Low VOC unsaturated polyester systems and uses thereof

• US 5,874,503 A
• Filed: 08/22/1997
• Issued: 02/23/1999
• Est. Priority Date: 05/01/1995
• Status: Expired due to Term

• Current Assignee: Lyondellbasell Advanced Polymers, Inc. (Lyondellbasell Industries NV)
• Original Assignee: Ferro Corporation
• Inventors: Drabeck, Gerald W., Wilcoxson, Jeffrey L., Thompson, Ronald E., Dusek, Dianna B., Birch, Timothy W., Scheibelhoffer, Anthony S.
• Primary Examiner(s): Acquah, Samuel A.
• Application Number:
  US08/916,478
• Time in Patent Office: 550 Days
• Field of Search: 528/274, 528/295.5, 528/296, 528/302, 524/445, 524/449, 525/10, 525/12, 525/15, 525/43, 525/44, 525/168, 525/437, 525/444, 525/445, 525/446
• US Class Current: 525/168
• CPC Class Codes: C08F 212/00 Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
• CPC Class Codes: C08F 283/01 on to unsaturated polyesters C08F283/004 takes precedence
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C09D 167/06 Unsaturated polyesters having carbon-to-carbon unsaturation
• CPC Class Codes: C09D 167/08 Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids

Abstract

This invention relates to a polyester resin comprising (A) from about 5% to about 50% by weight reactive diluent and (B) from about 50% to about 95% by weight of an unsaturated polyester resin prepared from at least one component selected from the group consisting of (i) from about 0.5% up to about 8% by mole of a polyhydric alcohol, having at least three hydroxyl groups, and at least one transesterification catalyst, (ii) from about 2% up to about 12% by mole of a reaction product of a polyol and a fatty carboxylic acid, and (iii) from about 2% up to about 12% by mole of a fatty reactant selected from the group consisting of a fatty primary alcohol, a fatty epoxide, a fatty monocarboxylic acid and mixtures thereof, wherein each member of the group has up to about 100 carbon atoms. In another aspect, the invention relates to mixtures of the above polyester resins with conventional polyester resins. Methods of reducing volatile organic compound emissions are also part of the invention. The present invention provide resins and methods which have low emissions of volatile organic compounds and when used in curable compositions have good gel times and final cured properties.

Claims

1. A polyester resin comprising (A) from about 5% to about 50% by weight reactive diluent and (B) from about 50% to about 95% by weight of an unsaturated polyester resin prepared from at least one component selected from the group consisting of from about 0.5% up to about 8% by mole of a polyhydric alcohol having at least three hydroxyl groups and at least one transesterification catalyst, (ii) from about 2% up to about 12% by mole of a reaction product of a polyol and a fatty carboxylic acid, and (iii) from about 2% up to about 12% by mole of a fatty reactant selected from the group consisting of a fatty primary alcohol, a fatty epoxide, a fatty monocarboxylic acid and mixtures thereof, wherein each member of the group has up to about 100 carbon atoms.

16. The gelcoat of claim 1 further comprising at least one surface tension agent.

2. A gelcoat comprising (A) from about 5% to about 50% by weight reactive diluent, (B) from about 50% to about 95% by weight of an unsaturated polyester resin system having an acid number of less than about 30 and prepared from at least one polycarboxylic acid or derivative thereof, at least one polyhydric alcohol, and at least one component selected from the group consisting from about 0.5% up to about 8% by mole of a polyhydric alcohol having at least three hydroxyl groups and at least one transesterification catalyst, (ii) from about 2% up to about 12% by mole of a reaction product of a polyol and a fatty carboxylic acid, and (iii) from about 2% up to about 12% by mole of a fatty reactant selected from the group consisting of a fatty primary alcohol, a fatty epoxide, a fatty monocarboxylic acid and mixtures thereof, wherein each member of the group has up to about 100 carbon atoms, and at least one thixotropic agent.

3. The gelcoat of claim 2, wherein the reactive diluent is a vinyl monomer.

4. The gelcoat of claim 2, wherein the reactive diluent is selected from the group consisting of styrene, α

-methylstyrene, vinyltoluene, divinylbenzene, and mixtures thereof.

