CA2046192C - Deformable surgical device - Google Patents
Deformable surgical device Download PDFInfo
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- CA2046192C CA2046192C CA002046192A CA2046192A CA2046192C CA 2046192 C CA2046192 C CA 2046192C CA 002046192 A CA002046192 A CA 002046192A CA 2046192 A CA2046192 A CA 2046192A CA 2046192 C CA2046192 C CA 2046192C
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F5/00—Orthopaedic methods or devices for non-surgical treatment of bones or joints; Nursing devices; Anti-rape devices
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/064—Surgical staples, i.e. penetrating the tissue
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/041—Mixtures of macromolecular compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L31/125—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L31/129—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix containing macromolecular fillers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/064—Surgical staples, i.e. penetrating the tissue
- A61B17/0644—Surgical staples, i.e. penetrating the tissue penetrating the tissue, deformable to closed position
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
- A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
- A61B17/72—Intramedullary pins, nails or other devices
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
- A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
- A61B17/80—Cortical plates, i.e. bone plates; Instruments for holding or positioning cortical plates, or for compressing bones attached to cortical plates
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
- A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
- A61B17/84—Fasteners therefor or fasteners being internal fixation devices
- A61B17/86—Pins or screws or threaded wires; nuts therefor
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B2017/00004—(bio)absorbable, (bio)resorbable, resorptive
Abstract
A deformable surgical repair device is manu-factured from either an absorbable copolymer comprising a plurality of first and second linkages or an absorb-able blend of a first and second polymer. The copolymer first linkages and the first polymer in the blend are selected from the group consisting of glycolic acid ester and lactic acid ester linkages, and mixtures thereof. The copolymer second linkages and the second polymer in the blend are selected from the group con-sisting of 1,3-dioxan-2-one; 1,4-dioxan-2-one and e-caprolactone linkages. The plurality of first linkages or the first polymer comprise at least about 50 up to about 90 mole percent of the respective copolymer or blend. The device can be combined with a reinforcing component prepared from a biocompatible polymer. The device can be further manufactured from a nonabsorbable material comprising a fluorinated hydrocarbon polymer.
The device can be a fracture fixation device, or a surgical clip or staple.
The device can be a fracture fixation device, or a surgical clip or staple.
Description
_1_ 31,256 DEFORMABLE SURGICAL DEVICE
This invention relates to absorbable and partially absorbable polymeric materials possessing an enhanced ability for permanent deformation at room temperature through a crazing mechanism. This invention also relates to the use of these materials in medical device applications that require the material to be reshapable. One such application is in absorbable maxillofacial bone fixation plates where complex frac-ture site surface contours are often encountered.
Another application is in absorbable surgical clips and staples where improved toughness and ductility are desirable.
The modification of glassy polymeric materials for improved toughness is well known in the nonabsorb-able polymer prior art. Perhaps the most notable example of a toughened glassy plastic is high impact polystyrene. Many other nonabsarbable polymers have been modified for improved toughness or impact resis-tance. Generally, toughness and impact resistance have been improved by incorporating a discontinuous rubbery phase in the parent polymer matrix. This has been done by physical blending or by preparation of block or graft copolymers. Similar concepts have been applied to thermosets such as epoxy resins. Although increases of ductility in nonabsaorbable rubber modified plastics have been reported, the primary purpose of the modifica-tion has been to impart impact resistance and toughness.
This property modification method has not been put to use in medical devices, either absorbable or nonabsorbable.
PART A DRSCRIPTION
This invention relates to absorbable polymeric materials possessing an enhanced ability for permanent deformation at room temperature through a crazing mechanism. This invention also relates to the use of these materials in medical device applications that require the material to be reshapable. Applications where these materials may be useful include the follow-ing:
1. Absorbable maxillofacial bone fixation plates.
2. Absorbable bone screws or other fastening devices.
This invention relates to absorbable and partially absorbable polymeric materials possessing an enhanced ability for permanent deformation at room temperature through a crazing mechanism. This invention also relates to the use of these materials in medical device applications that require the material to be reshapable. One such application is in absorbable maxillofacial bone fixation plates where complex frac-ture site surface contours are often encountered.
Another application is in absorbable surgical clips and staples where improved toughness and ductility are desirable.
The modification of glassy polymeric materials for improved toughness is well known in the nonabsorb-able polymer prior art. Perhaps the most notable example of a toughened glassy plastic is high impact polystyrene. Many other nonabsarbable polymers have been modified for improved toughness or impact resis-tance. Generally, toughness and impact resistance have been improved by incorporating a discontinuous rubbery phase in the parent polymer matrix. This has been done by physical blending or by preparation of block or graft copolymers. Similar concepts have been applied to thermosets such as epoxy resins. Although increases of ductility in nonabsaorbable rubber modified plastics have been reported, the primary purpose of the modifica-tion has been to impart impact resistance and toughness.
This property modification method has not been put to use in medical devices, either absorbable or nonabsorbable.
PART A DRSCRIPTION
This invention relates to absorbable polymeric materials possessing an enhanced ability for permanent deformation at room temperature through a crazing mechanism. This invention also relates to the use of these materials in medical device applications that require the material to be reshapable. Applications where these materials may be useful include the follow-ing:
1. Absorbable maxillofacial bone fixation plates.
2. Absorbable bone screws or other fastening devices.
3. Absorbable surgical clips and staples.
4. Absorbable bone fixation rods and screws.
Although not specifically exemplified, it is recognized that a number of materials could be envi-sioned which could possess similar properties to the exemplified copolymers. To have similar properties, it is necessary that the material have a continuous "hard"
phase and a "soft" phase. Tt is preferred that the soft phase be discontinuous, although this is not required.
To form separate hard and soft phases, the hard and soft species must not be fully miscible in their final polymeric form. The final polymeric form could be a block or graft copolymer or a blend of homopolymers and/or copolymers. Alternatively, controlled blending methods could be employed with otherwise miscible polymers to minimize phase mixing in the final article.
The following is a list of possible alternative materi-als which are included in this invention:
1. Block copolymers forming "hard" and "soft"
phases.
A. Hard phase forming monomers 1. 1-Lactide, d-lactide ar meso-lactide 2. dl-Lactide, variable ratios of d to 1 i~~~~a~,~~
3. Glycolide 4. Mixtures of glycolide and lactide 5. Other monomers or mixtures of monomers that form absorbable polymers with glass 'transition temperatures above room ' temperature.
B. Soft phase forming monomers 1. Trimethylene carbonate (1,3-dioxan-2-one) 2. p-Dioxanone (1,4-dioxan-2-one) 3. e-caprolactone (2-oxepanone or oxepan-2-one) 4. Mixtures of 1, 2 or 3, above 5. Other monomers or mixtures of monomers that form absorbable - polymers with glass transition temperatures below room temperature.
2. Blends of '°hard" and °°soft°' absorbable poly-mers A. Hard phase forming polymers 1. Poly(1-lactide), poly(d-lactide) or poly(meso-lactide) 2. Copolymers of 1-lactide, d-lactide or meso-lactide 3. Polyglycolide 4. Lactide-glycolide copolymers 5. Other polymers or copolymers with glass transition temperatures above room temperature.
B. Soft phase forming polymers 1. Poly(trimethylene carbonate) 2. Polyp-dioxanone) 3. Poly(e-caprolactone) 4. Copolymers of 1, 2, or 3, above _4_ 5. Other polymers or copolymers with glass transition temperatures below room temperature.
The selection of a preferred material will depend on the desired physical properties of the final article. The preferred material will also be determined by the desired in vivo degradation and absorption rates.
Several variables can be adjusted to obtain the desired properties. Absorption rate is known to be affected by composition and crystallinity. Fox example a hard phase of poly(1-lactide) would provide a slow degradation rate due to its hydrophobic, crystalline nature, whereas a copolymer of glycolide and dl-lactide in equal amounts would provide a fast degradation rate due to its more hydrophilic, noncrystalline nature. If increased stiffness or strength is required, an absorbable fiber or fabric reinforcement can be added to make a composite structure. Further improvement of the composite proper-ties can be made by manipulating the location of the reinforcement within the composite, fax example, if the reinforcement is placed in the center plane of a lami-nated structure, the composite.would be expected to be stiffer in tension (forces applied parallel to the plane) than in flexion (forces applied normal to the plane), allowing reshaping by bending.
The present invention discloses medical devices made from block copolymers. The block copolymer is composed of a lactide or a lactide/glycolide copolymer and a low glass transition temperature or a rubbery polymer such as polytrimethylene carbonate. It is the presence of the rubbery or soft block which imparts the deformability in bending to the surgical repair devices described in this application.
The following embodiments summarize the Part A
inventions:
1. An article of manufacture comprising a deformable surgical repair device, the deformable surgical repair device manufactured from a copolymer, the copolymer selected from the group consisting of a block and graft copolymer, the copolymer comprising a plurality of first linkages selected from the group consisting of glycolic acid ester and lactic acid ester linkages,, and mixtures thereof, and a plurality of second Linkages selected from the group consisting of 1,3-dioxan-2-one; 1,4-dioxan-2-one and e-caprolactone linkages, the plurality of first linkages comprising at least about 50 up to about 90 mole percent of the copolymer.
2. The article of embodiment 1 wherein the copolymer is a block copolymer.
3. The article of embodiment 2 wherein the plurality of first linkages comprises lactic acid ester linkages.
4, The article of embodiment 2 wherein the plurality of first linkages comprises glycolic acid ester linkages.
5. The article of embodiment 3 or 4 wherein the plurality of second linkages comprises 7.,3-dioxan-2--one linkages.
Although not specifically exemplified, it is recognized that a number of materials could be envi-sioned which could possess similar properties to the exemplified copolymers. To have similar properties, it is necessary that the material have a continuous "hard"
phase and a "soft" phase. Tt is preferred that the soft phase be discontinuous, although this is not required.
To form separate hard and soft phases, the hard and soft species must not be fully miscible in their final polymeric form. The final polymeric form could be a block or graft copolymer or a blend of homopolymers and/or copolymers. Alternatively, controlled blending methods could be employed with otherwise miscible polymers to minimize phase mixing in the final article.
The following is a list of possible alternative materi-als which are included in this invention:
1. Block copolymers forming "hard" and "soft"
phases.
A. Hard phase forming monomers 1. 1-Lactide, d-lactide ar meso-lactide 2. dl-Lactide, variable ratios of d to 1 i~~~~a~,~~
3. Glycolide 4. Mixtures of glycolide and lactide 5. Other monomers or mixtures of monomers that form absorbable polymers with glass 'transition temperatures above room ' temperature.
