Polyester process

• US 6,063,827 A
• Filed: 07/22/1998
• Issued: 05/16/2000
• Est. Priority Date: 07/22/1998
• Status: Expired due to Term

• Current Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Original Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Inventors: Sacripante, Guerino G., Bayley, Robert D., Li, Dongming, Saban, Marko D., Foucher, Daniel A., Toth, Alan E. J., Kittelberger, J. Stephen
• Primary Examiner(s): Acquah, Samuel A.
• Application Number:
  US09/120,649
• Time in Patent Office: 664 Days
• Field of Search: 528/190, 528/193, 528/194, 528/195, 528/219, 528/275, 528/298, 528/302, 528/303, 528/306, 528/307, 528/308, 528/308.6, 524/777, 524/779, 524/788, 430/107, 430/114, 522/6, 522/104, 522/165
• US Class Current: 522/6
• CPC Class Codes: C08G 63/58 Cyclic ethers C08G59/00 takes precedence; Cyclic carbonates; Cyclic sulfites ; Cyclic orthoesters
• CPC Class Codes: C08G 63/676 in which at least one of the two components contains aliphatic unsaturation
• CPC Class Codes: C08G 63/83 Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof C08G63/823 takes precedence
• CPC Class Codes: G03G 9/08755 Polyesters

Abstract

A process for the preparation of an unsaturated polyester which comprises (i) reacting an organic diol with a cyclic akylene carbonate in the presence of a first catalyst to thereby form a polyalkoxy diol, and (ii) optionally adding thereto a further amount of cyclic alkylene carbonate in the presence of a second catalyst, and (iii) subsequently polycondensing the resulting mixture with a dicarboxylic acid.

Claims

1. A process for the preparation of an unsaturated polyester which comprises (i) reacting an organic diol with a cyclic alkylene carbonate in the presence of a first catalyst of an alkali carbonate to thereby form a polyalkoxy diol, and (ii) adding thereto a further amount of cyclic alkylene carbonate in the presence of a second catalyst of an alkali alkoxide, and (iii) subsequently polycondensing the resulting mixture with a dicarboxylic acid.

2. A process in accordance with claim 1 wherein the preparation of said unsaturated polyester comprises (i) reacting an organic diol in an amount of from about 0.95 to about 1.05 mole equivalents with a cyclic akylene carbonate in an amount of from about 1.95 to about 2.05 mole equivalents, in the presence of said first alkali carbonate catalyst in an amount of from about 0.001 to about 0.1 mole equivalents, to thereby form a polyalkoxy diol, and wherein the polyalkoxy diol is comprised of isomers with from about 2 to about 5 weight percent of isomer I, from about 95 to about 99 weight percent of isomer II, and from about 0 to about 3 weight percent of isomer III, and the sum of I, II, and III is about 100 percent and wherein said isomers are of the following formulas ##STR8## and followed by subsequently polycondensing the resulting polyalkoxy diol with said dicarboxylic acid in an amount of from about 0.95 to about 1.05 mole equivalents, wherein R is an aromatic component, R'"'"' is hydrogen or alkyl, and a is zero, 1, or 2, or a mixture of zero, 1, and 2.

3. A process in accordance with claim 1 wherein the preparation of the unsaturated polyester comprises (i) reacting an organic diol in an amount of from about 0.95 to about 1.05 mole equivalents with a cyclic akylene carbonate in an amount of from about 1.95 to about 2.05 mole equivalents, in the presence of said first alkali carbonate catalyst in an amount of from about 0.001 to about 0.1 mole equivalents;

adding thereto (ii) from about 0.05 to about 0.45 mole equivalents of cyclic alkylene carbonate in the presence of said second alkali alkoxide catalyst in an amount of from about 0.001 to about 0.1 mole equivalents, to thereby form a polyalkoxy diol comprised of isomers with from about 0 to about 1 weight percent of isomer I, from about 85 to about 97 weight percent of isomer II, and from about 3 to about 15 weight percent of isomer III, and the sum of I, II, and III is about 100 percent and wherein said isomers are of the formulas ##STR9## and followed by subsequently polycondensing the resulting polyalkoxy diol with a dicarboxylic acid in an amount of from about 0.95 to about 1.05 mole equivalent, wherein a is zero, 1, 2, or a mixture of zero, 1 and 2.

