CA1139043A - ISOMORPHIC COPOLYMERS OF .epsilon.-CAPROLACTONE AND 1,5-DIOXEPAN-2-ONE - Google Patents
ISOMORPHIC COPOLYMERS OF .epsilon.-CAPROLACTONE AND 1,5-DIOXEPAN-2-ONEInfo
- Publication number
- CA1139043A CA1139043A CA000342613A CA342613A CA1139043A CA 1139043 A CA1139043 A CA 1139043A CA 000342613 A CA000342613 A CA 000342613A CA 342613 A CA342613 A CA 342613A CA 1139043 A CA1139043 A CA 1139043A
- Authority
- CA
- Canada
- Prior art keywords
- dioxepan
- caprolactone
- copolymers
- percent
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- 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
Abstract
ABSTRACT
ISOMORPHIC COPOLYMERS OF .epsilon.-CAPROLACTONE AND
1,5-DIOXEPAN-2-ONE
Isomorphic copolymers of .epsilon.-caprolactone with from about 3 to 15 percent 1,5-dioxepan-2-one have melting points in the range of 54 to 66°C and may be extruded into fibers having elongations in the range of 120 to 235 percent. The copolymers are useful for the preparation of filaments, films and molded articles for general and surgical applica-tions including surgical sutures and casts.
ISOMORPHIC COPOLYMERS OF .epsilon.-CAPROLACTONE AND
1,5-DIOXEPAN-2-ONE
Isomorphic copolymers of .epsilon.-caprolactone with from about 3 to 15 percent 1,5-dioxepan-2-one have melting points in the range of 54 to 66°C and may be extruded into fibers having elongations in the range of 120 to 235 percent. The copolymers are useful for the preparation of filaments, films and molded articles for general and surgical applica-tions including surgical sutures and casts.
Description
~TH-4$~
ISOMORPHIC COPOL~ERS OF ~ CAPROLACTONE AND
1,5-DIO B PA~-2-ONE
BACKGROUND OF THE INVEN~ION
This inYention relates to copo}ymers of lacto~es and ethe~ lac~ones,and, more particularly, to copolymers of -caprolactone with 1,5-dioxepan-2-one. The copolymers of the present invention are characterized by significantly lower melting points than comparable homopolymers of poly-caprolactone, making such copolymers particularly desirable for use in temperature sensitive applications such as form-ing medical ca5ts for broken bones~
The copolymers of the present inve~tion can be processed into fibers, films and sheeks. The fibers are characterized by having significantly higher elongation and tensile strength values than comparable homopolymexs of caprolactone. Such ~ibers are useful as surgical sutures and in a variety of other textile and medical applications.
Hornopolymers and various copolymers of capro lactone are well-~nown in the art. Monomers of 1,5 dioxepan-2-one an~ their utility for the production of polymers which can be used in resins, ibers, plastic5 ~ ad-hesives and surface coatings are also known as disclosed,for example, in British Patent No. 1,272~733. The specific copolymers o the present invention and the ncvel propex~
ties thereor have not, however, been suggested in the priox art.
SU.~MARY
The novel compositions of the present invention comprise isomorphic copolymers of ~-caprolactone with from about 3 to 15 percent 1,5-dioxepan-2-one. Purified mono-mers are reacted in the presence of a catalyst and atelevated temperatures to obtain a copolymer product having an inherent viscosity in excess of 1.5. The copolymers of the present invention have melting points as low as 54C, as compa~-ed to 70C for comparable homopolymers o~ capro-lactone. Fibers prepared from the copolymers by melt ex-trusion have elongations as high as 235 percent, a~ com-pared to about 124 percent for comparable homopolymers of caprolactone.
