Polymerizable Silicone Copolymer Macromers and Polymers Made Therefrom

Abstract

A polymerizable dimethicone copolyol macromer composition is synthesized by reacting itaconic anhydride with a dimethicone copolyol. During the reaction itaconic anhydride spontaneously isomerizes to citraconic anhydride which in turn is esterified by the dimethicone copolyol. The obtained macromers are copolymerizable with olefinically unsaturated monomers. Polymers containing the macromer repeating units are useful in a variety of applications including personal care, textile and industrial formulations to deliver softness, lubricity, fixative, water repellency, gloss, surface modification, and surfactant properties.

Description

Claims

1. A free radically polymerizable macromer represented by the formula:

2. A macromer of claim 1 wherein said cyclic anhydride residue is represented by the formulae:

3. A free radically polymerizable macromer composition comprising the reaction product of maleic anhydride and a dimethicone copolyol containing at least one terminal and/or pendant hydroxyl group.

4. A composition of claim 3 wherein said dimethicone copolyol is represented by the formula:

5. A composition of claim 3 wherein said dimethicone copolyol is represented by the formula:

6. A process for making a free radically polymerizable dimethicone copolyol macromer comprising: a) mixing itaconic anhydride with a dimethicone copolyol to form a reaction mixture;b) allowing said itaconic anhydride in said reaction mixture to isomerize to form isomerization products thereof; andc) reacting said reaction mixture containing said isomerization products at a suitable temperature and permitting the esterification of said isomerization products with said dimethicone copolyol.

7. A process of claim 6 wherein said dimethicone copolyol contains a terminal and/or a pendant hydroxyl group.

8. A process of claim 7 wherein said dimethicone copolyol is represented by the formula:

9. A process of claim 6 wherein said dimethicone copolyol is represented by the formula:

10. A process of claim 6 wherein said isomerization products of itaconic anhydride includes citraconic anhydride.

11. A process of claim 6 wherein said reaction mixture is reacted at a temperature ranging from about 75° C. to about 90° C.

12. A process of claim 6 wherein said reaction mixture is reacted in the presence of an esterification catalyst at a temperature ranging between ambient room temperature and 90° C.

13. A process of claim 12 wherein said esterification catalyst is selected from sulfuric acid, elemental tin, elemental zinc, elemental titanium, organo titanate compounds, organo tin compounds, organo zinc compounds, zinc oxide, magnesium oxide, calcium oxide, stannous oxide, and alkali metal acetates.

14. A polymer polymerized from a monomer composition comprising at least one dimethicone copolyol macromer selected from formulae III and IV:

15. A polymer of claim 14 wherein said monomer composition further comprises one or more monomers selected from: a) at least one non-ionic vinyl monomer;b) at least one acidic vinyl monomer;c) at least one cationic vinyl monomer;d) at least one associative vinyl monomer;e) at least one semihydrophobic vinyl monomer;f) at least one crosslinking monomer; and mixtures thereof.

16. A polymer of claim 15 wherein said non-ionic vinyl monomer is selected from at least one monomer represented by the formulae: CH2═C(X)Z;CH2═CH—OC(O)R7 wherein, X is H or methyl; and Z is —C(O)OR8, —C(O)NH2, —C(O)NHR8, —C(O)N(R8)2, —C6H4R8, —C6H4OR8, —C6H4Cl, —C6H11, —C6H7(R8)(R8)(R8), —CN, —NHC(O)CH3, —NHC(O)H, N-(2-pyrrolidonyl), N-caprolactamyl, —C(O)NHC(CH3)3, —C(O)NHCH2CH2—N-ethyleneurea, —Si(R7)3, —C(O)O(CH2)xSi(R7)3, —C(O)NH(CH2)xSi(R7)3, or —(CH2)xSi(R7)3; x is an integer ranging from about 1 to about 6; R7 independently represents linear and branched C1 to C18 alkyl; R8 independently represents linear and branched C1 to C30 alkyl, hydroxy substituted C2 to C30 alkyl, and halogen substituted C1 to C30 alkyl.

17. A polymer of claim 15 wherein said acidic vinyl monomer contains at least one acidic group selected from a carboxylic acid group and salts thereof, a sulfonic acid group and salts thereof, and a phosphonic acid group and salts thereof.

18. A polymer of claim 17 wherein said acidic vinyl monomer is selected from acrylic acid, methacrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid, C1 to C18 alkyl monoesters of maleic, fumaric, itaconic, or aconitic acid, anhydrides of dicarboxylic acids, vinyl sulfonic acid, 2-sulfoethyl methacrylate, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, allyloxybenzene sulfonic acid, vinyl phosphonic acid, allyl phosphonic acid, 3-acrylamidopropyl phosphonic acid; and salts thereof; and mixtures thereof.