4. A process in accordance with claim 1 wherein there is formed a crosslinked polyester generated by the reactive extrusion of a peroxide and said unsaturated polyester.

5. A process in accordance with claim 1 wherein said first catalyst is sodium carbonate.

6. A process in accordance with claim 1 wherein said second catalyst is lithium butoxide.

7. A process in accordance with claim 1 wherein said reacting is accomplished in the presence of heat.

8. A process in accordance with claim 1 wherein said reacting is accomplished by heating at a temperature of from about 160°

C. to about 215°

C.

9. A process in accordance with claim 1 wherein said reacting is accomplished by heating at a temperature of from about 180°

C. to about 200°

C.

10. A process in accordance with claim 1 wherein said polycondensing is accomplished by heating.

11. A process in accordance with claim 1 wherein said polycondensing is accomplished by heating at a temperature of from about 185°

C. to about 225°

C.

12. A process in accordance with claim 1 wherein said polycondensing is accomplished by heating at a temperature of from about 185°

C. to about 225°

C. for a duration of from about 1 to about 5 hours, followed by reducing the pressure from about 760 Torr to about 1 Torr over a period of from about 1 to about 6 hours.

13. A process in accordance with claim 1 wherein subsequent to said polycondensing the reaction mixture is cooled.

14. A process in accordance with claim 13 wherein said cooling is from about 25°

C. to about 40°

C.

15. A process in accordance with claim 13 wherein said cooling is to about 25°

C.

16. A process in accordance with claim 1 wherein there is formed a crosslinked polyester generated by the reactive extrusion of a peroxide and said unsaturated polyester.

17. A process in accordance with claim 16 wherein said crosslinking is represented by a gel content of from about 3 to about 75 percent.

18. A process in accordance with claim 16 wherein said crosslinking is represented by a gel content of from about 3 to about 45 percent.

19. A process in accordance with claim 1 wherein there is formed an unsaturated polyester resin of poly(propoxylated bisphenol co-fumarate), poly(ethoxylated bisphenol co-fumarate), poly(butyloxylated bisphenol co-fumarate), poly(co-propoxylated bisphenol co ethoxylated bisphenol co-fumarate), poly(1,2-propylene fumarate), poly(propoxylated bisphenol co-maleate), poly(ethoxylated bisphenol co-maleate), poly(butyloxylated bisphenol co-maleate), poly(co-propoxylated bisphenol co ethoxylated bisphenol co-maleate), poly(1,2-propylene maleate), poly(propoxylated bisphenol co-itaconate), poly(ethoxylated bisphenol co-itaconate), poly(butyloxylated bisphenol co-itaconate), poly(co-propoxylated bisphenol co ethoxylated bisphenol co-itaconate), or poly(1,2-propylene itaconate).

20. A process in accordance with claim 1 wherein said diol is 1,2-propanediol, 1,3-propanediol, 1,3- butane diol, pentylene glycol, hexylene glycol, diphenol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2-bis-(4-hydroxy phenyl) propane, 2,2-bis-(3-hydroxy phenyl) propane, 2,2-bis-(2-hydroxy phenyl) propane, 2,2-bis-(3-hydroxy phenyl) propane, 2,2-bis-(5-hydroxy phenyl) propane, bisphenol A, ethoxylated bisphenol A, bis-(4-hydroxy phenyl) methane, 1,1-bis-(4-hydroxy phenyl) ethane, cis-1,4-dihydroxy-cyclohexane, trans-1,4-dihydroxy-cyclohexane, cis-1,2-dihydroxy-cyclohexane, trans-1,2-dihydroxy-cyclohexane, trans-1,3-dihydroxy-cyclohexane, cis-1,3-dihydroxy-cyclohexane, and mixtures thereof and which diol is optionally selected in an amount of from about 0.90 mole equivalents to about 1.1 mole equivalents, based on about 1 mole equivalent of dicarboxylic acid utilized.

