Polyester compositions

Abstract

The disclosure of this application is directed to unsaturated polyester compositions, containing as a low-profile additive a carboxyl containing thermoplastic polymer of a vinyl ester of an aliphatic, saturated monocarboxylic acid, which have particular utility in molding applications to form aesthetically attractive thermoset articles characterized by excellent physical properties, as for example, impact strength and by excellent surface properties such as excellent smoothness and gloss, excellent receptiveness to paints and excellent reproduction of the surface contours of the mold in which they are formed into shaped, thermoset articles.

What is claimed is: 
     
       1. A composition, suitable for use in molding, comprising an ethylenically unsaturated monomer, an unsaturated polyester which is the condensation product of an ethylenically unsaturated polycarboxylic acid or anhydride and a polyol, and, as a low profile additive, in an amount of from about 1 to about 85 weight percent, based on weight of said unsaturated polyester, a carboxyl containing polymer of a vinyl ester of an aliphatic, saturated monocarboxylic acid, wherein said carboxyl containing polymer contains from about 0.2 to about 5 weight percent of a polymerized carboxyl containing comonomer, and at least about 5 weight percent of polymerized vinyl alkanoate. 
     
     
       2. A composition as defined in claim 1 wherein the vinyl ester polymer is present in an amount of about 1 to about 60 percent by weight based on the weight of the unsaturated polyester. 
     
     
       3. A composition as defined in claim 1 wherein the carboxyl containing polymer is a polymer of a vinyl ester of an aliphatic, saturated monocarboxylic acid and an ethylenically unsaturated carboxylic acid. 
     
     
       4. A composition as defined in claim 1 wherein the vinyl ester of an aliphatic, saturated monocarboxylic acid has the formula: ##STR4## wherein R" is hydrogen or a saturated, aliphatic hydrocarbon radical having a maximum of 20 carbon atoms. 
     
     
       5. A composition as defined in claim 1 wherein R" is a saturated, aliphatic hydrocarbon radical having a maximum of 8 carbon atoms. 
     
     
       6. A composition as defined in claim 1 wherein the said vinyl ester is vinyl acetate. 
     
     
       7. A composition as defined in claim 1 wherein the unsaturated polyester is a condensation reaction product of a mixture containing a polyol and an acid having the formula:   C.sub.n H.sub.2n-2 --(COOH).sub.2     wherein n is an integer having a value of 2 to 20 inclusive.   
     
     
       8. A composition as defined in claim 1 wherein the polyol has the formula: ##STR5## wherein the sum of m+p is 1 to 20 inclusive, R 1  and R 2  are hydrogen or alkyl. 
     
     
       9. A composition as defined in claim 1 wherein the polyol has the formula:   HO--(C.sub.a H.sub.2a O).sub.x H     wherein a has a maximum value of 6, x has a value of 2 to 10 inclusive.   
     
     
       10. A composition as defined in claim 1 wherein the polyol is propylene glycol and the acid anhydride is maleic acid anhydride. 
     
     
       11. A composition as defined in claim 1 wherein the monomer is styrene. 
     
     
       12. A composition as defined in claim 1 containing a peroxide. 
     
     
       13. The cured product of the composition defined in claim 12. 
     
     
       14. A composition as defined in claim 1 wherein the unsaturated polyester is the condensation reaction product of a mixture containing polyol, an unsaturated polycarboxylic acid or anhydride thereof and an aromatic acid or anhydride thereof. 
     
     
       15. A composition as defined in claim 14 wherein the aromatic acid is phthalic acid. 
     
     
       16. A composition as defined in claim 14 wherein the aromatic acid anhydride is phthalic acid anhydride. 
     
     
       17. A composition as defined in claim 1 containing a polymerizable ethylenically unsaturated monomer in an amount of about 10 to about 60 percent by weight based on the combined weight of said monomer and said polyester and a Group I, II or IV metal oxide or hydroxide thickener in an amount of about 0.5 to about 75 percent by weight based on the weight of said polyester. 
     
     
       18. A composition as defined in claim 1 containing a polymerizable ethylenically unsaturated monomer in an amount of about 10 to about 60 percent by weight based on the combined weight of said monomer and said polyester, a Group I, II or IV metal oxide or hydroxide in an amount of about 0.5 to about 75 percent by weight based on the weight of said polyester and wherein the carboxyl containing vinyl polymer is a polymer of vinyl acetate having an average of at least one carboxyl group per molecule and is present in an amount of about 1 to about 60 percent by weight based on the weight of the said polyester. 
     