DESCRIPTION OF PREFERRED E~ODlMENTS
The isomorphic copolymers of the present inven-tion are prepared by the random polymeriza~lon of purified ~-caprolactone with from about 3 to 15 percent by weight of 1,5-dioxepan-2 one monomer in the presence of an organo-metallic catalyst such as stannous octoate. The copolymershave a high degree of crystallinity, at least about 40 per-cent as a result of the sequential isomorphism associated with the polymer chain. The crystallinity o the copolymers of the present. invention is comparable to that of ~-capro-lactone homopolymer.
The preparation of the copolymers o~ the presentinvention is specifically illustrated by the Example~ pre-sented herea~ter. In the Examples, inherent ~iscosity (ninh) was obtained on solutions of polymer or fiber (1 g per liter) in hexafluoroisopropanol (HFIP) at 25C. Melt-ing temperatures (Tm) were determined by remelting on a DuPont 990 DSC apparatus using 5 mg samples of polymer and heating at a rate sf 10~C per minute under nitrogen.
Crystallinity was determined by the method of ~ermanns and Weidinger using a DuPont 310 curve analyzer.
Continuous filaments were prepared ~y melt ex-truding the polymer in a conventional manner, and the fila-ments were drawn 6X at room temperature to achieve molecular ~.~ 3~
orientation. The drawn filaments were eYaluatea for straight tensile strength, knot strength, elongation and Young's modulus fQllowing conventional, single-filament textile test-ing procedures.
EXAMæLE I
Poly-~-Caprolactone Control Polymer ~ -Caprolactone was purified by vacuum distillation to 99.9~ percent as determined by gas chromatography. The purified lactone ~22.8 g, 0.Z0 mole) and a catalytic amoun~
of stannous octoate (0.06 ml o~ 0.33 M toluene solution, 20 mmole) were heated in a sealed ampul, equipped for mag-netic stirring, for 22 hrs at 170C. The polymer was iso-lated and melt spun into continuous filaments. The proper-ties of the polymer and filaments are presented in Table I.
EXAMPLE II
95/5 Isomorphic Copolyester of ~-Caprolactone and 1,5-Dioxepan 2-One Purified ~-caprolactone (21.7 g, 07190 mole), 1,5-dioxepan~2-one (1.16 g, 0.010 mole) and a catalytic amount of stannous octoate (0.06 ml of 0.33 M toluene solu-tion, 0~020 mmole) were heated in a sealed ampul, e~uipped for magnetic stirring, for 22 hrs at 170~C. The polymer was isolated, and melt spun into continuous filaments. The properties o~ the polymer and drawn filaments are presented in Table I.
EXA~LE III
90/10 Isomorphic Copolyester of ~-Caprolactone and 1,5-Dioxepan-2-One Purified ~-caprolactone (ZS.65 g, 0.225 mole), 1,5-dioxepan-2-one (2.93 g, 0.025 mole), and a catalytic amount of stannous octoate (0.07 ml of 0~33 M solution in toluene, 0.0Z5 mmole) were heated in a magnetically-stirred, sealed ~mpul at 760 mm nitrogen accordlng to th~ following scheme: 16 hrs at 100C, 8 hrs at 150C, ar.d 18 hrs at 170C. The polymer was isol~ted and melt spun into con-tinuous ~ilaments. The properties of ~he ~olymer and drawn filaments are presented in Table I.
EXAMPLE IV
85/15 Isomorphic Copolyester of Caprolactone and 1,5-Dioxepan-2-One Purified -caprolactone (19.4 g, 0.170 mole), 1,5-dioxepan-2-one (3.4~ g, 0.030 mole) and a catalytic amount of stannous octoate (0.06 ~1 of 0.33 M toluene solu-tion, 20 mmole) were h~ated in a sealed ampul, equipped for magnetic stirriny, for 22 hrs at 170C. The polymer was isolated and melt spun into continuous filaments. The properties of the polymer and drawn filaments are pre~ented in.Table I.
TABLE I
Example No.
