmoriHonite, silicates, tin (IV) chloride, ferric chloride and boron trifluoride. Moreover, in the presence of acidic catalysts, lactones, secondary addition products, and cyclic ethers can also be formed, the amount of which depends on the reaction conditions, the catalyst and the type of reaction partner.

The reaction time and reaction temperature can vary over a very wide range and depend in part on the presence of a catalyst. The carbonyl-containing acyclic compound is usually contacted with the double bond compound in solution at about 50-220 ° C for about 4-40 hours.

Typically, the double bond compound is dissolved in a suitable solvent, such as tetrahydrofuran, xylene or mineral oil, and the resulting solution is heated to about 50-220 ° C. Subsequently, a hydrate of the carbonyl-containing compound or a half-dial with methanol, butanol or other appropriate alcohol is dissolved in a suitable solvent, such as tetrahydrofuran, dioxane or butanol, and the resulting solution is added to a heated solution of the double bond compound. The resulting reaction mixture is heated with stirring until it appears from the infrared and NME spectra of the sample taken from the mixture that the total amount of carbonyl-containing monomer has been added to the double bonds of the unsaturated polymer. Generally, depending on the reaction temperature and concentration, a reaction time of from 4 to 40 hours is sufficient to convert most of the starting materials into a reaction product formed by a single and / or multiple addition per molecule.

Alternatively, the reaction partners may be approx

The reaction is carried out at 80-200 ° C for 3 to 100 minutes depending on the polyolefin used, the reactivity of the carbonyl-containing compound and the use of the catalyst.

If necessary, the reaction products may be isolated by evaporation of the solvent or by adding a polar solvent, such as acetone, to the reaction mixture to cause precipitation of the polymer containing the functional groups.

The following examples are provided to illustrate the invention in more detail, but are not intended to be limiting.

Example 1

A mixture of 6.12 g of ketomalonate and 8.84 g of 1-octadecene was stirred at 160-170 ° C for 3 hours in a flask equipped with a magnetic stirrer. The temperature was then raised to 200 ° C and maintained at this temperature for 30 hours. The reaction mixture solidified on cooling. The mass spectrum of the solid recrystallized from diethyl ether showed a molecular ion (426) and the infrared spectrum showed a strong absorption band at 3 microns for a hydroxyl group and 5.82 microns for a very intense ester carbonyl group. The peaks in the CMR spectrum of the addition reaction product of the double bond compound are those of the olefins and the carbonyl group in the ester, consistent with the structure of the desired compound of formula (A).

Example 2

100 g of polyisobutylene, having a weight average molecular weight of 950, was mixed with 34.0 g of diethyl ketomalonate in a flask and the resulting mixture was heated to 200 ° C. magnetic stirrer for about 40 hours. The reaction mixture was kept in a rotary evaporator at about 100 ° C for 8 hours. The evaporation residue is characterized by (a) an intense absorption band at 5.85 microns in the infrared spectrum indicating an ester carbonyl group, and (b) a saponification number of 92.

3 «example

100 g of polyisobutylene succinic anhydride having an average molecular weight of 1050 and a saponification number of 55 were mixed with 17 g of diethyl ketomalonate and kept at about 200 ° C for 48 hours.

The reaction mixture was kept in a rotary evaporator at about 100 ° C for 8 hours. The resulting evaporation residue is characterized by an intense absorption band at 5.65 microns in the infrared spectrum and an intense absorption band at 5.85 microns in the ester carbonyl group.

EXAMPLE 4 A mixture of 9 grams of polyisobutylene having an average molecular weight of 950, 10 grams of maleic anhydride and 17.4 grams of diethyl ketomalonate was heated at about 210 ° C for 40 hours. The cooled reaction mixture was dissolved in 500 mL of cyclohexane and the solution was filtered and kept on a rotary evaporator at about 100 for 8 hours. The resulting evaporation residue is characterized by an infrared spectrum with an intense absorption band at 5.65 microns for anhydride and 5.85 microns for ester at 5.65 microns. an intense absorption band indicating the presence of a carbonyl group.

Example 5

In 100 ml of xylene containing 4 g of diethyl ketomalonate was dissolved 10 g of Vistalon-75C4, containing 55,000% of ethylene, 43% of propylene and 5% of ethylidene norbornene (ENB). is an average molecular weight SNB terpolymer. The resulting mixture was heated to 155 ° C under nitrogen and maintained at this temperature for 5θ hours. The cooled reaction mixture was added to 1 liter of acetone to precipitate the functionalized polymer from the solution. The dried polymer, which contains 5.04% oxygen, is characterized by having an intense band of 5.82 microns of carbonyl ester in the infrared spectrum of the film formed, which is in accordance with formula (B) for the addition reaction products of double bond compounds. with its illustrated structure.