     
       19. A composition as defined in claim 17 wherein the thickener is a Group II metal oxide. 
     
     
       20. A composition as defined in claim 17 wherein the thickener is a Group II metal hydroxide. 
     
     
       21. A composition as defined in claim 17 wherein the thickener is a Group IV metal oxide. 
     
     
       22. A composition as defined in claim 17 wherein the thickener is a Group IV metal hydroxide. 
     
     
       23. A composition as defined in claim 17 wherein the thickener is calcium hydroxide. 
     
     
       24. A composition as defined in claim 17 wherein the polyol is ethylene glycol and the acid is fumaric acid. 
     
     
       25. A composition as defined in claim 17 wherein the polyol is propylene glycol and the acid anhydride is maleic acid anhydride. 
     
     
       26. A composition as defined in claim 17 wherein the ethylenically unsaturated monomer is a vinyl monomer. 
     
     
       27. A composition as defined in claim 26 wherein the vinyl monomer is styrene. 
     
     
       28. The thermoset product of the composition defined in claim 26. 
     
     
       29. A composition as defined in claim 17 wherein the thickener is a Group I metal oxide. 
     
     
       30. A composition as defined in claim 17 wherein the thickener is a Group I metal hydroxide. 
     
     
       31. A composition comprising (A) an unsaturated polyester which is the condensation product of at least one ethylenically unsaturated dicarboxylic acid with at least one dihydric alcohol, (B) an ethylenically unsaturated monomer, and (C) 1 to 60 percent by weight, based on the combined weight of the unsaturated polyester and the ethylenically unsaturated monomer, of a polymer containing, in combined form, vinyl acetate and about 0.2 to about 5 percent by weight of ethylenically unsaturated carboxylic acid. .Iadd. 
     
     
       32.  A composition as defined in claim 1 wherein the low profile additive is present in an amount of from about 3 to about 35 weight percent, based on the weight of the unsaturated polyester. .Iaddend. .Iadd.33. A composition as defined in any of claims 1-9, 11, 13, 17-20, or 32 wherein the carboxyl containing polymer contains about 1 weight percent of a polymerized carboxyl containing comonomer. .Iaddend. .Iadd.34. A composition as defined in any of claims 1-9, 11, 13, 17-20, or 32 wherein the carboxyl containing polymer contains at least about 40 percent of polymerized vinyl alkanoate. .Iaddend. .Iadd.35. A composition as defined in claim 34 wherein the carboxyl containing polymer contains about 1 weight percent of a polymerized carboxyl containing comonomer. .Iaddend. .Iadd.36. A composition as defined in claim 31 wherein the ethylenically unsaturated carboxylic acid is present in an amount of about 1 weight percent. .Iaddend. .Iadd.37. A composition as defined in claim 31 wherein the vinyl acetate is present in an amount of at least about 40 weight percent. .Iaddend. .Iadd.38. A composition as defined in claim 37 wherein the ethylenically unsaturated carboxylic acid is present in an amount of about 1 weight percent. .Iaddend. .Iadd.39. A composition as defined in any of claims 31 or 36-38 wherein the ethylenically unsaturated carboxylic acid is acrylic acid, methacrylic acid, or maleic acid. .Iaddend. 
     
     
        .Iadd.     A composition comprising (A) an unsaturated polyester which is the condensation product of at least one ethylenically unsaturated dicarboxylic acid with at least one dihydric alcohol, (B) an ethylenically unsaturated monomer, and (C) 1 to 60 percent by weight, based on the combined weight of the unsaturated polyester and the ethylenically unsaturated monomer, of a thermoplastic polymer of a vinyl ester of a saturated aliphatic monocarboxylic acid containing, in combined form, at least one polymerizable ethylenically unsaturated monomer and from about 0.2 to about 5 percent by weight of ethylenically unsaturated carboxylic acid. .Iaddend. .Iadd.41. A composition as defined in claim 40 wherein said thermoplastic polymer is prepared from a polymerizable, ethylenically unsaturated monomer selected from the group consisting of vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene bromide, methyl acrylate, ethyl acrylate, butyl acrylate, n-octyl acrylate, 2-ethyl hexyl acrylate, n-decyl acrylate, glycidal methacrylate, acrylamide, n-methyl acrylamide, n,n-dimethylacrylamide, methyl acrylamide, n-methyl methacrylamide, n,n-dimethyl methacrylamide, acrylonitrile, chloroacrylonitrile, methacrylonitrile, ethacrylonitrile, vinyl naphthalene, dimethyl maleate, dibutyl maleate, vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, 2-chloroethyl vinyl ether, methyl vinyl ketone, ethyl vinyl ketone, isobutyl vinyl ketone, vinyl pyridine, n-vinyl carbazole, n-vinyl pyrrolidene, ethyl methylene malonate, isobutylene, ethylene, trichloroethylene, propylene, and vinyl norbornene. .Iaddend.