B. Soft phase forming monomers 1. Trimethylene carbonate (1,3-dioxan-2-one) 2. p-Dioxanone (1,4-dioxan-2-one) 3. e-caprolactone (2-oxepanone or oxepan-2-one) 4. Mixtures of 1, 2 or 3, above 5. Other monomers or mixtures of monomers that form absorbable - polymers with glass transition temperatures below room temperature.
2. Blends of '°hard" and °°soft°' absorbable poly-mers A. Hard phase forming polymers 1. Poly(1-lactide), poly(d-lactide) or poly(meso-lactide) 2. Copolymers of 1-lactide, d-lactide or meso-lactide 3. Polyglycolide 4. Lactide-glycolide copolymers 5. Other polymers or copolymers with glass transition temperatures above room temperature.
B. Soft phase forming polymers 1. Poly(trimethylene carbonate) 2. Polyp-dioxanone) 3. Poly(e-caprolactone) 4. Copolymers of 1, 2, or 3, above _4_ 5. Other polymers or copolymers with glass transition temperatures below room temperature.
The selection of a preferred material will depend on the desired physical properties of the final article. The preferred material will also be determined by the desired in vivo degradation and absorption rates.
Several variables can be adjusted to obtain the desired properties. Absorption rate is known to be affected by composition and crystallinity. Fox example a hard phase of poly(1-lactide) would provide a slow degradation rate due to its hydrophobic, crystalline nature, whereas a copolymer of glycolide and dl-lactide in equal amounts would provide a fast degradation rate due to its more hydrophilic, noncrystalline nature. If increased stiffness or strength is required, an absorbable fiber or fabric reinforcement can be added to make a composite structure. Further improvement of the composite proper-ties can be made by manipulating the location of the reinforcement within the composite, fax example, if the reinforcement is placed in the center plane of a lami-nated structure, the composite.would be expected to be stiffer in tension (forces applied parallel to the plane) than in flexion (forces applied normal to the plane), allowing reshaping by bending.
The present invention discloses medical devices made from block copolymers. The block copolymer is composed of a lactide or a lactide/glycolide copolymer and a low glass transition temperature or a rubbery polymer such as polytrimethylene carbonate. It is the presence of the rubbery or soft block which imparts the deformability in bending to the surgical repair devices described in this application.
The following embodiments summarize the Part A
inventions:
1. An article of manufacture comprising a deformable surgical repair device, the deformable surgical repair device manufactured from a copolymer, the copolymer selected from the group consisting of a block and graft copolymer, the copolymer comprising a plurality of first linkages selected from the group consisting of glycolic acid ester and lactic acid ester linkages,, and mixtures thereof, and a plurality of second Linkages selected from the group consisting of 1,3-dioxan-2-one; 1,4-dioxan-2-one and e-caprolactone linkages, the plurality of first linkages comprising at least about 50 up to about 90 mole percent of the copolymer.
2. The article of embodiment 1 wherein the copolymer is a block copolymer.
3. The article of embodiment 2 wherein the plurality of first linkages comprises lactic acid ester linkages.
4, The article of embodiment 2 wherein the plurality of first linkages comprises glycolic acid ester linkages.
5. The article of embodiment 3 or 4 wherein the plurality of second linkages comprises 7.,3-dioxan-2--one linkages.
6. An article of manufacture comprising a deformable fracture fixation device, the deformable fracture fixation device manufactured from a copolymer, the copolymer selected from the group consisting of a block and graft copolymer, the copolymer having a plurality of first linkages comprising lactic acid ester linkages and a plurality of second linkages selected from the group consisting of 1,3-dioxan-2-one and 1,4-dioxan-2-one linkages, the plurality of lactic acid ester linkages comprising more than 50 to about 80 weight percent of the copolymer.
7. The article of embodiment 6 wherein the copolymer is a block copolymer.
~'~~c~~.,~~m 8. The article of embodiment 7 wherein the plurality of lactic acid ester linkages comprises about 80 weight percent of the copolymer.
~'~~c~~.,~~m 8. The article of embodiment 7 wherein the plurality of lactic acid ester linkages comprises about 80 weight percent of the copolymer.
9. The article of embodiment 8 wherein the plurality of second linkages comprises 1,3-dioxan-2-one linkages.
10. An article of manufacture comprising a deformable surgical repair device, the deformable surgical repair device manufactured from a blend of a first and a second absorbable polymer, the first absorb-able polymer comprising a plurality of linkages selected from the group consisting of glycolic acid ester and lactic acid ester linkages, and mixtures thereof, and the second absorbable polymer comprising a plurality of linkages selected from the group consisting of 1,3-dioxan-2-one; 1,4-dioxan-2-one and e-caprolactone linkages, the first absorbable polymer comprising at least about 50 up to about 90 weight percent of the blend.
11. The article of embodiment 10 wherein the first absorbable polymer is a homopolymer.
12. The article of embodiment 11 wherein the first absorbable homopolymer consists essentially of lactic acid ester linkages.
13. The article of embodiment 10 wherein the first absorbable polymer is a copolymer.
14. The article of embodiment 12 wherein the second absorbable polymer comprises a plurality of linkages selected from the group consisting of 1,3-dioxan-2-one and 1,4-dioxan-2-one linkages.
15. The article of embodiments 1, 2, 3, 10, 11, 12 or 14 wherein the deformable surgical repair device is a fracture fixation device.
16. The article of embodiment 15 wherein the fracture fixation device is a bone plate.
-7_ 17. The article of embodiments 1, 2, 3, 10, 11, 12 or 14 wherein the deformable surgical repair device is a clip.
-7_ 17. The article of embodiments 1, 2, 3, 10, 11, 12 or 14 wherein the deformable surgical repair device is a clip.
18. The article of embodiments 1, 2, 3, 10, 11, 12 or 14 wherein the deformable surgical repair device is a staple.
19. A surgical composite structure for mammalian tissue comprising:
a) a reinforcing component prepared from a plurality of fibers, plurality of the fibers manufactured from a biocompatible polymer, and b) a bioabsorbable component comprising a copolymer the copolymer selected from the group consisting of a block and graft copolymer, the copolymer comprising a plurality of first linkages selected from the group consisting of glycolic acid ester and lactic acid ester linkages, and mixtures thereof, and a plurality of second linkages selected from the group consisting of 1,3-dioxan-2-one: 1,4-dioxan-2-one and e-caprolactone linkages, the plurality of first linkages comprising at least about 50 up to about 90 mole percent of the copolymer.
a) a reinforcing component prepared from a plurality of fibers, plurality of the fibers manufactured from a biocompatible polymer, and b) a bioabsorbable component comprising a copolymer the copolymer selected from the group consisting of a block and graft copolymer, the copolymer comprising a plurality of first linkages selected from the group consisting of glycolic acid ester and lactic acid ester linkages, and mixtures thereof, and a plurality of second linkages selected from the group consisting of 1,3-dioxan-2-one: 1,4-dioxan-2-one and e-caprolactone linkages, the plurality of first linkages comprising at least about 50 up to about 90 mole percent of the copolymer.
20. The structure of embodiment 19 wherein the reinforcing component is manufactured from an absorbable biocompatible polymer.
21. The structure of embodiment 20 wherein the absorbable biocompatible polymer is selected from the group consisting of a homopolymer or copolymer of polyglycolic acid, polylactic acid, polyhydroxy butyrate and blends of the same, and poly(d-lactic acid) blended with poly(1-lactic acid).
22. The structure of embodiment 19 wherein the reinforcing component is manufactured from a nonabsorbable biocompatible polymer.
~~A~.~~s 23. The structure of embodiment 22 wherein the nonabosrbable biocompatible polymer is selected from the group consisting of polyethylene terephthalate, silk, nylon, polypropylene, polyethylene and polyoxymethylene and blends of the same.
~~A~.~~s 23. The structure of embodiment 22 wherein the nonabosrbable biocompatible polymer is selected from the group consisting of polyethylene terephthalate, silk, nylon, polypropylene, polyethylene and polyoxymethylene and blends of the same.
24. The structure of embodiment 19, 20, 21, 22 or 23 wherein the bioabsorbable component comprises a block copolymer.
25. The structure of embodiment 24 wherein the plurality of first linkages in the block copolymer comprises lactic acid ester linkages.
26. The structure of embodiment 24 wherein the plurality of first linkages in the block copolymer comprises glycolic acid ester linkages.
27. The structure of embodiment 25 or 26 wherein the plurality of second linkages in the block copolymer comprises 1,3-dioxan-2-one linkages.
28. A surgical composite structure for mammalian tissue comprising:
a) a reinforcing component prepared from a plurality of fibers, plurality of the fibers manufactured from biocompatible polymer, and b) a bioabsorbable component comprising a blend of a first and second absorbable polymer, the first absorbable polymer comprising a plurality of linkages selected from the group consisting of glycolic acid ester and lactic acid ester linkages, and mixtures thereof, and the second absorbable polymer comprising a plurality of linkages selected from the group consisting of 1,3-dioxan-2-one;
1,4-dioxan-2-one and e-caprolactone linkages, the first absorbable polymer comprising at least about 50 up to about 90 weight percent of the blend.
a) a reinforcing component prepared from a plurality of fibers, plurality of the fibers manufactured from biocompatible polymer, and b) a bioabsorbable component comprising a blend of a first and second absorbable polymer, the first absorbable polymer comprising a plurality of linkages selected from the group consisting of glycolic acid ester and lactic acid ester linkages, and mixtures thereof, and the second absorbable polymer comprising a plurality of linkages selected from the group consisting of 1,3-dioxan-2-one;
1,4-dioxan-2-one and e-caprolactone linkages, the first absorbable polymer comprising at least about 50 up to about 90 weight percent of the blend.
29. The structure of embodiment 28 wherein the reinforcing component is manufactured from an absorbable biocompatible polymer.
30. The structure of embodiment 29 wherein the absorbable biocompatible polymer is selected from the group consisting of a homopolymer or copolymer of polyglycolic acid, polylactic acid, polyhydroxy butyrate and blends of the same, and poly(d-lactic acid) blended with poly(1-lactic acid).
31. The structure of embodiment 28 wherein the reinforcing component is manufactured from a nonabsorbable biocompatible polymer.
32. The structure of embodiment 31 wherein the nonabsorbable biocompatible polymer is selected from the group consisting of polyethylene terephthalate, silk, nylon, polypropylene, polyethylene and polyoxymethylene arid blends of the same.
33. The structure of embodiment 28, 29, 30, 31 or 32 wherein the first absorbable polymer in the bioabsorbable component is a homopolymer.
34. The structure of embodiment 33 wherein the first absorbable homopolymer in the bioabsorbable component consists essentially of lactic acid ester linkages.
35. The structure of embodiment 28, 29, 30, 31 or 32 wherein the first absorbable polymer in the bioabsorbable component is a copolymer.
