Esterification catalyst, polyester process and polyester article
View Patent ↗A catalyst composition for producing polyesters comprises: a) an organometallic compound obtained by reacting an orthoester or condensed orthoester of titanium, zirconium or aluminum, an alcohol containing at least two hydroxyl groups, a 2-hydroxy carboxylic acid and a base; and b) at least one compound comprising germanium, antimony or tin. Polyesters obtained by esterification reaction in the presence of the catalyst compositions according to the present invention exhibit improved melt properties and are particularly suitable for production of textile and commercial fibers, films and rigid packaging.
1. A catalyst composition suitable for use as a catalyst for the preparation of an ester comprising
(a) a preformed metal-organic compound which is the product resulting from the reaction of
(i) an orthoester or condensed orthoester of titanium, zirconium, or aluminum,
(ii) an alcohol containing at least two hydroxyl groups,
(iii) a 2-hydroxy carboxylic acid, and
(iv) an organic base selected from the group consisting of quaternary ammonium hydroxide compounds; and
(b) at least one compound of germanium, antimony or tin.
2. A catalyst composition as claimed in claim 1 , wherein the metal-organic compound is a reaction product of a titanium orthoester.
3. A catalyst composition as claimed in claim 1 , wherein said alcohol is a dihydroxy alcohol.
4. A catalyst composition according to claim 3 wherein the metal-organic compound comprises titanium or zirconium and contains from 2 to 12 moles of dihydroxy alcohol per mole of titanium or zirconium.
5. A catalyst composition as claimed in claim 1 , wherein said carboxylic acid is lactic acid, citric acid, malic acid or tartaric acid.
6. A catalyst composition according to claim 1 wherein the metal-organic compound comprises titanium or zirconium and contains from 1 to 4 moles of 2-hydroxy carboxylic acid per mole of titanium or zirconium.
7. A catalyst composition as claimed in claim 1 , wherein said base is tetrabutyl ammonium hydroxide, tetraethylammonium hydroxide, trimethyl(2-hydroxyethyl)ammonium hydroxide, or benzyltrimethyl ammonium hydroxide.
8. A catalyst composition as claimed in claim 1 , wherein the metal-organic compound comprises the reaction product of a titanium orthoester, citric acid, a dihydric alcohol and an inorganic base in which the mole ratio of titanium:acid:dihydric alcohol: base is in the range 1:1.5-3.5:4-10:2-12.
9. A catalyst composition according to claim 1 , wherein the compound of germanium is germanium dioxide or a salt of germanium.
10. A catalyst composition according to claim 1 , wherein the compound of antimony is antimony trioxide or a salt of antimony.
11. A catalyst composition according to claim 1 , wherein the compound of tin is a tin salt, a dialkyl tin oxide, a dialkyl tin dialkanoate or an alkylstannoic acid.
12. A catalyst composition according to claim 1 , wherein the weight ratio of component (a) to component (b) is up to 1:1000, calculated as weight of Ti, Zr or Al in component (a) to weight of Ge, Sb or Sn in component (b).
13. A process for the production of a polyester comprising the reaction of a compound selected from the group consisting of terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, dimethyl 2,6 naphthalate or naphthalene dicarboxylic acid with an alcohol selected from the group consisting of 1,2-ethanediol, 1,4-butanediol, 1,3 propane diol, 1,6-hexanediol, trimethylol-propane and pentaerythritol in the presence of a catalyst composition comprising:
(a) a preformed metal-organic compound which is the product resulting from the reaction of
(i) an orthoester or condensed orthoester of titanium, zirconium, or aluminum,
(ii) an alcohol containing at least two hydroxyl groups,
(iii) a 2-hydroxy carboxylic acid, and
(iv) an organic base selected from the group consisting of quaternary ammonium hydroxide compounds; and
(b) at least one compound of germanium, antimony or tin.
14. A process as claimed in claim 13 in which the esterification reaction is a direct esterification or a transesterification and the catalyst is present in an amount in the range 0.2 to 1200 parts per million calculated as parts by weight of metal with respect to weight of product ester.
15. A process as claimed in claim 13 , wherein the esterification is a polyesterification and the catalyst is present in an amount in the range 5 to 500 parts per million calculated as parts by weight of metal with respect to weight of product polyester.
16. A process for the manufacture of a polyester article comprising:
(i) reacting together a compound selected from the group consisting of terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, dimethyl 2,6 naphthalate and naphthalene dicarboxylic acid with an alcohol selected from the group consisting of 1,2-ethanediol, 1,4-butanediol, 2,3-propanediol, 1,6-hexanediol, trimethylol-propane and pentaerythritol in the presence of a catalyst composition comprising:
(a) a preformed metal-organic compound which is the product resulting from the reaction of an orthoester or condensed orthoester of titanium, zirconium; or aluminum, an alcohol containing at least two hydroxyl groups, a 2-hydroxy carboxylic acid, and an organic base selected from the group consisting of quaternary ammonium hydroxide compounds, and
(b) at least one compound of germanium, antimony and tin,
(ii) optionally subjecting the resulting polymer to a solid phase polymerisation reaction, to form a polyester material having an intrinsic viscosity of at least 0.5 dl/g, as measured by the method of ASTM D-4603, and
(iii) forming said polyester article from said polymer in the melt phase and
(iv) cooling.
17. The process of claim 16 wherein said polyester article is a polyester fiber, and further comprising the additional step of drawing said polyester fiber.
18. A polyester article containing residues of a catalyst composition comprising:
(a) a preformed metal-organic compound which is the product resulting from the reaction of an orthoester or condensed orthoester of titanium, zirconium, or aluminum, an alcohol containing at least two hydroxyl groups, a 2-hydroxy carboxylic acid, and an organic base selected from the group consisting of quaternary ammonium hydroxide compounds, and
(b) at least one compound of germanium, antimony or tin.