Claims (8)

Claims CLAIMS 1. Compounds prepared by contacting hydrocarbons having R 1, R 1, R _c , R 4 and Βθ independently of one another for the formation of hydrogen in the formula (II) for a sufficient time and at a temperature. C 1 -C 10 alkyl, C 5 -C 1 -C 6 alkenyl, or C 1 -C 8 substituted alkyl, or C ⁵ -C 10 substituted alkenyl substituted with alkoxy, halogen, cyano, hydroxy, ΗΟζΟ The radicals of the formula - (x = 1-10) -, acyl groups, acyloxy groups and commodity groups; and acyclic compounds containing carbonyl groups of the formula (III) - Q is HOH, MeOH, EtOH or n-BuOH; - n is an integer greater than 0, 1 or 1; and - X and Y are hydroxy, -OR- ^ is a group containing from R 1 to C 1 -C 18 alkyl, R 1 is -C 1 -C 18 alkyl, and R 8 is hydrogen or from C 1 to C 18 -alkyl. R8 is a group of formula (a) having from about 1 to 18 carbon atoms, Rg from hydrogen or from C1 to C18 alkyl, from NR1 to R6 having from 1 to 18 carbon atoms in R8 and R6 alkyl group, R 1 is hydrogen or R 1 -C 18 -alkyl, ♦ ··· ·· · < • * • · 9 9 9 _ 16 _ .......... ♦ · ' Βθ is hydrogen or C 1 -C 18 alkyl having the formula -ΟΟΟΗθ, cyano or R? -SR ?? a group of the general formula. Compounds according to claim 1, which are prepared using C 8 -C 30 olefinic hydrocarbons. Compounds according to claim 1, which are prepared using olefinic polymers having an allylic type of hydrogen having a molecular weight of about 500 to 10,000,000. 4o. A compound according to claim 2 or J which is prepared using hydrocarbons substituted with a cyano group, a hydroxy group, a HOCCl (C 1 -C 4 O) - (x = 1-10) alkoxy group. , a halogen atom, a group of formula (b), a group of formula (c), a group of formula (cL) containing W is CH or a nitrogen atom, V is an atom of oxygen, sulfur or SO 4, (g) or a radical of formula (f) wherein X is hydroxy; -OR 1 - (C 1 -C 18) -alkyl, -R 1 - (C 1 -C 18) alkyl, -R 1 - (C 1 -C 18) -alkyl, (C 1 -C 18) alkyl, (C 1 -C 18) , R £ is hydrogen or · » - 17 having from about 1 to about 18 carbon atoms or a hydrogen having from about 1 to about 18 carbon atoms or from about 1 to about 18 carbon atoms having from about 1 to about 18 carbon atoms; -ΟΟΟΕθ, a cyano group, or -SE ₉ having a C 1 -C 18 alkyl group. The compound according to claim 2, which is prepared by contacting the starting materials in a solvent at about 50-220 ° C for about 4-40 hours. 6. A compound according to claim 5, which is prepared by contacting the starting materials at about 80-200 ° C for about 5 to 500 minutes. 7. A compound according to claim 5 or claim 6, which is prepared by contacting the starting materials in the presence of an acidic catalyst, 8- Compounds of formula (I) - E _& E ^, Εθ, E _d and Εθ is - independently selected from hydrogen, about 1-10 carbon atoms, 5-10 carbon atoms or is about l ΙΟθ carbon atoms substituted alkyl, illet18 - • * νν «· · ···· ·· · »· 4 · V • · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ve C 5 -C 10 substituted alkenyl substituted with alkoxy, halogen, cyano, hydroxy, (C 1 -C 4) -alkyl, acyl, acyloxy; groups and groups of goods; as well as X and Y are hydroxy; A group of the general formula containing a C 1 -C 18 alkyl group, -NR 1 -R 2 -C 2 alkyl group containing a R 1 -C 1 alkyl group and a hydrogen atom or a C 1 -C 18 alkyl group Rg is hydrogen or about A group of general formula (a) having from 1 to 18 carbon atoms, a radical of formula -NR ^ R ^ having from 1 to 18 carbon atoms R ^ and R ^, a hydrogen having from 1 to 4 carbon atoms or ORg, Rg is hydrogen or about A -COOR8 group containing a C 1 -C 18 alkyl group, a cyano group or R? -SR containing from about 1 to about 18 carbon atoms in the alkyl group; a group of the general formula.