36. The structure of embodiment 35 wherein the second absorbable polymer in the bioabsorbable component comprises a plurality of linkages selected from the group consisting of 1,3-dioxan-2-one and 1,4-dioxan-2-one linkages.
Referring to the embodiments in this Part A, subparagraphs 5, 6, 9, 10 and 14, above, and generally as described in this specification, some polymers have been described as linkages of one or more monomers.
Some of these monomers are described as cyclic esters, e.g. 1,4-dioxan-2-one. It is to be understood that any person skilled in the art implicitly knows how to make and how to use these monomers to form the polymer linkages and that, therefore, the description of these linkages by the use of this monomeric nomenclature is adequate.
Referring to the embodiments in this Part A, subparagraphs 1, 6, 10 and 15, above, it is to be clear-ly understood that the surgical repair and fracture fixation devices include, but are not limited to, those embodiments described in this Part A, subparagraphs 16 to 18, above. Thus, other devices, e.g. a bone pin, bone rod, bone screw, trocar, prosthetic tubular arti-cle, and similar or related molded or extruded devices, axe within the scope of this invention.
Referring to this Part A, subparagraphs 19 and 28, above, the plurality of fibers in the reinforcing component can be matted, chopped, woven, knitted, unidirectional or a fiber tow. The plurality of fibers can also be composed of laminated plies wherein each ply consists of continuous, unidirectional fibers, woven fabric or knitted fabric and the direction of fibers between adjacent plies need not be the same.
Referring, generally, to this Part A, subpara-graphs 19 to 36, above, in the fabrication of the composite structure, it is to be understood that the melting point of the bioabsorbable component must be less than the melting point of the reinforcing compo-nent. See also, generally, Example 12.
Referring to the embodiments in this Part A, subparagraphs 20 and 29, above, it is to be understood that other absorbable polymers can be used beside those described in this Part A, subparagraphs 21 and 30, above, respectively. Other absorbable polymers include those described in the '°Part A Description", above, ~~~~f ~,~
subparagraphs 1A and 2A, which description is not exclusive.
The inventions are further described in the following examplese Example 2 L-Lactide-Trimethylene Carbonate Block Copolymer Polymerization grade 1,3-d9.oxan-2-one (trimethylene carbonate, hereafter abbreviated TMC) (97.58, 0.995 mole), diethylene glycol (hereafter abbreviated DEG) (4.20x10 2g, 4.0x10 4 mole), and Dabco T-9 catalyst (a stannous 2-ethylhexanoate catalyst formulation sold by Air Products, Inc., USA, hereafter abbreviated T-9j (1.35x10 2g, 3.3x10 5 moles) were combined in a stirred reactor at 182°C. The temperature was raised to 188oC and the mixture was stirred for 1 1/2 hours at this temperature. Polymerization grade 1-lactide (52.58, 0.364 mole) was added and the tempera-ture was increased to 200°C. After 45 minutes, the polymer was discharged from the reactor and allowed to solidify.
The resulting polymer had an inherent viscosi-ty (hereafter abbreviated IV) of 0.89 dL/g (0.5g/dL
conc. in CHC13). The convention to be used to define copolymer composition in this and subsequent examples is "mole percent lactide." This refers to the content of units in the copolymer which would be formed by incorpo-ration of a certain mole percent of lactide monomer into the copolymer. The composition of this copolymer was found to be 20.7 mole percent 1-lactide by 1H NMR.
The polymer was dissolved in methylene chloride (5 g/dL) and a film of about 0.003 inch thickness was cast.
The resulting material was found to be rubbery at room temperature.
Example 2 L-Lactide-Trimethylene Carbonate Block Copolymer Polymerization grade TMC (97.58, 0.995 mole), DEG
(4.20x10 2g, 4.0x10 4 mole), and T-9 catalyst (1.35x10 2g, 3.3x10 5 moles) were combined in a stirred reactor at 180°C and stirred at 40 RPM for 1 hour and 20 minutes. Polymerization grade 1-lactide (52.58, 0.364 mole) was added and the temperature was increased to 200oC. After 1 hour, the polymer was discharged from the reactor and allowed to solidify. The solid polymer was then devolatilized under reduced pressure at 25oC to remove residual monomer.
The resulting copolymer had an inherent viscosity of 0.64 dL/g (0.5 g/dL cone. in CHC13). The composition was found to be 25.7 mole percent 1-lactide by 1H NMR.
The polymer was dissolved in methylene chlo-ride (5 g/dL) and a film of about 0.003 inch thickness was cast. The resulting material was found to be rubbery at room temperature.
Example 3 L-Lactide-Trimethylene Carbonate Block Copolymer Polymerization grade TMC (64.998, 0.637 mole), DEG (1.83x10 2g, 1.73x10-4 mole), and T-9 catalyst (8.0x10-3g, 2.0x10-5 moles) were combined in a stirred reactor at 180°C and stirred at 40 RPM for 35 minutes.
Polymerization grade 1-lactide (154.298, 1.07 mole) was added and the temperature was increased to 190oC. After 4 hours, the polymer was discharged from the reactor and allowed to solidify.
The resulting copolymer had an inherent viscosity of 1.01 dL/g (0.5 g/dL conc. in CHC13) . The composition was found to be 62.6 mole percent 1-lactide by 1H NMR.
The plaque to be used for test specimen preparation was formed using a heated hydraulic press.
At a press temperature of 200°C, about 23 grams of dry polymer granules were pressed in a 4 1/4 inch by 4 1/4 inch by 1/16 inch steel frame between Teflon' (DuPont Co., DE, USA) coated release liner fabric at 500 pounds of pressure for 4 minutes followed by a pressure f ~~~~ r increase to 5000 pounds for 4 minutes. The hot plaques were cooled between chilled aluminum plates. The plaques were removed from the frame and annealed in the press at 130°C for 15 minutes at about 250 pounds (14 psi) pressure.
This material was found to undergo ductile defarmation through crazing when bent at room tempera-ture.
Example 4 L-Lactide-Trimethvlene Carbonate Block Copolymer Polymerization grade TMC (64.998, 0.637 mole), DEG (1.83x10 2g, 1.73x10 4 mole), and T-9 catalyst (2.06x10 2 moles) were combined in a stirred reactor at 180°C and stirred at 40 RPM for 35 minutes. Polymeriza-tion grade 1-lactide (154.298, 1.07 mole) was added and the temperature was increased to 190°C. After 1 hour and 45 minutes, the polymer was discharged from the reactor and allowed to solidify. The polymer was ground cryogenically and dried in vacuum at 105oC for 18 hours.
The resulting copolymer had an inherent viscosity of 1.44 dL/g (0.5 g/dL conc. in CHC13). The composition was found to be 60.5 mole percent 1-lactide by 1H NMR.
A plaque to be used for test specimen prepara-tion was formed according to Example 3.
This material was found to undergo ductile deformation through crazing when bent at room tempera-tore.
Example 5 L-Lactide-TrimethvleneCarbonate Block Conolvmer Polymerization grade TMC (45.948, 0.450 mole), DEG (1.59x10 2g, 1.49x10 4 mole), and T-9 catalyst (1.81x10 2g, 4.48x10 5 moles) were combined in a stirred reactor at 180°C and stirred at 40 RPM for 30 minutes.
Polymerization grade 1-lactide (151.358, 1.07 mole) was added and the temperature was increased to 195°C. After 2 hours, the polymer was discharged from the reactor and allowed to solidify. The solid polymer was ground cryogenically and was then devolatilized under reduced pressure at 105°C to remove residual monomer.
The resulting copolymer had an inherent viscosity of 1.49 dL/g (0.5 g/dL cone in CHC13). The composition was found to be 68.3 mole percent 1-lactide by 1H NMR.
A plaque to be used for test specimen prepara-tion was formed according to Example 3.
The material was found to undergo ductile deformation through crazing when bent at room tempera-ture.
Example 6 D1-Lactide-Trimethylene Carbonate Block Copolymer Polymerization grade TMC (33.28, 0.325 mole), DEG (1.72x10-2g, 1.62x10-4 mole), and T-9 catalyst (7.6x10-38,_1.87x10 5 moles) were combined in a stirred reactor at 180°C and stirred at 40 RPM for 35 minutes.
Polymerization grade dl-lactide (186.88, 1.296 mole) was added and the temperature was increased to 195°C. After 3 hours and 40 minutes the polymer was discharged from the reactor and allowed to solidify. The solid polymer was ground cryogenically and was then devolatilized under reduced pressure at 25°C for 18 hours to remove residual monomer.
The resulting copolymer had an inherent viscosity of 1. 05 dL/g ( 0 . 5 g/dL cone . in CHC13 ) . The composition was found to be 78.6 mole percent dl-lactide by 1H NMR.
A plaque.to be used for test specimen prepara-tion was formed according to Example 3.
This material was found to undergo ductile deformation through crazing when bent at room tempera-ture.
Example 7 L-Lactide-Trimeth~~lene Carbonate Block Copolymer Polymerization grade TMC (33.28, 0,325 mole), DEG (1,72x10-2g, 1.62x10-4 mole), and T-9 catalyst (7.6x10 3g, 1.87x10 5 moles) were combined in a stirred reactor at 180°C and stirred at 40 RPM for 35 minutes.
Polymerization grade 1-lactide (186.8g, 1.296 mole) was added and the temperature was increased to 195°C. After 3 hours and 40 minutes, the polymer was discharged from the reactor and allowed to solidify. The solid polymer was ground cryogenically and was then devolatilized under reduced pressure at 150oC for. 18 hours to remove residual monomer.
The resulting copolymer had an inherent viscosity of 1.56 dL/g (0.5 g/dL conc. in CHC13). The composition was found to be 79.1 mole percent 1-lactide by 1H NMR.
A plaque to be used for test specimen prepara-tion was formed according to Example 3.
This material was found to undergo ductile deformation through crazing when bent at room tempera-ture.
Example 8 LLactide-Trimethvlene Carbonate Block Cobolvmer Polymerization grade TMC (16.1g, 0,158 mole), DEG (1.67x10-2g, 1.57x10 4 mole), and T-9 catalyst (6.37x10 3g, 1.57x10-5 moles) were combined in a stirred reactor at 180°C and stirred at 40 RPM for 27 minutes.
Polymerization grade 1-lactide (203.9g 1.415 mole) was added and the temperature was increased to 195°C. After 6 hours, the polymer was discharged from the reactor and allowed to solidify. The solid polymer was ground cryogenically and was then devolatilized under reduced pressure at 100°C for 18 hours to remove residual monomer.
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The resulting copolymer had an inherent viscosity of 1. 41 dL/g ( 0 . 5 g/dL conc . in CHC13 ) . The composition was found to be 89.6 mole percent 1-lactide by 1H NMR.