I II III IV
POLYMER
~-Caprolactone/
1,5-dioxepan-Z-one100/0 95/5 90/10 85/15 ~inh 1.80 1.82 1.57 1.66 Tm,C, DSC, reheating 70 66 54 56 FI
25 Diameter, mils 8.6 7.6 7.0 6.8 Tensile strength, psi44,800 57,300 54,500 44,100 Knot strength, psi37,90035,30036,300 44~100 Elongation, % 124 235 173 120 Young's modulua., psi95 3000 105,000106,000 113,000 30 ~inh 1.90 1.81 1.77 1.66 Crys~allini~y, % 40 42 43 42 ET~-458 As illustrated by the preceding Examples, the co-polymers of the present inventio~ aford a means by which the melting point of polycaprolactone may be depressed while maintaining a high degree of polymer crystallinity, thereby - 5 improving the physical properties of the filaments produced therefrom. Filaments comprising copolymers containing 3 to 10 percent 1,5-dioxepan-2-one are characterized by elonga-tions in excess o 150 percen~ and tensile ~trengths in ex cess o 50,000 psi. A remarkable increase in filament elongation and tensile s~rength is observed wi~h incorpora-tion cf only 5 percen~ 1,5-dioxepan 2~-one comonomer, with these values decreasing as the amount of comonomer is in-creasedO A minimum polymer melting point o~ 54C is ob-served at 10 percent 1,5-dioxepan-2-one.
The 90/10 copolymer of ~-caprolactone and 1 r 5-dioxepan-2-one is a particularly preferred composition for use in medical applicationssuch as surgical sutures and casts because of its very low melting point and excellent physical propertiesO
Copolymers containing in excess of 15 percent 1,5-dioxepan-2-one may be prepaxed and used in molding ap-plications although physical prope;rties o such polymers are generally inferior to those compositions containing 3 to 15 percent 1~5-dioxepan-2-one, especially in the form of filaments.
Thermo-formable medical devices such as casts ~or hroken limbs may be constructed of woven or nonwoven fi-brous mats and/or ~ilms or sheets of the copolymers of the pre~ent invention. Such devices may be heated to near the melting point, ~ormed around the broken limb with no thermal damage to the patient, ~nd allowed to cool whereupon the device becomes rigid and provides mechanical support or the broken }imb.
ISOMORPHIC COPOL~ERS OF ~ CAPROLACTONE AND
1,5-DIO B PA~-2-ONE
BACKGROUND OF THE INVEN~ION
This inYention relates to copo}ymers of lacto~es and ethe~ lac~ones,and, more particularly, to copolymers of -caprolactone with 1,5-dioxepan-2-one. The copolymers of the present invention are characterized by significantly lower melting points than comparable homopolymers of poly-caprolactone, making such copolymers particularly desirable for use in temperature sensitive applications such as form-ing medical ca5ts for broken bones~
The copolymers of the present inve~tion can be processed into fibers, films and sheeks. The fibers are characterized by having significantly higher elongation and tensile strength values than comparable homopolymexs of caprolactone. Such ~ibers are useful as surgical sutures and in a variety of other textile and medical applications.
Hornopolymers and various copolymers of capro lactone are well-~nown in the art. Monomers of 1,5 dioxepan-2-one an~ their utility for the production of polymers which can be used in resins, ibers, plastic5 ~ ad-hesives and surface coatings are also known as disclosed,for example, in British Patent No. 1,272~733. The specific copolymers o the present invention and the ncvel propex~
ties thereor have not, however, been suggested in the priox art.
SU.~MARY
The novel compositions of the present invention comprise isomorphic copolymers of ~-caprolactone with from about 3 to 15 percent 1,5-dioxepan-2-one. Purified mono-mers are reacted in the presence of a catalyst and atelevated temperatures to obtain a copolymer product having an inherent viscosity in excess of 1.5. The copolymers of the present invention have melting points as low as 54C, as compa~-ed to 70C for comparable homopolymers o~ capro-lactone. Fibers prepared from the copolymers by melt ex-trusion have elongations as high as 235 percent, a~ com-pared to about 124 percent for comparable homopolymers of caprolactone.