21. A process in accordance with claim 1 wherein said diol is 2,2-bis-(4-hydroxy phenyl) propane or bisphenol A.

22. A process in accordance with claim 1 wherein the dicarboxylic acid is fumaric acid, malonic acid, itaconic acid, 2-methylitaconic acid, maleic acid, maleic anhydride, adipic acid, succinic acid, suberic acid, 2-ethyl succinic acid, glutaric acid, dodecylsuccinic acid, 2-methyladipic acid, pimelic acid, azeilic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,2-cyclohexanedioic acid, 1,3-cyclohexanedioic acid, 1,4-cyclohexanedioic acid, dialkyl esters wherein alkyl contains from about 2 to about 22 carbon atoms, and are esters of malonate, succinate, fumarate, itaconate, terephthalate, isophthalate, phthalate, cyclohexanedioate, mixtures thereof, and which diacids are optionally selected in an amount of from about 0.95 mole equivalent to about 1.1 mole equivalents, based on about 1 mole equivalent of organic diol utilized.

23. A process in accordance with claim 1 wherein the dicarboxylic acid is fumaric acid.

24. A process in accordance with claim 1 wherein the cyclic alkylene carbonate is ethylene carbonate, propylene carbonate, butylene carbonate, or mixtures thereof, and which alkylene carbonate is selected in an amount of from about 1.90 mole equivalents to about 2.45 mole equivalents, based on about 1 mole equivalent of organic diol utilized.

25. A process in accordance with claim 1 wherein said first alkali catalyst is sodium carbonate.

26. A process in accordance with claim 1 wherein the alkali carbonate is potassium carbonate, sodium carbonate, rubidium carbonate, cesium carbonate, beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, manganese carbonate, or barium carbonate and mixtures thereof and which alkali carbonate is selected in an amount of from about 0.001 mole equivalent to about 0.01 mole, based on about 1 mole equivalent of organic diol utilized.

27. A process in accordance with claim 1 wherein the alkali carbonate is potassium carbonate.

28. A process in accordance with claim 27 wherein the second catalyst is an alkali alkoxide.

29. A process in accordance with claim 1 wherein the alkyl alkoxide is lithium methoxide, lithium ethoxide, lithium propoxide, lithium butoxide, lithium isopropoxide, lithium isobutoxide, lithium t-butoxide, potassium methoxide potassium ethoxide, potassium propoxide, potassium butoxide, potassium isopropoxide, potassium isobutoxide, potassium t-butoxide, sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, sodium isopropoxide, sodium isobutoxide, sodium t-butoxide, or mixtures thereof, and which alkali alkoxide is selected in an amount of from about 0.001 mole equivalent to about 0.05 mole equivalent, based on about 1 mole equivalent of organic diol utilized.

30. A process in accordance with claim 1 wherein the alkyl alkoxide is potassium t-butoxide.

31. A process in accordance with claim 1 wherein said first catalyst is selected in an amount of from about 0.01 to about 0.1 mole percent by weight of the unsaturated polyester.

32. A process in accordance with claim 1 wherein said second catalyst is selected in an amount of from about 0.01 to about 0.1 mole percent by weight of the unsaturated polyester.

33. A process in accordance with claim 4 wherein the peroxide is an aliphatic peroxide, an aromatic peroxide, or mixtures thereof.

34. A process in accordance with claim 33 wherein the peroxide is benzoyl peroxide, lauryl peroxide, t-butyl peroxide, propyl peroxide, or stearyl peroxide.

35. A process in accordance with claim 2 wherein a polyester resin is formed by (i) reacting an organic diol in an amount of from about 0.95 to about 1.05 mole equivalents, with a cyclic akylene carbonate in an amount of from about 1.95 to about 2.05 mole equivalents, and a catalyst in an amount of from about 0.001 to about 0.1 mole equivalents at a temperature of from about 175°

C. to about 205°

C., for a duration of from about 1 to about 6 hours; and

followed by polycondensing with a dicarboxylic acid in an amount of from about 0.95 to about 1.05 mole equivalents.

36. A process in accordance with claim 1 wherein said polyester resin is formed by (i) reacting an organic diol in an amount of from about 0.95 to about 1.05 mole equivalent, with a cyclic akylene carbonate in an amount of from about 1.95 to about 2.05 mole equivalents, and a catalyst in an amount of from about 0.001 to about 0.1 mole equivalent, at a temperature of from about 175°

C. to about 205°

C.;

(ii) adding thereto a cyclic akylene carbonate in an amount of from about 0.05 to about 0.35 mole equivalent, with a second alkali alkoxide catalyst in an amount of from about 0.001 to about 0.1 mole equivalent, at a temperature of from about 185°

C. to about 205°

C.; and

(iii) followed by polycondensing with a dicarboxylic acid in an amount of from about 0.95 to about 1.05 mole equivalent.