A plaque to be used for test specimen prepara-tion was formed according to Example 3.
This material was found to undergo a small amount of ductile deformation and crazing before break-ing when bent at room temperature.
Example 9 L-Lactide-Trimethylene Carbonate Block Copolymer Polymerization grade TMC (7.668, 0.075 mole), DEG (1.69x10-2g, 1.59x10-4 mole), and T-9 catalyst (1.82x10 2g, 4.45x10 5 moles) were combined in a stirred reactor at 180°C and stirred at 40 RPM for 21 minutes.
Polymerization grade 1--lactide (205.348, 1.425 mole) was added and the temperature was increased to 195°C. After 3 hours and 40 minutes, the polymer was discharged from the reactor and allowed to solidify. The solid polymer was ground cryogenically and was then devolatilized under reduced pressure at 100°C for 18 hours to remove residual monomer.
The resulting copolymer had an inherent viscosity of 1.65 dL/g (0.5 g/dL cone. in CHC13). The composition was found to be 95.3 mole percent 1-lactide by 1H NMR.
A plaque to be used for test specimen prepara-tion was formed according to Example 3.
This material was not found to undergo ductile deformation when bent at room temperature.
Example 10 Thermal Analysis Of Lactide-TMC Copolymers Samples of copolymers from Examples 3 to 9 were analyzed by differential scanning calorimetry (DSC). Scanning conditions were from -40°C to 200°C at 20°C minimum under nitrogen. Those copolymers which formed two amorphous phases are identified by two glass i~d~~C~~~,~"-~
,ty, -17°
transition temperatures (Tg(1) and Tg(2)). All samples except Example 5, which was made using dl-lactide, also had a crystalline phase characterized by the melting point (Tm) and the enthalpy of fusion (aHf). The results of this analysis are shown in Table 1.
Table 1 Polymer From Mole % T~(1) T~(2) ~m oHf Example1-Lac ( C) ( C) ( C) (cal/g) 3 62.5 -8.8 55.8 167.6 7.28 4 60.5 -12.5 57.8 171.4 8.76 68.3 -10.3 57.3 171.1 8.86 6 78.8 (dl) -4.1 49.4 - --7 79.1 -12.5 59.4 172.7 11.63 8 89.6 -- 60.3 175.0 11.85 9 95.3 - 65.8 174.8 12.12 Example 11 Mechanical Testingr of Lactide-TMC Copolymers Plaques made in Examples 4 through 8 were cut into specimens for testing according to ASTM methods D638 (tensile) and D790 (flexural). 'rhe results of this testing are included in Table 2. Far the tensile tests, five replicates were used, and the mean values are reported in Table 2. The flexural values reported in Table 2 are the means for four replicates.
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For a bone plate application, it is considered desirable to have the highest modulus and yield strength, while maintaining ductility. The preferred composition for the bone plate application, in the case of lactide-TMC
block copolymers, would, therefore, be 80 to 90 percent lactide. Above 90 percent lactide, the sample loses ductility, and below 80 percent lactide, the modulus and yield strength continue to decrease without any advan-tage in ductility as measured by strain at break in flexure.
Examt~le 12 Composite Fabrication A composite was fabricated in the following manner. Poly(glycolic acid) (PGA) fiber (100 g/denier) was wound around a 7 3/4" square stainless steel plate.
The fiber covered both si3es of the plate over a section measuring 3°° X 7 3/4°° with the long dimension aligned with the fiber. The weight of fiber used for this operation was 12.0 g.
A 10 g/dL solution of the polymer of Example 7 was prepared in methylene chloride. Polymer was then brushed onto the fiber and air dried. This was repeated several times. The material was then consolidated in a heated press at 170°C and cooled to room temperature.
This allowed for the fiber to be cut and the two halves removed from front and back side of the plate. Addi-tional polymer solution was applied to the two sections.
This was continued until a total of 19.0 g of polymer was added to the fiber. The two halves were then vacuum pressed to a thickness of 1/16" at a temperature of 170°C. The composite was removed from the press and annealed at 110°C in an air oven for twenty minutes.
The final weight fraction of PGA in the composite was 39%.
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The plate was cut into 1/2" X 2 1/2" tensile specimens and tested according to ASTM D638 (Amer. Soc.
of Testing Materials, PA, USA). The tensile modulus was 0.99 X 106 psi and the tensile strength was 37.0 X 103 psi.
Two tensile specimens were strained in flexure (ASTM D790) to 5% in an Instron test machine (Instron Gorp., MA, USA). When the load was relieved, the specimens were permanently deformed to approximately 2%
strain. Flexural modulus was 1.27 X 106 psi and flexural stress at 5% strain was 21.6 X 103 psi.
Part B
The prior art discloses certain nonabsorbable materials that contain o.05 to 20 percent polytetra-fluoroethylene ("PTFE") microfibrous particles. The PTFE is described as useful as an additive to improve viscosity and melt elasticity of certain thermoplastics.
The prior art also discloses a method fox making a molding composition containing 10 to 20 percent PTFE
with a thermoplastic polymer. The composition was found to provide improved impact strength. The prior art also discloses a composition of polyethylene terephthalate with 0.1 to 2.0 percent by weight of a PTFE emulsion incorporated therein. The PTFE additive is said to improve the processability. It also discloses that PTFE
also unexpectedly increases the ultimate elongation of the final compositions. No mention is made in any of the prior art of the usefulness of the materials as deformable articles. No mention of their usefulness in medical products is made. Also, no mention of their usefulness with absorbable polymers is made. In summa-ry, none of the prior art mentions the usefulness as medical devices of absorbable materials combined with PTFE, which can be permanently deformed at room tempera-ture through crazing.
The following embodiments summarize the Part B
inventions:
1. An article of manufacture comprising a deformable surgical repair device, the deformable surgical xepair device manufactured from an absorbable material, the absorbable material having a polymer comprising linkages selected from the group consisting of glycolic acid ester, lactic acid ester, 1,3-dioxan -2-one and 1,4-dioxan-2-one linkages, the surgical repair device further manufactured from a nonabsorbable material.
2. The article of embodiment 1 wherein the nonabsorbable material comprises a polymer prepared from a fluorinated hydrocarbon.
3. The article of embodiment 2 wherein the absorb-able material comprises a homopolymer.
4. The article of embodiment 3 wherein the absorb-able material comprises a homopolymer consisting essen-tially of glycolic acid ester linkages.
5. The article of embodiment 1, 2 or 3 wherein the absorbable material comprises a homopolymer consisting essentially of lactic acid ester linkages.
6. The article of embodiment 1 or 2 wherein the absorbable material comprises a copolymer comprising glycolic acid ester and lactic acid ester linkages.
7. An article of manufacture comprising a deformable tissue repair device, the deformable tissue repair device manufactured from an absorbable material, the absorbable material having a first homopolymer consisting essentially of linkages selected from the group consisting of glycolic acid ester, lactic acid ester and 1,4-dioxan-2-one linkages blended with a second copolymer comprising at least two different linkages selected from the group consisting of glycolic acid ester, lactic acid ester, 1,3-dioxan-2-one, 1,4-dioxan-2-one and e-caprolactone linkages, the tissue a ~~~~r'~~
repair device further manufactured from a nonabsorbable material.
8. The article of embodiment 7 caherein the non-absorbable material comprises a polymer prepared from a fluorinated hydrocarbon.
9. The article of embodiment 8 wherein the first homopolymer consists essentially of glycolic acid ester linkages.
10. The article of embodiment 7 or 8 wherein the first homopolymer consists essentially of lactic said ester linkages.
11. The article of embodiment 9 wherein the second copolymer comprises glycolic acid ester and trimethylene carbonate linkages.
12. The article of embodiment 7, 8, 9 or 11 wherein the second copolymer comprises glycolic acid ester and lactic acid ester linkages.
13. The article of embodiment 2, 3, 4, 8, 9 or 11 wherein the nonabsorbable material is polytetrafluoro-ethylene.
14. An article of manufacture comprising a deformable surgical repair device, the deformable surgical repair device manufactured from an absorbable material, the absorbable material having a first homopolymer comprising linkages selected from the grpup consisting of glycolic acid ester, lactic acid ester and 1,4-dioxan-2-one linkages blended with a second copolymer comprising at least two different linkages selected from the group consisting of glycolic acid ester, lactic acid ester, 1,3-dioxan-2-one, 1,4-dioxan-2-one and e-caprolactone linkages, the deformable surgical repair device further manufactured from a nonabsorbable material, the nonabsorbable materi-al comprising a polymer selected from the group consist-ing of polytetrafluoroethylene and a fluorinated ethylene-propylene copolymer, the nonabsorbable material ~~~~.c~~,~, a comprising more than about 1/100th of one percent to less than about one percent by weight of the device.
15. The article of embodiment 14 wherein the first homopolymer consists essentially of glycolic acid ester linkages.
16. The article of embodiment 14 wherein the first homopolymer consists essentially of lactic acid ester linkages.
17. The article of embodiment 15 wherein the second copolymer comprises glycolic acid ester and trimethylene carbonate linkages.
18. The article of embodiment 14, 15, 16 or 17 wherein the nonabsorbable material is polytetrafluoroethylene.
19. The article of embodiment 18 wherein the nonabsorbable material comprises more than about 1/50th to less than about one-half of one percent by weight of the device.
20. The article of embodiment 19 wherein the nonabsorbable material comprises about 1/l0th of one percent.
21. The article of embodiment 2, 3, 4, 8, 9, 11, 14, 15 or 17 wherein the nonabsorbable material is micropulverized.
22. The article of embodiment 2, 3, 4, 8, 9, 11, 14, 15 or 17 wherein the nonabsorbable material is in microfibrillar form.
23. The article of embodiment 2, 3, 4, 8, 9 11, 14, 15 or 17 wherein the deformable repair device is a fracture fixation device.
24. The article of embodiment 23 wherein the fracture fixation device is a bone plate.
25. The article of embodiment 2, 3, 4, 8, 9, 11, 14, 15 or 17 wherein the deformable repair device is a clip.
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26. The article of embodiment 2, 3, 4, 8, 9, 11, 14, 15 or 17 wherein the deformable repair device is a staple.
Referring to the embodiments in this Part B, subparagraphs 1 and 7 above, it is to be clearly under-stood that the nonabsorbable material is limited to those nonabsorbable compositions of matter which promote crazing. The mechanics of crazing of a polymeric material is well known in the prior art, although it is to be noted that the prior art almost always teaches that a crazing mechanism is not an advantage. There-fore, the invention described in this application teaches away from the known prior art.
Referring to the embodiments in this Part B, subparagraphs 1, 7 and 14, above, and generally as described in this specification, some polymers have been described as linkages of one or more monomers. Some of these monomers are described as cyclic esters, e.g.