DESCRIPTION OF PREFERRED E~ODlMENTS
The isomorphic copolymers of the present inven-tion are prepared by the random polymeriza~lon of purified ~-caprolactone with from about 3 to 15 percent by weight of 1,5-dioxepan-2 one monomer in the presence of an organo-metallic catalyst such as stannous octoate. The copolymershave a high degree of crystallinity, at least about 40 per-cent as a result of the sequential isomorphism associated with the polymer chain. The crystallinity o the copolymers of the present. invention is comparable to that of ~-capro-lactone homopolymer.
The preparation of the copolymers o~ the presentinvention is specifically illustrated by the Example~ pre-sented herea~ter. In the Examples, inherent ~iscosity (ninh) was obtained on solutions of polymer or fiber (1 g per liter) in hexafluoroisopropanol (HFIP) at 25C. Melt-ing temperatures (Tm) were determined by remelting on a DuPont 990 DSC apparatus using 5 mg samples of polymer and heating at a rate sf 10~C per minute under nitrogen.
Crystallinity was determined by the method of ~ermanns and Weidinger using a DuPont 310 curve analyzer.
Continuous filaments were prepared ~y melt ex-truding the polymer in a conventional manner, and the fila-ments were drawn 6X at room temperature to achieve molecular ~.~ 3~
orientation. The drawn filaments were eYaluatea for straight tensile strength, knot strength, elongation and Young's modulus fQllowing conventional, single-filament textile test-ing procedures.
EXAMæLE I
Poly-~-Caprolactone Control Polymer ~ -Caprolactone was purified by vacuum distillation to 99.9~ percent as determined by gas chromatography. The purified lactone ~22.8 g, 0.Z0 mole) and a catalytic amoun~
of stannous octoate (0.06 ml o~ 0.33 M toluene solution, 20 mmole) were heated in a sealed ampul, equipped for mag-netic stirring, for 22 hrs at 170C. The polymer was iso-lated and melt spun into continuous filaments. The proper-ties of the polymer and filaments are presented in Table I.
EXAMPLE II
95/5 Isomorphic Copolyester of ~-Caprolactone and 1,5-Dioxepan 2-One Purified ~-caprolactone (21.7 g, 07190 mole), 1,5-dioxepan~2-one (1.16 g, 0.010 mole) and a catalytic amount of stannous octoate (0.06 ml of 0.33 M toluene solu-tion, 0~020 mmole) were heated in a sealed ampul, e~uipped for magnetic stirring, for 22 hrs at 170~C. The polymer was isolated, and melt spun into continuous filaments. The properties o~ the polymer and drawn filaments are presented in Table I.
EXA~LE III
90/10 Isomorphic Copolyester of ~-Caprolactone and 1,5-Dioxepan-2-One Purified ~-caprolactone (ZS.65 g, 0.225 mole), 1,5-dioxepan-2-one (2.93 g, 0.025 mole), and a catalytic amount of stannous octoate (0.07 ml of 0~33 M solution in toluene, 0.0Z5 mmole) were heated in a magnetically-stirred, sealed ~mpul at 760 mm nitrogen accordlng to th~ following scheme: 16 hrs at 100C, 8 hrs at 150C, ar.d 18 hrs at 170C. The polymer was isol~ted and melt spun into con-tinuous ~ilaments. The properties of ~he ~olymer and drawn filaments are presented in Table I.
EXAMPLE IV
85/15 Isomorphic Copolyester of Caprolactone and 1,5-Dioxepan-2-One Purified -caprolactone (19.4 g, 0.170 mole), 1,5-dioxepan-2-one (3.4~ g, 0.030 mole) and a catalytic amount of stannous octoate (0.06 ~1 of 0.33 M toluene solu-tion, 20 mmole) were h~ated in a sealed ampul, equipped for magnetic stirriny, for 22 hrs at 170C. The polymer was isolated and melt spun into continuous filaments. The properties of the polymer and drawn filaments are pre~ented in.Table I.
