Method of ring-opening polymerization, and related compositions and articles

Patent metadata

Field	Value
Publication number	US-9388275-B2
Application number	US-47570009-A
Country	US
Kind code	B2
Filing date	Jun 1, 2009
Priority date	Jun 1, 2009
Publication date	Jul 12, 2016
Grant date	Jul 12, 2016

Abstract

Methods to form a polymer by ring-opening polymerization include reacting, a mixture comprising a monomer, an accelerator, an initiator, and a catalyst comprising a 1,1,1,3,3,3-hexafluoropropan-2-ol-2-yl group to form the polymer. Also disclosed are polymers including a residual amount of the catalyst in an amount greater than 0 weight percent.

First claim

The invention claimed is:

1. A method, comprising:
reacting, to form a polymer by ring-opening polymerization, a mixture comprising:
a monomer,
an accelerator in an amount of 0.1 to 5 mol %,
an initiator in an amount of 0.1 to 5 mol %, and
a catalyst comprising one or more 1,1,1,3,3,3-hexafluoropropan-2-ol-2-yl groups in an amount of 1 to 5 mol %, wherein the mol % are based on moles of the monomer.

2. The method of claim 1 , wherein the mixture further comprises a solvent.

3. The method of claim 1 , wherein the mixture is free of a solvent.

4. The method of claim 1 , wherein the catalyst is of formula (1)
R 1 —C(CF 3 ) 2 OH  (1),

wherein R 1 represents a hydrogen or a substituent having from 1 to 20 carbons selected from the group consisting of alkyl group, substituted alkyl group, cycloalkyl group, substituted cycloalkyl group, heterocycloalkyl group, substituted heterocycloalklyl group, aryl group, substituted aryl group, and combinations thereof.

5. The method of claim 1 , wherein the catalyst is of formula (2):

wherein R 2 is a bridging group having a valence of 2 containing from 1 to 20 carbons selected from the group consisting of an alkylene group, a substituted alkylene group, a cycloalkylene group, substituted cycloalkylene group, a heterocycloalkylene group, substituted heterocycloalkylene group, an arylene group, a substituted arylene group, and combinations thereof.

6. The method of claim 1 , wherein the catalyst is selected from the group consisting of 4-HFA-St, 4-HFA-Tol, HFTB, NFTB, HFIP, 3,5-HFA-MA, 3,5-HFA-St, 1,3-HFAB, 1,4-HFAB, and combinations thereof.

7. The method of claim 1 , wherein the one or more 1,1,1,3,3,3-hexafluoropropan-2-ol-2-yl groups are bound to a support by a linking group.

8. The method of claim 7 , wherein the linking group comprises a C 1 -C 12 alkyl group, C 1 -C 12 heteroalkyl group, ether group, thioether group, amino group, ester group, amide group, or a combination of the foregoing linking groups.

9. The method of claim 7 , wherein the support comprises a polymer, a crosslinked polymer bead, an inorganic particle, or a metallic particle.

10. The method of claim 1 , wherein the monomer is a cyclic ester.

11. The method of claim 10 , wherein the cyclic ester is selected from the group consisting of lactide, beta-butyrolactone, gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, epsilon-caprolactone, and combinations thereof.

12. The method of claim 1 , wherein the monomer is a cyclic carbonate.

13. The method of claim 10 , wherein the cyclic carbonate is selected from the group consisting of trimethylenecarbonate, tetramethylene carbonate, pentamethylene carbonate, MODC-A, MODC-M, MODC-TB, MODC-E, and combinations of the foregoing cyclic carbonates.

14. The method of claim 1 , wherein reacting is at a temperature of from 15° C. to 200° C.

15. A polymer formed by the method of claim 1 , comprising a residual amount greater than 0 wt % of the catalyst.

16. The polymer of claim 15 , wherein the polymer has a polydispersity index of 1.01 to 1.35.

17. The polymer of claim 15 , wherein the polymer is polylactide or poly(3-hydroxybutyrate), and the polymer has a tacticity which is isotactic, atactic, or syndiotactic.

18. An article comprising the polymer of claim 15 .

19. A method, comprising:
reacting, to form a polymer by ring-opening polymerization, a mixture comprising:
a cyclic ester and/or cyclic carbonate monomer,
0.1 to 5.0 mol % a nitrogen base accelerator,
0.1 to 5.0 mol % an alcohol initiator based on an equivalent molecular weight per hydroxyl group in the alcohol initiator, and
1 to 5 mol % of a catalyst comprising one or more 1,1,1,3,3,3-hexafluoropropan-2-ol-2-yl groups; wherein mol % is based on moles of the monomer.

Assignees

• Coulembier Olivier
• Hedrick James L
• Nelson Alshakim
• Rice Julia E
• Sanders Daniel P
• IBM
• Univ Mons Hainaut

Inventors

• Coulembier Olivier
• Hedrick James L
• Nelson Alshakim
• Rice Julia E
• Sanders Daniel P

Classifications

• C08G63/823 Primary

  for the preparation of polylactones or polylactides · CPC title

• C08G63/06

  derived from hydroxycarboxylic acids · CPC title