1,4-dioxan-2-one. It is to be understood that any person skilled in the art implicitly knows how to make and how to use these monomers to form the polymer linkages and that therefore the description of these linkages by the use of this monomeric nomenclature is adequate.
Referring to the embodiments in this Part B, subparagraphs 1, 7, 14 and 23, above, it is to be clearly understood that the surgical repair, tissue repair and fracture fixation devices include, but are not limited to, those embodiments described in this Part B, subparagraphs 24 to 26 above. Thus, other devices, e.g. a bone pin, bone rod, bone screw, trocar, prosthet-ic tubular article and similar or related molded or extruded devices, are within the scope of this inven-tion.
Referring to the embodiments in this Part B, subparagraphs 21 and 22, above, a description of a micropulverized or microfibrillar fluorinated hydro-carbon polymer, and specifically polytetrafluoro-ethylene is disclosed in the prior art.
Part B DESCRIPTION
This invention relates to partially absorbable polymeric materials possessing an enhanced ability for permanent deformation at room temperature through a crazing mechanism. This invention also relates to the use of these materials in medical device applications that require the material to be reshapable. Applica-tions where these materials may be useful include the following:
_. Maxillofacial bone fixation plates.
2. Bone screws or other fastening devices.
3. Surgical clips and staples.
Although not specifically exemplified, it is recognized that a number of materials could be envi-sioned which could possess similar properties to the exemplified compositions. To have similar properties, it is necessary that the material have a continuous "hard" phase and a "soft°' phase. The soft phase in this invention is PTFE. The PTFE has been compounded with a normally rigid absorbable polymer, which forms the hard phase, by applying shear to the molten polymer in the presence of PTFE powder. The following is a list of alternative materials which are included in this inven-tion:
Hard phase forming absorbable polymers 1. Poly(1-lactide), poly(d-lactide) or poly(meso-lactide) 2. Copolymers of 1-lactide and d-lactide 3. Polyglycolide 4. Lactide-glycolide copolymers 5. Other polymers or copolymers with glass transition temperatures above room temperature.
The selection of a preferred material will depend on the desired physical properties of the final article. The preferred material will also be determined by the desired in vivo degradation and absorption rates.
Several variables can be adjusted to obtain the desired properties. Absorption rate is known to be affected by composition and crystallinity -- for example, a hard phase of poly(1-lactide) would provide a slow degrada-tion rate due to its hydrophobic, crystalline nature, whereas a copolymer of glycolide and dl-lactide in equal amounts would provide a fast degradation rate due to its more hydrophilic, noncrystalline nature. If increased stiffness or strength is required, a fiber or fabric reinforcement can be added to make a composite struc-ture. Further improvement of the composite properties can be made by manipulating the location of the rein-forcement within the composite -- for example, if the reinforcement is placed in the center plane of a lami-nated structure, the composite would be expected to be stiffer in tension (forces applied parallel to the plane) than in flexion (forces applied normal to the plane), allowing reshaping by bending.
-27_ The inventions are described in the following examples:
Example 13 Polvalvcolide Containing 0 1% Teflon Polyglycolide (63g) obtained from Davis & Geck, Wayne, NJ, USA was charged to the mixing head of an Electronic Plasti-corder manufactured by C. W. Brabender Instruments, Inc., NJ, USA. The polymer was heated to its melt temperature and mixed at 40 rpm while 0.063g of Teflon's DLX 6000 powder (DuPont, DE, USA) was added.
The mixing rate was increased to 75 rpm for two minutes and the molten mixture was removed from the mixing head and allowed to cool to room temperature.
Example 14 PolveLlycolide Containin~0% Teflon The procedure of Example 13 was used to prepare a blend of 0.63g of Teflon's DLX 6000 powder in 63g of polyglycolide.
Example 15 Polvalvcolide/Poly(Glycolide-co-trimethylene carbonate) (50/50 Weight Ratiol Containing 0.1% Teflon The procedure of Example 13 was used to mix 0.1~ by weight of Teflon's DLX 6000 powder into a 50/50 weight ratio blend of polyglycolide and poly(glyco-lide-co-trimethylene carbonate). The 50/50 weight ratio blend was obtained from Davis & Geck, Wayne, NJ, USA.
Example 16 Polyalycolide Polyp Glycolide-co-trimethylene carbonate) (75/25 Weight Ratio) Containing 0.1% Teflon The procedure of Example 13 was used to mix 0.1% by weight of Teflon'" DLX 6000 powder into a 75/25 weight ratio blend of polyglycolide and poly(glyco-lide-co-trimethylene carbonate).
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Example 17 Molded Plaques The polymer-Teflon" blends of Examples 13 to 16 were molded into 1/16°' thick plaques by heating each of the blends at a temperature of 230°C. and a pressure of 555 psi for one (1) minute between two Teflon'" coated aluminum plates separated by a 1/16"
thick spacer.
The plaques were allowed to cool to room temperature and were then cut into 1/4" wide strips for manual testing of how readily the strips cauld be deformed at ambient temperature. The results of the manual testing are summarized in Table I.
Example 18 Control Control strips were fabricated according to the procedure of Example 17, above, from polyglycolide that did not contain Teflon"' particles. The control strips were then manually tested as described above.
The results of the manual testing of the control strips are summarized in Table 3.
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Referring to the embodiments in this Part A, subparagraphs 5, 6, 9, 10 and 14, above, and generally as described in this specification, some polymers have been described as linkages of one or more monomers.
Some of these monomers are described as cyclic esters, e.g. 1,4-dioxan-2-one. It is to be understood that any person skilled in the art implicitly knows how to make and how to use these monomers to form the polymer linkages and that, therefore, the description of these linkages by the use of this monomeric nomenclature is adequate.
Referring to the embodiments in this Part A, subparagraphs 1, 6, 10 and 15, above, it is to be clear-ly understood that the surgical repair and fracture fixation devices include, but are not limited to, those embodiments described in this Part A, subparagraphs 16 to 18, above. Thus, other devices, e.g. a bone pin, bone rod, bone screw, trocar, prosthetic tubular arti-cle, and similar or related molded or extruded devices, axe within the scope of this invention.
Referring to this Part A, subparagraphs 19 and 28, above, the plurality of fibers in the reinforcing component can be matted, chopped, woven, knitted, unidirectional or a fiber tow. The plurality of fibers can also be composed of laminated plies wherein each ply consists of continuous, unidirectional fibers, woven fabric or knitted fabric and the direction of fibers between adjacent plies need not be the same.
Referring, generally, to this Part A, subpara-graphs 19 to 36, above, in the fabrication of the composite structure, it is to be understood that the melting point of the bioabsorbable component must be less than the melting point of the reinforcing compo-nent. See also, generally, Example 12.
Referring to the embodiments in this Part A, subparagraphs 20 and 29, above, it is to be understood that other absorbable polymers can be used beside those described in this Part A, subparagraphs 21 and 30, above, respectively. Other absorbable polymers include those described in the '°Part A Description", above, ~~~~f ~,~
subparagraphs 1A and 2A, which description is not exclusive.
The inventions are further described in the following examplese Example 2 L-Lactide-Trimethylene Carbonate Block Copolymer Polymerization grade 1,3-d9.oxan-2-one (trimethylene carbonate, hereafter abbreviated TMC) (97.58, 0.995 mole), diethylene glycol (hereafter abbreviated DEG) (4.20x10 2g, 4.0x10 4 mole), and Dabco T-9 catalyst (a stannous 2-ethylhexanoate catalyst formulation sold by Air Products, Inc., USA, hereafter abbreviated T-9j (1.35x10 2g, 3.3x10 5 moles) were combined in a stirred reactor at 182°C. The temperature was raised to 188oC and the mixture was stirred for 1 1/2 hours at this temperature. Polymerization grade 1-lactide (52.58, 0.364 mole) was added and the tempera-ture was increased to 200°C. After 45 minutes, the polymer was discharged from the reactor and allowed to solidify.
The resulting polymer had an inherent viscosi-ty (hereafter abbreviated IV) of 0.89 dL/g (0.5g/dL
conc. in CHC13). The convention to be used to define copolymer composition in this and subsequent examples is "mole percent lactide." This refers to the content of units in the copolymer which would be formed by incorpo-ration of a certain mole percent of lactide monomer into the copolymer. The composition of this copolymer was found to be 20.7 mole percent 1-lactide by 1H NMR.
The polymer was dissolved in methylene chloride (5 g/dL) and a film of about 0.003 inch thickness was cast.
The resulting material was found to be rubbery at room temperature.
Example 2 L-Lactide-Trimethylene Carbonate Block Copolymer Polymerization grade TMC (97.58, 0.995 mole), DEG
(4.20x10 2g, 4.0x10 4 mole), and T-9 catalyst (1.35x10 2g, 3.3x10 5 moles) were combined in a stirred reactor at 180°C and stirred at 40 RPM for 1 hour and 20 minutes. Polymerization grade 1-lactide (52.58, 0.364 mole) was added and the temperature was increased to 200oC. After 1 hour, the polymer was discharged from the reactor and allowed to solidify. The solid polymer was then devolatilized under reduced pressure at 25oC to remove residual monomer.
The resulting copolymer had an inherent viscosity of 0.64 dL/g (0.5 g/dL cone. in CHC13). The composition was found to be 25.7 mole percent 1-lactide by 1H NMR.
The polymer was dissolved in methylene chlo-ride (5 g/dL) and a film of about 0.003 inch thickness was cast. The resulting material was found to be rubbery at room temperature.
Example 3 L-Lactide-Trimethylene Carbonate Block Copolymer Polymerization grade TMC (64.998, 0.637 mole), DEG (1.83x10 2g, 1.73x10-4 mole), and T-9 catalyst (8.0x10-3g, 2.0x10-5 moles) were combined in a stirred reactor at 180°C and stirred at 40 RPM for 35 minutes.
Polymerization grade 1-lactide (154.298, 1.07 mole) was added and the temperature was increased to 190oC. After 4 hours, the polymer was discharged from the reactor and allowed to solidify.
The resulting copolymer had an inherent viscosity of 1.01 dL/g (0.5 g/dL conc. in CHC13) . The composition was found to be 62.6 mole percent 1-lactide by 1H NMR.
The plaque to be used for test specimen preparation was formed using a heated hydraulic press.
At a press temperature of 200°C, about 23 grams of dry polymer granules were pressed in a 4 1/4 inch by 4 1/4 inch by 1/16 inch steel frame between Teflon' (DuPont Co., DE, USA) coated release liner fabric at 500 pounds of pressure for 4 minutes followed by a pressure f ~~~~ r increase to 5000 pounds for 4 minutes. The hot plaques were cooled between chilled aluminum plates. The plaques were removed from the frame and annealed in the press at 130°C for 15 minutes at about 250 pounds (14 psi) pressure.