TABLE I
Example No.
I II III IV
POLYMER
~-Caprolactone/
1,5-dioxepan-Z-one100/0 95/5 90/10 85/15 ~inh 1.80 1.82 1.57 1.66 Tm,C, DSC, reheating 70 66 54 56 FI
25 Diameter, mils 8.6 7.6 7.0 6.8 Tensile strength, psi44,800 57,300 54,500 44,100 Knot strength, psi37,90035,30036,300 44~100 Elongation, % 124 235 173 120 Young's modulua., psi95 3000 105,000106,000 113,000 30 ~inh 1.90 1.81 1.77 1.66 Crys~allini~y, % 40 42 43 42 ET~-458 As illustrated by the preceding Examples, the co-polymers of the present inventio~ aford a means by which the melting point of polycaprolactone may be depressed while maintaining a high degree of polymer crystallinity, thereby - 5 improving the physical properties of the filaments produced therefrom. Filaments comprising copolymers containing 3 to 10 percent 1,5-dioxepan-2-one are characterized by elonga-tions in excess o 150 percen~ and tensile ~trengths in ex cess o 50,000 psi. A remarkable increase in filament elongation and tensile s~rength is observed wi~h incorpora-tion cf only 5 percen~ 1,5-dioxepan 2~-one comonomer, with these values decreasing as the amount of comonomer is in-creasedO A minimum polymer melting point o~ 54C is ob-served at 10 percent 1,5-dioxepan-2-one.
The 90/10 copolymer of ~-caprolactone and 1 r 5-dioxepan-2-one is a particularly preferred composition for use in medical applicationssuch as surgical sutures and casts because of its very low melting point and excellent physical propertiesO
Copolymers containing in excess of 15 percent 1,5-dioxepan-2-one may be prepaxed and used in molding ap-plications although physical prope;rties o such polymers are generally inferior to those compositions containing 3 to 15 percent 1~5-dioxepan-2-one, especially in the form of filaments.
Thermo-formable medical devices such as casts ~or hroken limbs may be constructed of woven or nonwoven fi-brous mats and/or ~ilms or sheets of the copolymers of the pre~ent invention. Such devices may be heated to near the melting point, ~ormed around the broken limb with no thermal damage to the patient, ~nd allowed to cool whereupon the device becomes rigid and provides mechanical support or the broken }imb.
Claims
1. An isomorphic copolymer of .epsilon.-caprolactone with from about 3 to 15 percent by weight 1,5-dioxepan-2-one.
2. A copolymer of Claim 1 having an inherent vis-cosity greater than about 1.4.
3. A copolymer of Claim 1 having a melting point of less than 70°C.
4. A copolymer of Claim 1 having a crystallinity of at least about 40 percent.
5. A copolymer of Claim 1 containing about 10 per-cent by weight 1,5-dioxepan-2-one and having a melting point of about 54°C.
6. A filament comprising a copolymer of Claim 1.
7. A filament of Claim 6 having a melting point of less than 70°C.
8. A filament of Claim 6 comprising a copolymer containing from about 3 to 10 percent 1,5-dioxepan-2-one and having an elongation in excess of 150 percent.