5. The gelcoat of claim 2, wherein the polyester resin has a Mw/Mn from about 2 to about 8.

6. The gelcoat of claim 2, wherein the polyester has an acid number of less than 30.

7. The gelcoat of claim 2, wherein the unsaturated polyester resin is prepared from about 35% to about 65% by mole of at least one polycarboxylic acids and from about 35% to about 65% by mole of polyhydric alcohols.

8. The gelcoat resin of claim 7, wherein the olefinically unsaturated carboxylic acids are a mixture of from about 40% to about 60% by mole of non-aromatic carboxylic acid having from about 3 to about 12 carbon atoms and from about 40% to about 60% by mole of an aromatic acid having from about 8 to about 18 carbon atoms.

9. The gelcoat of claim 8, wherein the non-aromatic carboxylic acid is maleic acid, anhydride or ester, or fumaric acid or ester, and the aromatic carboxylic acid or derivative is selected from the group consisting of phthalic anhydride, orthophthalic acid, isophthalic acid and terephthalic acid.

10. The gelcoat of claim 2, wherein the polyhydric alcohol of (i) is glycerol, pentaerythritol, trimethylolpropane or trimethylolethane.

11. The gelcoat of claim 2, wherein (ii) is a reaction product of a triol or higher polyol with a fatty acid.

12. The gelcoat of claim 2, wherein (ii) is a glycerol fatty acid ester having two hydroxyl groups.

13. The gelcoat of claim 2, wherein (iii) has from about 12 to about 90 carbon atoms.

14. The gelcoat of claim 2 further comprising an amount of a suppressant sufficient to reduce volatile emissions.

15. The gelcoat of claim 14, wherein the suppressant is a polyether, a polyether block copolymer, an alkoxylated alcohol, an alkoxylated fatty acid or a polysiloxane.

17. The gelcoat of claim 2, wherein the thixotropic agent is fumed silica, precipitated silica or an inorganic clay.

18. The gelcoat of claim 2 further comprising an amount of a suppressant sufficient to reduce volatile emissions.

22. The gelcoat of claim 2, wherein the unsaturated polyester resin system has an acid number of less than 25.

23. The gelcoat of claim 2, wherein the unsaturated polyester resin system has an acid number of less than 20.

19. A method of reducing volatile organic emissions in cured polyester coatings and articles comprising the steps of incorporating a polyester resin system comprising (A) from about 5% to about 50% by weight reactive diluent and (B) from about 50% to about 95% by weight of an unsaturated polyester resin prepared from at least one component selected from the group consisting of from about 0.5% up to about 8% by mole of a polyhydric alcohol having at least three hydroxyl groups and at least one transesterification catalyst, (ii) from about 2% up to about 12% by mole of a reaction product of a polyol and a fatty carboxylic acid, and (iii) from about 2% up to about 12% by mole of a fatty reactant selected from the group consisting of a fatty primary alcohol, a fatty epoxide, a fatty monocarboxylic acid and mixtures thereof, wherein each member of the group has up to about 100 carbon atoms into a curable composition, and curing the composition.

20. The method of claim 19 further comprising incorporating a conventional polyester resin in reactive diluent is incorporated in the curable composition.

21. The method of claim 19, further comprising incorporating an amount of a suppressant sufficient to suppress volatile organic compound emissions.

24. A gelcoat comprising (I) a polyester resin comprising (A) from about 5% to about 50% by weight reactive diluent and (B) from about 50% to about 95% by weight of an unsaturated carboxylic acid terminated polyester resin prepared from at least one polycarboxylic acid or derivative thereof, a monobasic carboxylic acid, at least polyhydric alcohol, and at least one component selected from the group consisting of (i) from about 0.5% up to about 8% by mole of a polyhydric alcohol, having at least three hydroxyl groups, and at least one transesterification catalyst, (ii) from about 2% up to about 12% by mole of a reaction product of a polyol and a fatty carboxylic acid, and (iii) from about 2% up to about 12% by mole of a fatty reactant selected from the group consisting of a fatty primary alcohol, a fatty epoxide, a fatty monocarboxylic acid and mixtures thereof, wherein each member of the group has up to about 100 carbon atoms, and at least one thixotropic agent.

25. The gelcoat of claim 24, wherein the unsaturated carboxylic acid terminated polyester resin is a benzoic acid terminated unsaturated polyester resin.