This material was found to undergo ductile defarmation through crazing when bent at room tempera-ture.
Example 4 L-Lactide-Trimethvlene Carbonate Block Copolymer Polymerization grade TMC (64.998, 0.637 mole), DEG (1.83x10 2g, 1.73x10 4 mole), and T-9 catalyst (2.06x10 2 moles) were combined in a stirred reactor at 180°C and stirred at 40 RPM for 35 minutes. Polymeriza-tion grade 1-lactide (154.298, 1.07 mole) was added and the temperature was increased to 190°C. After 1 hour and 45 minutes, the polymer was discharged from the reactor and allowed to solidify. The polymer was ground cryogenically and dried in vacuum at 105oC for 18 hours.
The resulting copolymer had an inherent viscosity of 1.44 dL/g (0.5 g/dL conc. in CHC13). The composition was found to be 60.5 mole percent 1-lactide by 1H NMR.
A plaque to be used for test specimen prepara-tion was formed according to Example 3.
This material was found to undergo ductile deformation through crazing when bent at room tempera-tore.
Example 5 L-Lactide-TrimethvleneCarbonate Block Conolvmer Polymerization grade TMC (45.948, 0.450 mole), DEG (1.59x10 2g, 1.49x10 4 mole), and T-9 catalyst (1.81x10 2g, 4.48x10 5 moles) were combined in a stirred reactor at 180°C and stirred at 40 RPM for 30 minutes.
Polymerization grade 1-lactide (151.358, 1.07 mole) was added and the temperature was increased to 195°C. After 2 hours, the polymer was discharged from the reactor and allowed to solidify. The solid polymer was ground cryogenically and was then devolatilized under reduced pressure at 105°C to remove residual monomer.
The resulting copolymer had an inherent viscosity of 1.49 dL/g (0.5 g/dL cone in CHC13). The composition was found to be 68.3 mole percent 1-lactide by 1H NMR.
A plaque to be used for test specimen prepara-tion was formed according to Example 3.
The material was found to undergo ductile deformation through crazing when bent at room tempera-ture.
Example 6 D1-Lactide-Trimethylene Carbonate Block Copolymer Polymerization grade TMC (33.28, 0.325 mole), DEG (1.72x10-2g, 1.62x10-4 mole), and T-9 catalyst (7.6x10-38,_1.87x10 5 moles) were combined in a stirred reactor at 180°C and stirred at 40 RPM for 35 minutes.
Polymerization grade dl-lactide (186.88, 1.296 mole) was added and the temperature was increased to 195°C. After 3 hours and 40 minutes the polymer was discharged from the reactor and allowed to solidify. The solid polymer was ground cryogenically and was then devolatilized under reduced pressure at 25°C for 18 hours to remove residual monomer.
The resulting copolymer had an inherent viscosity of 1. 05 dL/g ( 0 . 5 g/dL cone . in CHC13 ) . The composition was found to be 78.6 mole percent dl-lactide by 1H NMR.
A plaque.to be used for test specimen prepara-tion was formed according to Example 3.
This material was found to undergo ductile deformation through crazing when bent at room tempera-ture.
Example 7 L-Lactide-Trimeth~~lene Carbonate Block Copolymer Polymerization grade TMC (33.28, 0,325 mole), DEG (1,72x10-2g, 1.62x10-4 mole), and T-9 catalyst (7.6x10 3g, 1.87x10 5 moles) were combined in a stirred reactor at 180°C and stirred at 40 RPM for 35 minutes.
Polymerization grade 1-lactide (186.8g, 1.296 mole) was added and the temperature was increased to 195°C. After 3 hours and 40 minutes, the polymer was discharged from the reactor and allowed to solidify. The solid polymer was ground cryogenically and was then devolatilized under reduced pressure at 150oC for. 18 hours to remove residual monomer.
The resulting copolymer had an inherent viscosity of 1.56 dL/g (0.5 g/dL conc. in CHC13). The composition was found to be 79.1 mole percent 1-lactide by 1H NMR.
A plaque to be used for test specimen prepara-tion was formed according to Example 3.
This material was found to undergo ductile deformation through crazing when bent at room tempera-ture.
Example 8 LLactide-Trimethvlene Carbonate Block Cobolvmer Polymerization grade TMC (16.1g, 0,158 mole), DEG (1.67x10-2g, 1.57x10 4 mole), and T-9 catalyst (6.37x10 3g, 1.57x10-5 moles) were combined in a stirred reactor at 180°C and stirred at 40 RPM for 27 minutes.
Polymerization grade 1-lactide (203.9g 1.415 mole) was added and the temperature was increased to 195°C. After 6 hours, the polymer was discharged from the reactor and allowed to solidify. The solid polymer was ground cryogenically and was then devolatilized under reduced pressure at 100°C for 18 hours to remove residual monomer.
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The resulting copolymer had an inherent viscosity of 1. 41 dL/g ( 0 . 5 g/dL conc . in CHC13 ) . The composition was found to be 89.6 mole percent 1-lactide by 1H NMR.
A plaque to be used for test specimen prepara-tion was formed according to Example 3.
This material was found to undergo a small amount of ductile deformation and crazing before break-ing when bent at room temperature.
Example 9 L-Lactide-Trimethylene Carbonate Block Copolymer Polymerization grade TMC (7.668, 0.075 mole), DEG (1.69x10-2g, 1.59x10-4 mole), and T-9 catalyst (1.82x10 2g, 4.45x10 5 moles) were combined in a stirred reactor at 180°C and stirred at 40 RPM for 21 minutes.
Polymerization grade 1--lactide (205.348, 1.425 mole) was added and the temperature was increased to 195°C. After 3 hours and 40 minutes, the polymer was discharged from the reactor and allowed to solidify. The solid polymer was ground cryogenically and was then devolatilized under reduced pressure at 100°C for 18 hours to remove residual monomer.
The resulting copolymer had an inherent viscosity of 1.65 dL/g (0.5 g/dL cone. in CHC13). The composition was found to be 95.3 mole percent 1-lactide by 1H NMR.
A plaque to be used for test specimen prepara-tion was formed according to Example 3.
This material was not found to undergo ductile deformation when bent at room temperature.
Example 10 Thermal Analysis Of Lactide-TMC Copolymers Samples of copolymers from Examples 3 to 9 were analyzed by differential scanning calorimetry (DSC). Scanning conditions were from -40°C to 200°C at 20°C minimum under nitrogen. Those copolymers which formed two amorphous phases are identified by two glass i~d~~C~~~,~"-~
,ty, -17°
transition temperatures (Tg(1) and Tg(2)). All samples except Example 5, which was made using dl-lactide, also had a crystalline phase characterized by the melting point (Tm) and the enthalpy of fusion (aHf). The results of this analysis are shown in Table 1.
Table 1 Polymer From Mole % T~(1) T~(2) ~m oHf Example1-Lac ( C) ( C) ( C) (cal/g) 3 62.5 -8.8 55.8 167.6 7.28 4 60.5 -12.5 57.8 171.4 8.76 68.3 -10.3 57.3 171.1 8.86 6 78.8 (dl) -4.1 49.4 - --7 79.1 -12.5 59.4 172.7 11.63 8 89.6 -- 60.3 175.0 11.85 9 95.3 - 65.8 174.8 12.12 Example 11 Mechanical Testingr of Lactide-TMC Copolymers Plaques made in Examples 4 through 8 were cut into specimens for testing according to ASTM methods D638 (tensile) and D790 (flexural). 'rhe results of this testing are included in Table 2. Far the tensile tests, five replicates were used, and the mean values are reported in Table 2. The flexural values reported in Table 2 are the means for four replicates.
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For a bone plate application, it is considered desirable to have the highest modulus and yield strength, while maintaining ductility. The preferred composition for the bone plate application, in the case of lactide-TMC
block copolymers, would, therefore, be 80 to 90 percent lactide. Above 90 percent lactide, the sample loses ductility, and below 80 percent lactide, the modulus and yield strength continue to decrease without any advan-tage in ductility as measured by strain at break in flexure.
Examt~le 12 Composite Fabrication A composite was fabricated in the following manner. Poly(glycolic acid) (PGA) fiber (100 g/denier) was wound around a 7 3/4" square stainless steel plate.
The fiber covered both si3es of the plate over a section measuring 3°° X 7 3/4°° with the long dimension aligned with the fiber. The weight of fiber used for this operation was 12.0 g.
A 10 g/dL solution of the polymer of Example 7 was prepared in methylene chloride. Polymer was then brushed onto the fiber and air dried. This was repeated several times. The material was then consolidated in a heated press at 170°C and cooled to room temperature.
This allowed for the fiber to be cut and the two halves removed from front and back side of the plate. Addi-tional polymer solution was applied to the two sections.
This was continued until a total of 19.0 g of polymer was added to the fiber. The two halves were then vacuum pressed to a thickness of 1/16" at a temperature of 170°C. The composite was removed from the press and annealed at 110°C in an air oven for twenty minutes.
The final weight fraction of PGA in the composite was 39%.
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The plate was cut into 1/2" X 2 1/2" tensile specimens and tested according to ASTM D638 (Amer. Soc.
of Testing Materials, PA, USA). The tensile modulus was 0.99 X 106 psi and the tensile strength was 37.0 X 103 psi.
Two tensile specimens were strained in flexure (ASTM D790) to 5% in an Instron test machine (Instron Gorp., MA, USA). When the load was relieved, the specimens were permanently deformed to approximately 2%
strain. Flexural modulus was 1.27 X 106 psi and flexural stress at 5% strain was 21.6 X 103 psi.
Part B
The prior art discloses certain nonabsorbable materials that contain o.05 to 20 percent polytetra-fluoroethylene ("PTFE") microfibrous particles. The PTFE is described as useful as an additive to improve viscosity and melt elasticity of certain thermoplastics.
The prior art also discloses a method fox making a molding composition containing 10 to 20 percent PTFE
with a thermoplastic polymer. The composition was found to provide improved impact strength. The prior art also discloses a composition of polyethylene terephthalate with 0.1 to 2.0 percent by weight of a PTFE emulsion incorporated therein. The PTFE additive is said to improve the processability. It also discloses that PTFE
also unexpectedly increases the ultimate elongation of the final compositions. No mention is made in any of the prior art of the usefulness of the materials as deformable articles. No mention of their usefulness in medical products is made. Also, no mention of their usefulness with absorbable polymers is made. In summa-ry, none of the prior art mentions the usefulness as medical devices of absorbable materials combined with PTFE, which can be permanently deformed at room tempera-ture through crazing.