9. A filament of Claim 6 comprising a copolymer containing about 10 percent by weight 1,5-dioxepan-2-one.
10. A filament of Claim 9 having a melting point of about 54°C.
11. A film comprising a copolymer of Claim 1.
12. A molded article comprising a copolymer of
Claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/972,757 US4190720A (en) | 1978-12-26 | 1978-12-26 | Isomorphic copolymers of ε-caprolactone and 1,5-dioxepan-2-one |
| US972,757 | 1978-12-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1139043A true CA1139043A (en) | 1983-01-04 |
Family
ID=25520082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000342613A Expired CA1139043A (en) | 1978-12-26 | 1979-12-21 | ISOMORPHIC COPOLYMERS OF .epsilon.-CAPROLACTONE AND 1,5-DIOXEPAN-2-ONE |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4190720A (en) |
| CA (1) | CA1139043A (en) |
| DE (1) | DE2951778A1 (en) |
| FR (1) | FR2445348A1 (en) |
| GB (1) | GB2043084B (en) |
Families Citing this family (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4429080A (en) | 1982-07-01 | 1984-01-31 | American Cyanamid Company | Synthetic copolymer surgical articles and method of manufacturing the same |
| US4470416A (en) * | 1983-06-17 | 1984-09-11 | Ethicon, Inc. | Copolymers of lactide and/or glycolide with 1,5-dioxepan-2-one |
| US5152781A (en) * | 1987-12-17 | 1992-10-06 | Allied-Signal Inc. | Medical devices fabricated from homopolymers and copolymers having recurring carbonate units |
| US4916193A (en) * | 1987-12-17 | 1990-04-10 | Allied-Signal Inc. | Medical devices fabricated totally or in part from copolymers of recurring units derived from cyclic carbonates and lactides |
| US4891263A (en) * | 1987-12-17 | 1990-01-02 | Allied-Signal Inc. | Polycarbonate random copolymer-based fiber compositions and method of melt-spinning same and device |
| US5256764A (en) * | 1987-12-17 | 1993-10-26 | United States Surgical Corporation | Medical devices fabricated from homopolymers and copolymers having recurring carbonate units |
| US5274074A (en) * | 1987-12-17 | 1993-12-28 | United States Surgical Corporation | Medical devices fabricated from homopolymers and copolymers having recurring carbonate units |
| US4916207A (en) * | 1987-12-17 | 1990-04-10 | Allied-Signal, Inc. | Polycarbonate homopolymer-based fiber compositions and method of melt-spinning same and device |
| US5145945A (en) * | 1987-12-17 | 1992-09-08 | Allied-Signal Inc. | Homopolymers and copolymers having recurring carbonate units |
| US5120802A (en) * | 1987-12-17 | 1992-06-09 | Allied-Signal Inc. | Polycarbonate-based block copolymers and devices |
| DE68922497T2 (en) * | 1988-08-24 | 1995-09-14 | Marvin J Slepian | ENDOLUMINAL SEAL WITH BISDEGRADABLE POLYMERS. |
| US5082925A (en) * | 1990-08-16 | 1992-01-21 | Ethicon, Inc. | Homopolymers and copolymers of salicylate lactones |
| JP2717889B2 (en) * | 1991-04-12 | 1998-02-25 | 高砂香料工業株式会社 | Optically active ether lactones, optically active polymer thereof and method for producing the polymer |
| US5849035A (en) * | 1993-04-28 | 1998-12-15 | Focal, Inc. | Methods for intraluminal photothermoforming |
| US5925065A (en) * | 1993-06-11 | 1999-07-20 | United States Surgical Corporation | Coated gut suture |
| US5939191A (en) * | 1993-06-11 | 1999-08-17 | United States Surgical Corporation | Coated gut suture |
| JP3220331B2 (en) * | 1993-07-20 | 2001-10-22 | エチコン・インコーポレーテツド | Absorbable liquid copolymers for parenteral administration |
| CA2128912A1 (en) * | 1993-08-17 | 1995-02-18 | Zygmunt Teodorczyk | Modified phenol-aldehyde resin and binder system |
