Method for making polymers of alpha-hydroxy acids

• US 5,310,599 A
• Filed: 05/06/1993
• Issued: 05/10/1994
• Est. Priority Date: 05/06/1993
• Status: Expired due to Term

• Current Assignee: NatureWorks LLC (Cargill, Inc. (Agricultural Services Division))
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Ford, Thomas M.
• Primary Examiner(s): Kight, III, John
• Assistant Examiner(s): Dodson, Shelley A.
• Application Number:
  US08/057,817
• Time in Patent Office: 369 Days
• Field of Search: 528/354, 528/357, 525/415
• US Class Current: 528/354
• CPC Class Codes: C08G 63/08 Lactones or lactides
• CPC Class Codes: C08G 63/823 for the preparation of polylactones or polylactides

Abstract

A method providing a catalyzed ring opening polyester polymerization at a high reaction rate wherein the amount of organic acid in the reaction medium is maintained at an acid: catalyst ratio below 6:1.

Claims

1. A method for preparing polymers of alpha-hydroxy acids by catalyzed ring opening of cyclic diesters selected from the group consisting of lactide, glycolide and mixtures thereof and comprising up to 20 weight percent of a monomer selected from the group consisting of ##STR2## where n is 4 or 5, h, i, k and m are independently 1 or 2, each R is independently selected from hydrogen or hydrocarbyl containing up to 12 carbon atoms comprising the steps of:

a. forming a liquid phase dispersion of the cyclic diesters, monomer and ring-opening catalyst selected from the group consisting of tin compounds, yttrium compounds, compounds of lanthanum series rare earth metals having atomic numbers 57-71, titanates, zirconates, zinc compounds, antimony compounds and mixtures thereof, wherein the mole ratio of monomer to catalyst is 500-20,000;

1 and the mole ratio of organic acid to catalyst is less than 6;

1; and

b. maintaining (1) the temperature of the dispersion at 50-250 C., (2) the mole ratio of cyclic ester to catalyst at 500-20,000;

1 and (3) the mole ratio of organic acid to catalyst in the dispersion below 6;

1 to effect polymerization of the monomers to a conversion of at least 95% at a high rate.

2. The method of claim 1 in which the cyclic ester is selected from lactide, glycolide and mixtures thereof.

3. The method of claim 2 wherein the temperature is maintained at from about 160 C. to 220 C.

4. The method of claim 3 in which the method is carried out in an extruder.

5. The method of claim 4 in which the mole ratio of acid to catalyst is below 2:

1.

6. The method of claim 5 in which the mole ratio of cyclic ester to catalyst is 1,500-10,000:

1.

7. The method of claim 1 in which the dispersion contains a mixture of cyclic diester and a polymerizable comonomer to produce a random copolymer of the cyclic ester.

8. The method of claim 7 in which the comonomer is selected from the group consisting of epsilon caprolactone, delta valerolactone, 1,5-dioxepan-2-one, 1,4-dioxan-2-one, beta butyrolactone, beta propiolactone, 6-methyl-2,5-morpholinedione and mixtures thereof.