37. A process in accordance with claim 1 wherein the unsaturated polyester resin is obtained from (i) condensing about 0.95 to about 1.05 mole equivalent of an organic diol, with from about 1.95 to about 2.05 mole equivalent of an alkylene carbonate in the presence of a first alkali catalyst at a temperature of from about 175°

C. to about 205°

C.; and

(ii) optionally adding thereto a further amount of from about 0.05 to about 0.35 mole equivalent of said cyclic alkylene carbonate and a second catalyst a temperature of from about 185°

C. to about 205°

C., for a duration of from about 1 to about 3 hours; and

(iii) polycondensing with a dicarboxylic acid in an amount of from about 0.95 to about 1.05 mole equivalent, for a duration of from about 1 to 3 hours, and followed by reducing the pressure from about 760 Torr to about 1 Torr.

38. A process in accordance with claim 1 wherein said cyclic alkylene carbonate is employed in an amount of from about 1.9 equivalents to about 2.1 mole equivalents, based on about 1 mole equivalent of organic diol utilized.

39. A process in accordance with claim 1 wherein there is further added a cyclic alkylene carbonate in an amount of from about 0.05 mole equivalent to about 0.30 mole equivalent, based on about 1 mole equivalent of organic diol utilized.

40. A process in accordance with claim 1 wherein the unsaturated polyester resin is obtained from (i) condensing about 0.95 to about 1.05 mole equivalent of an organic diol, with from about 1.95 to about 2.05 mole equivalent of an alkylene carbonate in the presence of a first alkali catalyst at a temperature of from about 175°

C. to about 205°

C., for a duration of from about 1 to about 6 hours; and

(ii) optionally adding thereto a further amount of from about 0.05 to about 0.35 mole equivalent of a cyclic alkylene carbonate and said second catalyst a temperature of from about 185°

C. to about 205°

C., for a duration of from about 1 to about 3 hours; and

(iii) followed by a third step comprised of adding a dicarboxylic acid, heating the mixture of from about 185°

C. to about 220°

C., followed by reducing the pressure from about 760 Torr to about 1 Torr.

41. A process in accordance with claim 1 wherein the polyester resulting is poly(propoxylated bisphenol co-fumarate), poly(ethoxylated bisphenol co-fumarate), poly(butyloxylated bisphenol co-fumarate), poly(co-propoxylated bisphenol co ethoxylated bisphenol co-fumarate), or poly(propoxylated bisphenol co-maleate).

43. A process in accordance with claim 1 wherein the polyester is poly(propoxylated bisphenol), and the bis-alkoxy diol is propoxylated bisphenol A comprised of mixture of isomers of 4-(2-hydroxyethyl)-bisphenol A, bis 4,4'"'"'-(2-hydroxyethyl)-bisphenol A, 4-(2'"'"'-hydroxyethyl-2-oxyethyl)-4'"'"'-(2-hydroxyethyl)-bisphenol A and/or higher ordered propoxylated bisphenol A polyols, illustrated as monomers I, II and III, respectively, of Formula 2 ##STR10## wherein R is an aromatic component, R'"'"' is hydrogen or alkyl, and a is zero, 1, or 2, or a mixture of zero, 1, and 2.

44. A process in accordance with claim 1 wherein the polyester is poly(propoxylated bisphenol), and the diol is a bis-alkoxy diol of propoxylated bisphenol A comprised of mixture of isomers of 4-(2-hydroxyethyl)-bisphenol A, bis 4,4'"'"'-(2-hydroxyethyl)-bisphenol A, 4-(2'"'"'-hydroxyethyl-2-oxyethyl)-4'"'"'-(2-hydroxyethyl)-bisphenol A and/or higher ordered propoxylated bisphenol A polyols, illustrated as monomers I, II and III, respectively, of Formula 1 ##STR11## wherein a is zero, 1, 2, or a mixture of zero, 1 and 2.

45. A process in accordance with claim 43 wherein the isomers contain from about 2 to about 5 weight percent of isomer I, from about 90 to about 97 weight percent of isomer II, and from about 0 to about 3 weight percent of isomer III, and the sum of I, II, and III is about 100 percent.

