Soluble mono-alkyl stannoic acid catalyst and its use in preparing high molecular weight polyesters

• US 5,891,985 A
• Filed: 10/01/1997
• Issued: 04/06/1999
• Est. Priority Date: 10/09/1996
• Status: Expired due to Term

• Current Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Brugel, Edward Gus
• Primary Examiner(s): Acquah, Samuel A.
• Application Number:
  US08/942,116
• Time in Patent Office: 552 Days
• Field of Search: 528/271, 528/279, 528/283, 528/285, 528/308, 528/308.6, 524/783, 524/784, 502/102, 502/150, 502/170, 502/172
• US Class Current: 528/283
• CPC Class Codes: C07F 7/2224 Compounds having one or more tin-oxygen linkages
• CPC Class Codes: C08G 63/85 Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof C08G63/823 takes precedence

Abstract

A soluble mono-alkyl Stannoic Acid/glycol liquid phase catalyst produced from the reaction of a mono-alkyl Stannoic Acid and a glycol at a temperature of from at least 180° C., and its use in preparing high molecular weight polyester polymers.

Claims

1. A soluble mono-alkyl Stannoic Acid catalyst which is formed by heating a mono-alkyl Stannoic Acid with a glycol of the formula (I):

space="preserve" listing-type="equation">HO--R--OH (I)

wherein R is selected from C₂ to C₅₀ alkyl, cycloalkyl, aryl and combinations thereof at a temperature of at least 180°

C. whereby the mono-alkyl Stannoic Acid is selectively reacted with the glycol to yield a mono-alkyl Stannoic Acid/glycol liquid phase.

2. The soluble mono-alkyl Stannoic Acid catalyst of claim 1 in which the mono-alkyl Stannoic Acid and the glycol are heated to a temperature in the range of from 200°

C. to 210°

C.

3. In a process for preparing a high molecular weight polyester polymer from a low molecular weight reaction product obtained from (trans)esterifying one or more mono-, di- or tricarboxylic acids and one or more alkyl(aryl) glycols in the presence of a (trans)esterification catalyst, the improvement comprising (trans)esterifying said one or more mono-, di- or tricarboxylic acids and said one or more alkyl(aryl) glycols in the presence of a mono-alkyl Stannoic Acid/glycol liquid phase catalyst which is produced by reacting a mono-alkyl Stannoic Acid with an alkyl(aryl) glycol at a temperature in the range of at least 180°

C. at a glycol;

tin ratio in the range of from 3;

1 to 1000;

1 by weight.

4. The improvement according to claim 3 wherein the (trans)esterification catalyst further comprises a conventional catalyst selected from the group consisting of unreacted tin compounds, antimony oxide, antimony glycolates, titanates, germanium compounds and combinations thereof.

5. The improvement according to claim 4 wherein the glycol reactant in which the mono-alkyl Stannoic Acid is heated to produce the mono-alkyl Stannoic Acid/glycol catalyst corresponds to the alkyl(aryl) glycol portion of the high molecular weight polyester polymer reaction product.

6. The improvement according to claim 5 in which the one or more mono-, di- or tricarboxylic acids is a dicarboxylic acid selected from terephthalic acid and isophthalic acid;

the mono-alkyl Stannoic Acid is mono-butyl Stannoic Acid; and

the alkyl(aryl) glycol is a diol selected from 1,2-ethane diol, 1,3-propane diol and 1,4-propane diol.

7. The improvement according to claim 6 in which the mono-butyl Stannoic Acid and the diol are reacted at a temperature in the range of from 200°

C. to 210°

C.

8. A method for preparing a mono-alkyl Stannoic Acid/glycol soluble catalyst which comprises:

(a) heating a mono-alkyl Stannoic Acid selected from mono-butyl Stannoic Acid and mono-octyl Stannoic Acid in the presence of a glycol to a temperature of at least 180°

C. until the starting tin compound is selectively reacted with the glycol;

(b) allowing the reaction mixture to cool to yield a mono-alkyl Stannoic Acid/glycol liquid phase and a solid precipitate; and

optionally

(c) removing the solid precipitate from the mono-alkyl Stannoic Acid/glycol liquid phase.

9. The method of claim 8 in which the mono-alkyl Stannoic Acid and the glycol are heated to a temperature in the range of from 200°

C. to 210°

C.

10. A process for preparing a high molecular weight polyester polymer selected from poly(ethylene terephthalate), poly(1,3-propylene terephthalate) and poly(1,4-butylene terephthalate) which comprises:

(a) (trans)esterifying a dicarboxylic acid selected from terephthalic acid and isothalaic acid with a glycol selected from 1,2-ethanediol, 1,3-propanediol and 1,4-butanediol in the presence of a (trans)esterification catalyst which is a mono-alkyl Stannoic Acid/glycol liquid phase catalyst which is produced by reacting a mono-alkyl Stannoic Acid with a glycol selected from 1,2-ethanediol, 1,3-propanediol and 1,4-butanediol at a temperature in the range of from 200°

C. to 210°

C. at a tin;

glycol ratio in the range of from 3;

1 to 1000;

1 by weight to produce a low molecular weight pre-polymer, and

(b) polymerizing the pre-polymer to high molecular weight in a meltpolycondensation reaction or by solid state polymerization.

11. The process of claim 10 in which the (trans)esterification catalyst further comprises a conventional catalyst selected from the group consisting of unreacted tin compounds, antimony oxide, antimony glycolates, titanates, germanium oxides and combinations thereof.

12. The process of claim 11 in which polymerization to high molecular weight according to step (b) is carried out by introducing for step (b) a polymerization catalyst selected from the group consisting of a mono-alkyl Stannoic Acid/glycol liquid catalyst, unreacted tin compounds, antimony oxide, antimony glycolates, titanates, germanium oxides, and combinations thereof.