CA2433730A1 - Polymerization process using mono- and di-functional initiators to prepare fast crystallizing polylactone copolymers - Google Patents

Polymerization process using mono- and di-functional initiators to prepare fast crystallizing polylactone copolymers Download PDF

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Publication number
CA2433730A1
CA2433730A1 CA002433730A CA2433730A CA2433730A1 CA 2433730 A1 CA2433730 A1 CA 2433730A1 CA 002433730 A CA002433730 A CA 002433730A CA 2433730 A CA2433730 A CA 2433730A CA 2433730 A1 CA2433730 A1 CA 2433730A1
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Prior art keywords
functional
initiator
mono
monomer
polymerization
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CA002433730A
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French (fr)
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CA2433730C (en
Inventor
Hugh D. Newman, Jr.
Dennis D. Jamiolkowski
Sasa Andjelic
Rao S. Bezwada
Brian M. Kelly
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Ethicon Inc
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Ethicon Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/664—Polyesters containing oxygen in the form of ether groups derived from hydroxy carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes

Abstract

The present invention is directed to a process for making an absorbable polylactone copolymer prepared in part from about 2 to about 80 mole percent glycolide, which process utilizes a combination of a monofunctional polymerization initiator and a di-functional polymerization initiator, to achieve rates of crystallization of the copolymer of at least about 2 times faster than the rate of crystallization of a copolymer made by a similar process utilizing either the mono-functional or the di-functional polymerization initiator alone. Absorbable polylactone copolymers prepared by such processes and medical devices containing such copolymers are also disclosed.

Claims (19)

1. A polymerization process for making an absorbable crystallizable polylactone copolymer, comprising:
providing from about 2 to about 80 mole percent of a first lactone monomer comprising glycolide and from about 98 to about 20 mole percent of a second lactone monomer other than glycolide, combining the glycolide and lactone monomers with a mono-functional polymerization initiator and a di-functional polymerization initiator at a molar ratio of mono-functional:di-functional initiator of from 10:90 to 90:10;
polymerizing the glycolide and lactone monomers in the presence of the monofunctional and the di-functional polymerization initiators, thereby providing the absorbable polylactone copolymer.
2. The process of claim 1, wherein the molar ratio of mono-functional:di-functional initiator is from about 25:75 to about 85:15.
3. The process of claim 1, wherein the monofunctional initiator is selected from the group consisting of C4 or higher primary aliphatic alcohols and the di-functional initiator is selected from the group consisting of C4 or higher compounds possessing two primary aliphatic alcohol groups.
4. The process of claim 3, wherein the monofunctional initiator is dodecanol and the di-functional initiator is diethylene glycol.
5. The process of claim 4, wherein the monomer comprises from about 5 to about 10 mole percent glycolide monomer.
6. The process of claim 5, wherein the molar ratio of mono-functional;di-functional initiator is from about 40:60 to about 60:40.
7. The process of claim 6, wherein the monomer mixture comprises about 92 mole percent p-dioxanone monomer and about 8 mole percent glycolide monomer and the molar ratio of dodecanol:diethylene glycol is about 50:50.
8. The process of claim 1, wherein the rate of crystallization is at least about 2 times greater than the rate of crystallization of a polymer made from a polymerization process that utilizes either the mono-functional or di-functional initiator alone.
9. The process of claim 6, wherein the rate of crystallization is at least about 15 times greater than the rate of crystallization of a polymer made from a polymerization process that utilizes either the dodecanol or diethylene glycol alone.
10. The process of claim 2, wherein the monomer mixture comprises from about 70 to about 80 mole percent glycolide monomer.
11. The process of claim 10, wherein the molar ratio of mono-functional:di-functional initiator is 25:75.
12. The process of claim 11, wherein the mono-functional initiator is dodecanol and the di-functional initiator is diethylene glycol.
13. The process of claim 12, wherein the monomer mixture comprises about 76 mole percent glycolide monomer and about 24 mole percent s-caprolactone monomer.
14; The process of claim 13, wherein the rate of polymerization is at least about 15 times greater than the rate of polymerization of a polymerization process that utilizes either the dodecanol or diethylene glycol alone.
15. The process of claim 1, wherein the rate of polymerization is at least about 10 times greater than the rate of polymerization of a polymerization process that utilizes either the mono-functional or di-functional polymerization initiator alone.
16, The process of claim 1, wherein said lactone monomer is selected from the group consisting of L(-)-lactide, D(+)-lactide, meso-lactide, trimethylene carbonate, p-dioxanone, epsilon-caprolactone and combinations thereof.
17. The process of claim 1, wherein the molar ratio of mono-functional to di-functional initiator is from about 20:80 to about 65:35.
18. The process of claim 1, wherein the molar ratio of mono-functional to di-functional initiator is from about 25:75 to about 60:40.
19. An absorbable polylactone copolymer having an average crystal size (diameter) of about 25 microns or less made by the process comprising the steps of:
providing from about 2 to about 80 mole percent of a first lactone monomer comprising glycolide and from about 98 to about 20 mole percent of a second lactone monomer other than glycolide, combining the glycolide and lactone monomers with a monofunctional initiator and a di-functional initiator at a molar ratio of mono-functional:di-functional initiator of from 10:90 to 90:10;
polymerizing the glycolide and lactone monomers in the presence of the monofunctional and the di-functional polymerization initiators, thereby providing the absorbable polylactone copolymer.
CA2433730A 2002-06-28 2003-06-27 Polymerization process using mono- and di-functional initiators to prepare fast crystallizing polylactone copolymers Expired - Fee Related CA2433730C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/185,078 2002-06-28
US10/185,078 US6831149B2 (en) 2002-06-28 2002-06-28 Polymerization process using mono-and di-functional initiators to prepare fast crystallizing polylactone copolymers

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CA2433730A1 true CA2433730A1 (en) 2003-12-28
CA2433730C CA2433730C (en) 2012-04-10

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US (1) US6831149B2 (en)
EP (1) EP1375557B1 (en)
JP (1) JP4672244B2 (en)
AT (1) ATE335032T1 (en)
AU (1) AU2003205002B2 (en)
CA (1) CA2433730C (en)
DE (1) DE60307189T2 (en)
ES (1) ES2269925T3 (en)

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Also Published As

Publication number Publication date
AU2003205002A1 (en) 2004-01-22
CA2433730C (en) 2012-04-10
DE60307189T2 (en) 2007-07-05
ATE335032T1 (en) 2006-08-15
DE60307189D1 (en) 2006-09-14
US20040006199A1 (en) 2004-01-08
US6831149B2 (en) 2004-12-14
AU2003205002B2 (en) 2007-07-19
JP4672244B2 (en) 2011-04-20
ES2269925T3 (en) 2007-04-01
EP1375557B1 (en) 2006-08-02
JP2004131693A (en) 2004-04-30
EP1375557A1 (en) 2004-01-02

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