| US5442032A (en) * | 1994-03-15 | 1995-08-15 | Ethicon, Inc. | Copolymers of 1,4-dioxepan-2-one and 1,5,8,12-tetraoxacyclotetradecane-7-14-dione |
| US5665063A (en) * | 1994-06-24 | 1997-09-09 | Focal, Inc. | Methods for application of intraluminal photopolymerized gels |
| US5584858A (en) * | 1994-11-14 | 1996-12-17 | United States Surgical Corporation | Tubing fluid |
| US5584857A (en) * | 1994-11-14 | 1996-12-17 | United States Surgical Corporation | Suture coating and tubing fluid |
| US5779673A (en) * | 1995-06-26 | 1998-07-14 | Focal, Inc. | Devices and methods for application of intraluminal photopolymerized gels |
| FR2741351B1 (en) * | 1995-11-22 | 1998-01-16 | Solvay | SEMI-RIGID POLY-EPSILON-CAPROLACTONE FILM AND PROCESS FOR PRODUCING THE SAME |
| US5703200A (en) * | 1996-03-15 | 1997-12-30 | Ethicon, Inc. | Absorbable copolymers and blends of 6,6-dialkyl-1,4-dioxepan-2-one and its cyclic dimer |
| US5716376A (en) | 1996-06-28 | 1998-02-10 | United States Surgical Corporation | Absorbable mixture and coatings for surgical articles fabricated therefrom |
| US6352667B1 (en) | 1999-08-24 | 2002-03-05 | Absorbable Polymer Technologies, Inc. | Method of making biodegradable polymeric implants |
| WO2002013701A1 (en) * | 2000-08-17 | 2002-02-21 | Tyco Healthcare Group Lp | Sutures and coatings made from therapeutic absorbable glass |
| WO2004066927A2 (en) | 2003-01-24 | 2004-08-12 | Tyco Healthcare Group Lp | Bioabsorbable composition and coatings including same |
| US8263105B2 (en) | 2004-12-01 | 2012-09-11 | Tyco Healthcare Group Lp | Biomaterial drug delivery and surface modification compositions |
| US8974814B2 (en) * | 2007-11-12 | 2015-03-10 | California Institute Of Technology | Layered drug delivery polymer monofilament fibers |
| US20100094338A1 (en) * | 2008-10-15 | 2010-04-15 | Tyco Healthcare Group Lp | Hydroxamate-initiated polymers |
| US7923439B2 (en) * | 2008-10-15 | 2011-04-12 | Tyco Healthcare Group Lp | Hydroxamate compositions |
| US20100094340A1 (en) | 2008-10-15 | 2010-04-15 | Tyco Healthcare Group Lp | Coating compositions |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3190858A (en) * | 1959-12-03 | 1965-06-22 | Union Carbide Corp | Polymerization of cyclic esters |
| BE606009A (en) * | 1960-07-11 | |||
| GB1272733A (en) | 1970-01-20 | 1972-05-03 | Ici Ltd | Cyclic ether lactones |
| US3645941A (en) * | 1970-04-01 | 1972-02-29 | Eastman Kodak Co | Method of preparing 2-p-dioxanone polymers |
| US3852913A (en) * | 1972-07-28 | 1974-12-10 | Union Carbide Corp | Shaped biodegradable containers from biodegradable thermoplastic oxyalkanoyl polymers |
| US4045418A (en) * | 1975-01-28 | 1977-08-30 | Gulf Oil Corporation | Copolymers of D,L-lactide and epsilon caprolactone |
| US4052988A (en) * | 1976-01-12 | 1977-10-11 | Ethicon, Inc. | Synthetic absorbable surgical devices of poly-dioxanone |
-
1978
- 1978-12-26 US US05/972,757 patent/US4190720A/en not_active Expired - Lifetime
-
1979
- 1979-12-21 DE DE19792951778 patent/DE2951778A1/en not_active Withdrawn
- 1979-12-21 CA CA000342613A patent/CA1139043A/en not_active Expired
- 1979-12-21 GB GB7944174A patent/GB2043084B/en not_active Expired
- 1979-12-24 FR FR7931587A patent/FR2445348A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| GB2043084A (en) | 1980-10-01 |
| US4190720A (en) | 1980-02-26 |
| DE2951778A1 (en) | 1980-07-17 |
| FR2445348A1 (en) | 1980-07-25 |
| GB2043084B (en) | 1982-11-24 |
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