The following embodiments summarize the Part B
inventions:
1. An article of manufacture comprising a deformable surgical repair device, the deformable surgical xepair device manufactured from an absorbable material, the absorbable material having a polymer comprising linkages selected from the group consisting of glycolic acid ester, lactic acid ester, 1,3-dioxan -2-one and 1,4-dioxan-2-one linkages, the surgical repair device further manufactured from a nonabsorbable material.
2. The article of embodiment 1 wherein the nonabsorbable material comprises a polymer prepared from a fluorinated hydrocarbon.
3. The article of embodiment 2 wherein the absorb-able material comprises a homopolymer.
4. The article of embodiment 3 wherein the absorb-able material comprises a homopolymer consisting essen-tially of glycolic acid ester linkages.
5. The article of embodiment 1, 2 or 3 wherein the absorbable material comprises a homopolymer consisting essentially of lactic acid ester linkages.
6. The article of embodiment 1 or 2 wherein the absorbable material comprises a copolymer comprising glycolic acid ester and lactic acid ester linkages.
7. An article of manufacture comprising a deformable tissue repair device, the deformable tissue repair device manufactured from an absorbable material, the absorbable material having a first homopolymer consisting essentially of linkages selected from the group consisting of glycolic acid ester, lactic acid ester and 1,4-dioxan-2-one linkages blended with a second copolymer comprising at least two different linkages selected from the group consisting of glycolic acid ester, lactic acid ester, 1,3-dioxan-2-one, 1,4-dioxan-2-one and e-caprolactone linkages, the tissue a ~~~~r'~~
repair device further manufactured from a nonabsorbable material.
8. The article of embodiment 7 caherein the non-absorbable material comprises a polymer prepared from a fluorinated hydrocarbon.
9. The article of embodiment 8 wherein the first homopolymer consists essentially of glycolic acid ester linkages.
10. The article of embodiment 7 or 8 wherein the first homopolymer consists essentially of lactic said ester linkages.
11. The article of embodiment 9 wherein the second copolymer comprises glycolic acid ester and trimethylene carbonate linkages.
12. The article of embodiment 7, 8, 9 or 11 wherein the second copolymer comprises glycolic acid ester and lactic acid ester linkages.
13. The article of embodiment 2, 3, 4, 8, 9 or 11 wherein the nonabsorbable material is polytetrafluoro-ethylene.
14. An article of manufacture comprising a deformable surgical repair device, the deformable surgical repair device manufactured from an absorbable material, the absorbable material having a first homopolymer comprising linkages selected from the grpup consisting of glycolic acid ester, lactic acid ester and 1,4-dioxan-2-one linkages blended with a second copolymer comprising at least two different linkages selected from the group consisting of glycolic acid ester, lactic acid ester, 1,3-dioxan-2-one, 1,4-dioxan-2-one and e-caprolactone linkages, the deformable surgical repair device further manufactured from a nonabsorbable material, the nonabsorbable materi-al comprising a polymer selected from the group consist-ing of polytetrafluoroethylene and a fluorinated ethylene-propylene copolymer, the nonabsorbable material ~~~~.c~~,~, a comprising more than about 1/100th of one percent to less than about one percent by weight of the device.
15. The article of embodiment 14 wherein the first homopolymer consists essentially of glycolic acid ester linkages.
16. The article of embodiment 14 wherein the first homopolymer consists essentially of lactic acid ester linkages.
17. The article of embodiment 15 wherein the second copolymer comprises glycolic acid ester and trimethylene carbonate linkages.
18. The article of embodiment 14, 15, 16 or 17 wherein the nonabsorbable material is polytetrafluoroethylene.
19. The article of embodiment 18 wherein the nonabsorbable material comprises more than about 1/50th to less than about one-half of one percent by weight of the device.
20. The article of embodiment 19 wherein the nonabsorbable material comprises about 1/l0th of one percent.
21. The article of embodiment 2, 3, 4, 8, 9, 11, 14, 15 or 17 wherein the nonabsorbable material is micropulverized.
22. The article of embodiment 2, 3, 4, 8, 9, 11, 14, 15 or 17 wherein the nonabsorbable material is in microfibrillar form.
23. The article of embodiment 2, 3, 4, 8, 9 11, 14, 15 or 17 wherein the deformable repair device is a fracture fixation device.
24. The article of embodiment 23 wherein the fracture fixation device is a bone plate.
25. The article of embodiment 2, 3, 4, 8, 9, 11, 14, 15 or 17 wherein the deformable repair device is a clip.
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26. The article of embodiment 2, 3, 4, 8, 9, 11, 14, 15 or 17 wherein the deformable repair device is a staple.
Referring to the embodiments in this Part B, subparagraphs 1 and 7 above, it is to be clearly under-stood that the nonabsorbable material is limited to those nonabsorbable compositions of matter which promote crazing. The mechanics of crazing of a polymeric material is well known in the prior art, although it is to be noted that the prior art almost always teaches that a crazing mechanism is not an advantage. There-fore, the invention described in this application teaches away from the known prior art.
Referring to the embodiments in this Part B, subparagraphs 1, 7 and 14, above, and generally as described in this specification, some polymers have been described as linkages of one or more monomers. Some of these monomers are described as cyclic esters, e.g.
1,4-dioxan-2-one. It is to be understood that any person skilled in the art implicitly knows how to make and how to use these monomers to form the polymer linkages and that therefore the description of these linkages by the use of this monomeric nomenclature is adequate.
Referring to the embodiments in this Part B, subparagraphs 1, 7, 14 and 23, above, it is to be clearly understood that the surgical repair, tissue repair and fracture fixation devices include, but are not limited to, those embodiments described in this Part B, subparagraphs 24 to 26 above. Thus, other devices, e.g. a bone pin, bone rod, bone screw, trocar, prosthet-ic tubular article and similar or related molded or extruded devices, are within the scope of this inven-tion.
Referring to the embodiments in this Part B, subparagraphs 21 and 22, above, a description of a micropulverized or microfibrillar fluorinated hydro-carbon polymer, and specifically polytetrafluoro-ethylene is disclosed in the prior art.
Part B DESCRIPTION
This invention relates to partially absorbable polymeric materials possessing an enhanced ability for permanent deformation at room temperature through a crazing mechanism. This invention also relates to the use of these materials in medical device applications that require the material to be reshapable. Applica-tions where these materials may be useful include the following:
_. Maxillofacial bone fixation plates.
2. Bone screws or other fastening devices.
3. Surgical clips and staples.
Although not specifically exemplified, it is recognized that a number of materials could be envi-sioned which could possess similar properties to the exemplified compositions. To have similar properties, it is necessary that the material have a continuous "hard" phase and a "soft°' phase. The soft phase in this invention is PTFE. The PTFE has been compounded with a normally rigid absorbable polymer, which forms the hard phase, by applying shear to the molten polymer in the presence of PTFE powder. The following is a list of alternative materials which are included in this inven-tion:
Hard phase forming absorbable polymers 1. Poly(1-lactide), poly(d-lactide) or poly(meso-lactide) 2. Copolymers of 1-lactide and d-lactide 3. Polyglycolide 4. Lactide-glycolide copolymers 5. Other polymers or copolymers with glass transition temperatures above room temperature.
The selection of a preferred material will depend on the desired physical properties of the final article. The preferred material will also be determined by the desired in vivo degradation and absorption rates.
Several variables can be adjusted to obtain the desired properties. Absorption rate is known to be affected by composition and crystallinity -- for example, a hard phase of poly(1-lactide) would provide a slow degrada-tion rate due to its hydrophobic, crystalline nature, whereas a copolymer of glycolide and dl-lactide in equal amounts would provide a fast degradation rate due to its more hydrophilic, noncrystalline nature. If increased stiffness or strength is required, a fiber or fabric reinforcement can be added to make a composite struc-ture. Further improvement of the composite properties can be made by manipulating the location of the rein-forcement within the composite -- for example, if the reinforcement is placed in the center plane of a lami-nated structure, the composite would be expected to be stiffer in tension (forces applied parallel to the plane) than in flexion (forces applied normal to the plane), allowing reshaping by bending.
-27_ The inventions are described in the following examples:
Example 13 Polvalvcolide Containing 0 1% Teflon Polyglycolide (63g) obtained from Davis & Geck, Wayne, NJ, USA was charged to the mixing head of an Electronic Plasti-corder manufactured by C. W. Brabender Instruments, Inc., NJ, USA. The polymer was heated to its melt temperature and mixed at 40 rpm while 0.063g of Teflon's DLX 6000 powder (DuPont, DE, USA) was added.
The mixing rate was increased to 75 rpm for two minutes and the molten mixture was removed from the mixing head and allowed to cool to room temperature.
Example 14 PolveLlycolide Containin~0% Teflon The procedure of Example 13 was used to prepare a blend of 0.63g of Teflon's DLX 6000 powder in 63g of polyglycolide.
Example 15 Polvalvcolide/Poly(Glycolide-co-trimethylene carbonate) (50/50 Weight Ratiol Containing 0.1% Teflon The procedure of Example 13 was used to mix 0.1~ by weight of Teflon's DLX 6000 powder into a 50/50 weight ratio blend of polyglycolide and poly(glyco-lide-co-trimethylene carbonate). The 50/50 weight ratio blend was obtained from Davis & Geck, Wayne, NJ, USA.
Example 16 Polyalycolide Polyp Glycolide-co-trimethylene carbonate) (75/25 Weight Ratio) Containing 0.1% Teflon The procedure of Example 13 was used to mix 0.1% by weight of Teflon'" DLX 6000 powder into a 75/25 weight ratio blend of polyglycolide and poly(glyco-lide-co-trimethylene carbonate).
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Example 17 Molded Plaques The polymer-Teflon" blends of Examples 13 to 16 were molded into 1/16°' thick plaques by heating each of the blends at a temperature of 230°C. and a pressure of 555 psi for one (1) minute between two Teflon'" coated aluminum plates separated by a 1/16"
thick spacer.
The plaques were allowed to cool to room temperature and were then cut into 1/4" wide strips for manual testing of how readily the strips cauld be deformed at ambient temperature. The results of the manual testing are summarized in Table I.
Example 18 Control Control strips were fabricated according to the procedure of Example 17, above, from polyglycolide that did not contain Teflon"' particles. The control strips were then manually tested as described above.
The results of the manual testing of the control strips are summarized in Table 3.