19. A polyester article as claimed in claim 18 , which is a fibre, film or container.
20. A polyester article as claimed in claim 19 comprising an industrial fibre.
21. A polyester article as claimed in claim 19 comprising a fibre suitable for use as a textile fibre.
22. A tire cord comprising said industrial fiber of claim 20 .
23. A seat belt comprising said industrial fiber of claim 20 .
24. A rubber reinforced article comprising said tire cord of claim 22 .
25. A tire comprising said rubber reinforced article of claim 24 .
26. A safety restraint system comprising said seat belt of claim 23 .
27. A polyester article as claimed in claim 19 comprising a film.
28. A polyester article as claimed in claim 19 comprising a rigid packaging article.
29. A process for the manufacture of a polyester fiber comprising:
(i) reacting together a compound selected from the group consisting of terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, dimethyl 2,6 naphthalate and naphthalene dicarboxylic acid with an alcohol selected from the group consisting of 1,2-ethanediol, 1,4-butanediol 2,3-propanediol, 1,6-hexanediol, trimethylol-propane and pentaerythritol in the presence of a catalyst composition comprising: a preformed metal-organic compound which is the product resulting from the reaction of an orthoester or condensed orthoester of titanium, zirconium, or aluminum, an alcohol containing at least two hydroxyl groups, a 2-hydroxy carboxylic acid, and an organic base selected from the group consisting of quaternary ammonium hydroxide compounds, and
(ii) optionally subjecting the resulting polymer to a solid phase polymerisation reaction, to form a polyester material having an intrinsic viscosity of at least 0.5 dl/g, as measured by the method of ASTM D-4603, and
(iii) forming said polyester fiber from said polymer in the melt phase and
(iv) cooling.
30. The process of claim 29 further comprising the additional step of drawing said polyester fibre.
31. A polyester article according to claim 28 , wherein said rigid packaging article comprises a bottle.
32. A polyester article according to claim 28 , wherein said rigid packaging article comprises a jar.
33. A polyester article according to claim 28 , wherein said rigid packaging article comprises a clamshell package.
34. A process according to claim 29 , wherein the catalyst composition additionally contains at least one compound of germanium, antimony and tin.
35. A polyester material containing residues of a catalyst composition comprising a metal-organic compound consisting essentially of the product resulting from the reaction of:
(a) an orthoester or condensed orthoester of titanium, zirconium, or aluminium;
(b) an alcohol containing at least two hydroxyl groups;
(c) a 2-hydroxy carboxylic acid; and
(d) an organic base selected from the group consisting of tetraethyl ammonium hydroxide or benzyltrimethyl ammonium hydroxide.
36. A polyester material according to claim 35 , wherein the metal-organic compound is a reaction product of a titanium orthoester.
37. A polyester material according to claim 35 , wherein said carboxylic acid is selected from lactic acid, citric acid, malic acid and tartaric acid.
38. A polyester material according to claim 35 , wherein the metal-organic compound contains from 1 to 4 moles of 2-hydroxy carboxylic acid per mole of titanium or zirconium.
39. A catalyst composition consisting essentially of a metal-organic compound which is the product resulting from the reaction of:
(a) an orthoester or condensed orthoester of titanium, zirconium, or aluminium;
(b) an alcohol containing at least two hydroxyl groups;
(c) a 2-hydroxy carboxylic acid; and
(d) an organic base selected from the group consisting of tetraethyl ammonium hydroxide or benzyltrimethyl ammonium hydroxide.
40. A catalyst composition according to claim 39 , wherein the metal-organic compound is a reaction product of a titanium orthoester.
41. A catalyst composition according to claim 39 , wherein said carboxylic acid is selected from lactic acid, citric acid, malic acid and tartaric acid.
42. A catalyst composition according to claim 39 , wherein the metal-organic compound contains from 1 to 4 moles of 2-hydroxy carboxylic acid per mole of titanium or zirconium.
43. A catalyst composition according to claim 39 , consisting essentially of a metal-organic compound which is the product resulting from the reaction of:
(a) an orthoester or condensed orthoester of titanium or zirconium;
(b) a dihydric alcohol;
(c) a 2-hydroxy carboxylic acid selected from the group consisting of lactic acid, citric acid, malic acid and tartaric acid; and
(d) an organic base selected from the group consisting of tetraethylammonium hydroxide, or benzyltrimethyl ammonium hydroxide.
44. The polyester material of claim 35 , wherein the polyester material is in the form of a fiber.
45. The fiber of claim 44 , wherein the fiber has improved extensional viscosity.
46. The polyester fiber of claim 44 wherein said fiber is an industrial fiber.
47. The polyester fiber of claim 44 wherein said fiber is a textile fiber.
48. A tire cord comprising said industrial fiber of claim 46 .
49. A seat belt comprising said industrial fiber of claim 46 .
50. A rubber reinforced article comprising said tire cord of claim 48 .
51. A tire comprising said rubber reinforced article of claim 50 .
52. A safety restraint system comprising said seat belt of claim 49 .
53. The fiber of claim 45 wherein said fiber is industrial fiber.
54. The fiber of claim 45 wherein said fiber is a textile fiber.
55. A polyester fiber according to claim 44 , wherein the catalyst composition additionally contains at least one compound of germanium, antimony and tin.
56. A catalyst composition consisting of a metal-organic compound which is the product resulting from the reaction of:
(a) an orthoester or condensed orthoester of titanium, zirconium, or aluminium;
(b) an alcohol containing at least two hydroxyl groups;
(c) a 2-hydroxy carboxylic acid; and
(d) an organic base selected from the group consisting of tetraethyl ammonium hydroxide or benzyltrimethyl ammonium hydroxide.