46. A process in accordance with claim 1 wherein the preparation of an unsaturated polyester is comprised of (i) reacting bisphenol A or 2,2-bis(4-hydroxy phenyl) propane with a propylene carbonate in the presence of a first catalyst to thereby form a bis-alkoxy diol, and (ii) adding thereto said further amount of propylene carbonate in the presence of a second catalyst, and wherein the bis-alkoxy diol is comprised of the isomers of Formula 1 ##STR12## with from about 0 to about 1 weight percent of isomer I, from about 85 to about 97 weight percent of isomer II, and from about 3 to about 15 weight percent of isomer III, and the sum of I, II, and III is about 100 percent, and wherein a is zero, 1, 2, or 2.

47. A process in accordance with claim 2 wherein the aromatic R component is a radical moiety selected from the group consisting of selected from 2,2-bis-(4-hydroxy phenyl) propane, 2,2-bis-(3-hydroxy phenyl) propane, 2,2-bis-(2-hydroxy phenyl) propane, 2,2-bis-(3-hydroxy phenyl) propane, 2,2-bis-(5-hydroxy phenyl) propane, bisphenol A, ethoxylated bisphenol A, bis-(4-hydroxy phenyl) methane, 1,1 -bis-(4-hydroxy phenyl) ethane and hydroquinone.

48. A process in accordance with claim 3 wherein the aromatic R component is a radical moiety of 2,2-bis-(4-hydroxy phenyl) propane, 2,2-bis-(3-hydroxy phenyl) propane, 2,2-bis-(2-hydroxy phenyl) propane, 2,2-bis-(3-hydroxy phenyl) propane, 2,2-bis-(5-hydroxy phenyl) propane, bisphenol A, ethoxylated bisphenol A, bis-(4-hydroxy phenyl) methane, 1,1-bis-(4-hydroxy phenyl) ethane or hydroquinone.

42. A process for the preparation of crosslinked polyesters obtained from the reactive extrusion of a peroxide and an unsaturated polyester resin, and which resin is generated by (i) reacting an organic diol with a cyclic alkylene carbonate in the presence of a first catalyst to thereby form a polyalkoxy diol;

(ii) adding thereto a further amount of cyclic alkylene carbonate in the presence of a second catalyst; and

(iii) subsequently polycondensing the resulting mixture with a dicarboxylic acid, and wherein said first catalyst is an alkali carbonate, and wherein said second catalyst is an alkali alkoxide.

49. A process for the preparation of an unsaturated polyester which consists essentially of (i) reacting an organic diol with a cyclic alkylene carbonate in the presence of a first catalyst to thereby form a polyalkoxy diol, and (ii) adding thereto a further amount of said cyclic alkylene carbonate in the presence of a second catalyst, and (iii) subsequently polycondensing the resulting mixture with a dicarboxylic acid.

51. A process in accordance with claim 49 wherein there is formed a crosslinked polyester generated by the reactive extrusion of a peroxide and said unsaturated polyester.

52. A process in accordance with claim 49 wherein said first catalyst is potassium carbonate, and said second catalyst is potassium tertiary butoxide.

50. A process for the preparation of an unsaturated polyester which comprises reacting an organic diol in an amount of from about 0.95 to about 1.05 mole equivalents with a cyclic alkylene carbonate in an amount of from about 1.95 to about 2.05 mole equivalents, in the presence of a first alkali carbonate catalyst in an amount of from about 0.001 to about 0.1 mole equivalents, to thereby form a polyalkoxy diol, and wherein the polyalkoxy diol is comprised of isomers with from about 2 to about 5 weight percent of isomer I, from about 95 to about 99 weight percent of isomer II, and from about 0 to about 3 weight percent of isomer III, and the sum of I, II, and III is about 100 percent and wherein said isomers are of the following formulas ##STR13## and followed by subsequently polycondensing the resulting polyalkoxy diol with said dicarboxylic acid in an amount of from about 0.95 to about 1.05 mole equivalents, wherein R is an aromatic component, R'"'"' is hydrogen or alkyl, and a is zero, 1, or 2, or a mixture of zero, 1, and 2, and wherein the reaction with the cyclic alkylene carbonate is accomplished in the presence of an alkali alkoxide catalyst.