Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol

• US 8,586,701 B2
• Filed: 07/03/2007
• Issued: 11/19/2013
• Est. Priority Date: 10/28/2005
• Status: Active Grant

• Current Assignee: Eastman Chemical Company
• Original Assignee: Eastman Chemical Company
• Inventors: Barton, Benjamin Fredrick, Shackelford, Damon Bryan
• Primary Examiner(s): Tischler, Frances
• Application Number:
  US11/773,275
• Publication Number:
  US 20070276065A1
• Time in Patent Office: 2,331 Days
• Field of Search: 526/66, 528/272, 528/274, 528/307, 528/271, 528/308.6, 528/308.7
• US Class Current: 528/308.7
• CPC Class Codes: C08G 63/199 Acids or hydroxy compounds containing cycloaliphatic rings
• 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

Disclosed is a process for the preparation of high molecular weight, thermoplastic copolyesters by reacting a diester composition comprising a dialkyl ester of terephthalic acid with a diol composition comprising a first diol component comprising 2,2,4,4-tetramethyl-1,3-cyclobutanediol and a second diol component comprising 1,4-cyclohexanedimethanol. The diester composition can be reacted with the first diol component to produce a polyester oligomer that can be reacted further with the second diol component to produce a modified polyester oligomer. The modified polyester oligomer can then be heated to form a copolyester. The process reduces the precipitation of poly(1,4-cyclohexylene dimethylene) terephthalate in the reaction mixture.

Claims

1. A process for the preparation of a copolyester, comprising:

reacting a diester composition comprising dimethyl terephthalate with a first diol component comprising 2,2,4,4-tetramethyl-1,3-cyclobutanediol and a second diol component comprising 1,4-cyclohexanedimethanol, said reaction comprising

(i) reacting said first diol component comprising about 100 mole percent of said 2,2,4,4-tetramethyl-1,3-cyclobutanediol, based on the total moles of 2,2,4,4-tetramethyl-1,3-cyclobutanediol in said first and second diol components, and about 30 to about 80 mole percent of said 1,4-cyclohexanedimethanol, based on the total moles of 1,4-cyclohexanedimethanol in said first and second diol components, with said diester composition to form a polyester oligomer at a conversion of said 2,2,4,4-tetramethyl-1,3-cyclobutanediol of at least 50 mole percent, based on the total moles of said 2,2,4,4-tetramethyl-1,3-cyclobutanediol in said first and second diol components;

(ii) reacting said second diol component comprising about 20 to about 70 mole percent of said 1,4-cyclohexanedimethanol based on the total moles of 1,4-cyclohexanedimethanol in said first and second diol components, with said polyester oligomer of step (i) to form a modified polyester oligomer; and

(iii) heating said modified polyester oligomer to form a thermoplastic, random copolyester having an inherent viscosity of about 0.4 dL/g to about 1.0 dL/g;

wherein the molar ratio of all diols in said first and second diol components to all diesters in said diester composition is about 1.1 to about 1.5.

2. The process according to claim 1 wherein said diol:

diester molar ratio is about 1.1 to about 1.40.

3. The process according to claim 2 wherein said diol:

diester molar ratio is about 1.1 to about 1.20.

4. The process according to claim 1 wherein said thermoplastic copolyester comprises about 100 mole percent, based on the total diacid residues, of the residues of terephthalic acid and about 85 to greater than about 50 mole percent, based on the total diol residues, of the residues of 1,4-cyclohexanedimethanol and about 15 to less than about 50 mole percent of the residues of 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

5. The process according to claim 4 wherein said thermoplastic copolyester comprises diol residues comprising about 20 to about 40 mole percent of the residues of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and about 60 to about 80 mole percent of the residues of 1,4-cyclohexanedimethanol.

6. The process according to claim 1 wherein said inherent viscosity of said thermoplastic copolyester is about 0.5 to about 0.80 dL/g.

7. The process according to claim 1 wherein said inherent viscosity of said thermoplastic copolyester is about 0.55 to about 0.75 dL/g.

8. The process according to claim 1 wherein said thermoplastic copolyester has a glass transition temperature of about 85 to about 200°

C.

9. The process according to claim 8 wherein said thermoplastic copolyester has a glass transition temperature of about 100 to about 120°

C.

10. The process according to claim 9 wherein said thermoplastic copolyester has a glass transition temperature of about 110 to about 120°

C.

11. The process according to claim 1 further comprising adding said first diol component incrementally to said diester composition in step (i), adding said second diol component incrementally to said polyester oligomer in step (ii), or a combination thereof.

12. The process according to claim 11 wherein said addition of said first and second diol components in step (i) and (ii) each are carried out continuously.

13. The process according to claim 1 which is carried out in at least 2 reactors.

14. The process according to claim 1 which is carried out in the presence of a thermal stabilizer comprising triphenyl phosphate and a catalyst comprising at least one tin compound.

15. The process according to claim 1 wherein said thermoplastic copolyester has an inherent viscosity of about 0.5 to about 0.8 dL/g, a Tg of about 100 to about 120°

C., and comprises (a) diacid residues comprising 100 mole percent of the residues of terephthalic acid; and

(b) diol residues comprising about 20 to about 30 mole percent of the residues of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, and about 70 to about 80 mole percent of the residues of 1,4-cyclohexanedimethanol;

(c) about 1 to about 100 ppm phosphorus, based on the total weight of said thermoplastic copolyester, and (d) about 15 to about 400 ppm tin, based on the weight of said thermoplastic copolyester.