19. A polymer of claim 15 wherein said cationic vinyl monomer is selected from mono-(C1 to C4)alkylamino(C1 to C8)alkyl(meth)acrylate, a di-(C1 to C4)alkylamino(C1 to C8)alkyl(meth)acrylate, a mono-(C1 to C4)alkylamino(C1 to C8)alkyl(meth)acrylamide, a di-(C1 to C4)alkylamino(C1 to C8)alkyl(meth)acrylamide, a nitrogen-containing heterocyclic(meth)acrylamide, a nitrogen-containing heterocyclic(meth)acrylate; and salts thereof; and mixtures thereof.

20. A polymer of claim 19 wherein said cationic vinyl monomer is selected from 2-(N,N-dimethylamino)ethyl(meth)acrylate, 3-(N,N-dimethylamino)propyl(meth)acrylate, 4-(N,N-dimethylamino)butyl(meth)acrylate, (N,N-dimethylamino)-t-butyl(meth)acrylate, 2-tert-butylamino)ethyl(meth)acrylate, 2-(N,N-diethylamino)ethyl(meth)acrylate, 3-(N,N-diethylamino)propyl(meth)acrylate, 2-(N,N-dimethylamino)neopentyl acrylate, 4-N,N-diethylamino)butyl(meth)acrylate, 2-(N,N-dipropylamino)ethyl(meth)acrylate, 3-N,N-(dipropylamino)propyl(meth)acrylate, 4-N,N-dipropylamino)butyl(meth)acrylate, 3-(N,N-dimethylamino)propyl(meth)acrylate, 2-(4-morpholinyl)ethyl(meth)acrylate, 2-(4-morpholinyl)ethyl acrylate, N′-(2-N,N-dimethylamino)ethyl(meth)acrylamide, 2-(N,N-dimethylamino)propyl(meth)acrylamide, N′-3-(N,N-dimethylamino)propyl(meth)acrylamide, N-(2-pyridyl)acrylamide, N-2-imidazoyl)(meth)acrylamide, N-(4-morpholinyl)(meth)acrylamide, N-(4-morpholinyl)acrylamide, 2-vinyl pyridine, 4-vinyl pyridine, N-vinyl-2-methylimidazole, N-vinylimidazole, N-vinyl-4-methylimidazole, and N-vinyloxazolidone; and salts thereof; and mixtures thereof.

21. A polymer of claim 19 wherein said cationic vinyl monomer is selected from 3-trimethylammonium propyl(meth)acrylamide chloride, 3-trimethylammonium propyl acrylamide chloride, quaternized N,N-dimethylaminoethyl(meth)acrylate with C1 to C30 alkyl sulphate, quaternized N,N-dimethylaminoethyl(meth)acrylate with methylchloride, quaternized vinyl imidazole, methacryloyl ethyl betaine, and methacryloyl N-oxide.

22. A polymer of claim 15 wherein said associative vinyl monomer is selected from at least one monomer represented by the formula:

23. A polymer of claim 22 wherein said associative vinyl monomer is selected from cetyl polyethoxylated methacrylate, cetearyl polyethoxylated(meth)acrylate, stearyl polyethoxylated(meth)acrylate, arachidyl polyethoxylated(meth)acrylate, behenyl polyethoxylated(meth)acrylate, lauryl polyethoxylated(meth)acrylate, cerotyl polyethoxylated(meth)acrylate, montanyl polyethoxylated(meth)acrylate, melissyl polyethoxylated(meth)acrylate, lacceryl polyethoxylated(meth)acrylate, tristyryl phenolpolyethoxylated(meth)acrylate, hydrogenated castor oil polyethoxylated methacrylate, canola polyethoxylated(meth)acrylate, and cholesterol polyethoxylated(meth)acrylate, wherein the polyethoxylated portion of the monomer contains from about 5 to about 100 ethylene oxide repeating units.

24. A polymer of claim 15 wherein said semihydrophobic vinyl monomer is selected from at least one monomer represented by the formula:

25. A polymer of claim 24 wherein said semihydrophobic vinyl monomer is represented by at least one monomer of the formulae: CH2═CH—O(CH2)aO(C3H6O)b(C2H4O)cHCH2═CH—CH2O(C3H6O)d(C2H4O)eHwherein a is an integer of 2, 3, or 4; b is an integer in the range of 1 to about 10; c is an integer in the range of about 5 to about 50; d is an integer in the range of 1 to about 10; and e is an integer in the range of about 5 to about 50.

26. A polymer of claim 15 wherein said monomer composition comprises 0 to 5 weight percent (based on the weight of the total monomers of a crosslinking monomer.

27. A polymer of claim 15 wherein said monomer composition comprises at least 0.01 percent by weight based on the total monomer weight of a chain transfer agent.