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Claims (34)
1. An article of manufacture comprising a deformable at ambient temperature surgical clip or staple, the deformable at ambient temperature surgical clip or staple having a flexural strain at break of greater than about 25%, a flexural strain at yield of greater than about 3% and a Young's modulus of greater than about 200,000 psi, and manufactured from a copolymer, the copolymer selected from the group consisting of a block and graft copolymer having a hard and soft phase, the hard phase of said copolymer having a glass transition temperature above ambient temperature and comprising a plurality of first linkages selected from the group consisting of glycolic acid ester and lactic acid ester linkages, and mixtures thereof, and the soft phase of said copolymer having a glass transition temperature below ambient temperature and comprising a plurality of second linkages selected from the group consisting of 1,3-dioxan-2-one; 1,4-dioxan-2-one and ~-caprolactone linkages, the plurality of first linkages comprising at least about 50 up to about 90 mole percent of the copolymer.
2. The article of claim 1, wherein said copolymer is a block copolymer.
3. The article of claim 1 or 2, wherein said plurality of first linkages comprises lactic acid ester linkages.
4. The article of claim 1 or 2, wherein said plurality of first linkages comprises glycolic acid ester linkages.
5. The article of any one of claims 1 to 4, wherein said plurality of second linkages comprises 1,3-dioxan-2-one linkages.
6. An article of manufacture comprising a deformable at ambient temperature bone plate, the deformable at ambient temperature bone plate having a flexural strain at break of greater than about 25%, a flexural strain at yield of greater than about 3% and a Young's modulus of greater than about 200,000 psi, and manufactured from a copolymer, the copolymer selected from the group consisting of a block and graft copolymer having a hard and soft phase, the hard phase of said copolymer having a glass transition temperature above ambient temperature and having a plurality of first linkages comprising lactic acid ester linkages and the soft phase of said copolymer having a glass transition temperature below ambient temperature and comprising a plurality of second linkages selected from the group consisting of 1,3-dioxan-2-one and 1,4-dioxan-2-one linkages, the plurality of lactic acid ester linkages comprising more than 50 to about 90 weight percent of the copolymer.
7. The article of claim 6, wherein said copolymer is a block copolymer.
8. The article of claim 6 or 7, wherein said plurality of lactic acid ester linkages comprises about 80 weight percent of the copolymer.
9. The article of claim 6, 7 or 8, wherein the plurality of second linkages comprises 1,3-dioxan-2-one linkages.
10. An article of manufacture comprising a deformable at ambient temperature surgical clip or staple, the deformable at ambient temperature surgical clip or staple having a flexural strain at break of greater than about 25%, a flexural strain at yield of greater than about 3% and a Young's modulus of greater than about 200,000 psi, and manufactured from a blend of first, hard phase forming, absorbable polymer and a second, soft phase forming, absorbable polymer, the first absorbable polymer having a glass transition temperature above ambient temperature and comprising a plurality of linkages selected from the group consisting of glycolic acid ester and lactic acid ester linkages, and mixtures thereof, and the second absorbable polymer having a glass transition temperature below ambient temperature and comprising a plurality of linkages selected from the group consisting of 1,3-dioxan-2-one, 1,4-dioxin-2-one and ~-caprolactone linkages, said first absorbable polymer comprising at least about 50 up to about 90 weight percent of the blend.
11. The article of claim 20, wherein said first absorbable polymer is a homopolymer.
12. The article of claim 11, wherein said first absorbable homopolymer consists essentially of lactic acid ester linkages.
13. The article of claim 10, wherein said first absorbable polymer is a copolymer.
14. The article of ;any one of claims 10 to 13, wherein said second absorbable polymer comprises a plurality of linkages selected from the group consisting of 1,3-dioxin-2-one and 1,4-dioxin-2-one linkages.
15. The article of any one of claims 1 to 5, and 10 to 14, wherein the deformable surgical clip or staple is a clip.
16. The article of any one of claims 1 to 5, and 10 to 14, wherein the deformable surgical clip or staple is a staple.
17. A surgical composite structure for mammalian tissue, comprising:
a) a reinforcing component prepared from a plurality of fibers, the plurality of fibers manufactured from a biocompatible polymer; and b) a deformable at ambient temperature bioabsorbable component consolidated around said plurality of fibers to form a matrix, the bioabsorbable component comprising a copolymer, the copolymer selected from the group consisting of a block and graft copolymer, the copolymer comprising a plurality of first linkages selected from the group consisting of glycolic acid ester and lactic acid ester linkages, and mixtures thereof, and a plurality of second linkages selected from the group consisting of 1,3-dioxan-2-one; 1,4-dioxan-2-one and E-caprolactone linkages, the plurality of first linkages comprising at least about 50 up to about 90 mole percent of the copolymer.
a) a reinforcing component prepared from a plurality of fibers, the plurality of fibers manufactured from a biocompatible polymer; and b) a deformable at ambient temperature bioabsorbable component consolidated around said plurality of fibers to form a matrix, the bioabsorbable component comprising a copolymer, the copolymer selected from the group consisting of a block and graft copolymer, the copolymer comprising a plurality of first linkages selected from the group consisting of glycolic acid ester and lactic acid ester linkages, and mixtures thereof, and a plurality of second linkages selected from the group consisting of 1,3-dioxan-2-one; 1,4-dioxan-2-one and E-caprolactone linkages, the plurality of first linkages comprising at least about 50 up to about 90 mole percent of the copolymer.
18. The structure of claim 17, wherein the reinforcing component is manufactured from an absorbable biocompatible polymer.
19. The structure of claim 18, wherein the absorbable biocompatible polymer is selected from the group consisting of a homopolymer or copolymer of polyglycolic acid, polylactic acid, polyhydroxy butyrate and blends thereof, and poly(d-lactic acid) blended with poly(1-lactic acid).
20. The structure of claim 17, wherein the reinforcing component is manufactured from a nonabsorbable biocompatible polymer.
21. The structure of claim 20, wherein the nonabsorbable biocompatible polymer is selected from the group consisting of polyethylene terephthalate, silk, nylon, polypropylene, polyethylene, polyoxymethylene and blends thereof.
22. The structure of any one of claims 17 to 21, wherein the bioabsorbable component comprises a block copolymer.
23. The structure of claim 22, wherein said plurality of first linkages in the block copolymer comprises lactic acid ester linkages.
24. The structure of claim 22, wherein said plurality of first linkages in the block copolymer comprises glycolic acid ester linkages.
25. The structure of claim 23 or 24, wherein said plurality of second linkages in said block copolymer comprises 1,3-dioxan-2-one linkages.
26. A surgical composite structure for mammalian tissue, comprising:
a) a reinforcing component prepared from a plurality of fibers, the plurality of fibers manufactured from a biocompatible polymer; and b) a deformable at ambient temperature bioabsorbable component consolidated around said plurality of fibers to form a matrix, the bioabsorbable component comprising a blend of a first and second absorbable polymer, the first absorbable polymer comprising a plurality of linkages selected from the group consisting of glycolic acid ester and lactic acid ester linkages, and mixtures thereof, and the second absorbable polymer comprising a plurality of linkages selected from the group consisting of 1,3-dioxan-2-one; 1,4-dioxan-2-one and e-caprolactone linkages, the first absorbable polymer comprising at least about 50 up to about 90 weight percent of the blend.
a) a reinforcing component prepared from a plurality of fibers, the plurality of fibers manufactured from a biocompatible polymer; and b) a deformable at ambient temperature bioabsorbable component consolidated around said plurality of fibers to form a matrix, the bioabsorbable component comprising a blend of a first and second absorbable polymer, the first absorbable polymer comprising a plurality of linkages selected from the group consisting of glycolic acid ester and lactic acid ester linkages, and mixtures thereof, and the second absorbable polymer comprising a plurality of linkages selected from the group consisting of 1,3-dioxan-2-one; 1,4-dioxan-2-one and e-caprolactone linkages, the first absorbable polymer comprising at least about 50 up to about 90 weight percent of the blend.
27. The structure of claim 26, wherein the reinforcing component is manufactured from an absorbable biocompatible polymer.
28. The structure of claim 27, wherein the absorbable biocompatible polymer is selected from the group consisting of a homopolymer or copolymer of polyglycolic acid, polylactic acid, polyhydroxy butyrate and blends thereof, and poly(d-lactic acid) blended with poly(1-lactic acid).
29. The structure of claim 26, wherein the reinforcing component is manufactured from a nonabsorbable biocompatible polymer.
30. The structure of claim 29, wherein the nonabsorbable biocompatible polymer is selected from the group consisting of polyethylene terephthalate, silk, nylon, polypropylene, polyethylene, polyoxymethylene and blends thereof.
31. The structure of any one of claims 26 to 30, wherein said first absorbable polymer in the bioabsorbable component is a homopolymer.
32. The structure of claim 31, wherein the first absorbable homopolymer in said bioabsorbable component consists essentially of lactic acid ester linkages.
33. The structure of any one of claims 26 to 30, wherein said first absorbable polymer in the bioabsorbable component is a copolymer.
34. The structure of any one of claims 31 to 33, wherein said second absorbable polymer in said bioabsorbable component comprises a plurality of linkages selected from the group consisting of 1,3-dioxan-2-one and 1,4-dioxan-2-one linkages.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/548,802 | 1990-07-06 | ||
| US07/548,802 US5080665A (en) | 1990-07-06 | 1990-07-06 | Deformable, absorbable surgical device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2046192A1 CA2046192A1 (en) | 1992-01-07 |
| CA2046192C true CA2046192C (en) | 2003-12-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002046192A Expired - Lifetime CA2046192C (en) | 1990-07-06 | 1991-07-04 | Deformable surgical device |
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| US (3) | US5080665A (en) |
| EP (1) | EP0460439B1 (en) |
| JP (1) | JPH04231963A (en) |
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| AU (2) | AU652761B2 (en) |
| BR (1) | BR9102855A (en) |
| CA (1) | CA2046192C (en) |
| DE (1) | DE69133073T2 (en) |
| DK (1) | DK0460439T3 (en) |
| ES (1) | ES2177519T3 (en) |
| FI (1) | FI913284A (en) |
| IL (1) | IL98146A (en) |
| MX (1) | MX166882B (en) |
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| PT (1) | PT98204A (en) |
| TW (1) | TW205501B (en) |
| ZA (1) | ZA915229B (en) |
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- 1990-07-06 US US07/548,802 patent/US5080665A/en not_active Expired - Lifetime
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1991
- 1991-05-15 IL IL9814691A patent/IL98146A/en active IP Right Grant
- 1991-05-17 EP EP91107998A patent/EP0460439B1/en not_active Expired - Lifetime
- 1991-05-17 DK DK91107998T patent/DK0460439T3/en active
- 1991-05-17 DE DE69133073T patent/DE69133073T2/en not_active Expired - Lifetime
- 1991-05-17 ES ES91107998T patent/ES2177519T3/en not_active Expired - Lifetime
- 1991-06-24 MX MX2636391A patent/MX166882B/en unknown
- 1991-07-02 JP JP91187004A patent/JPH04231963A/en active Pending
- 1991-07-04 PT PT98204A patent/PT98204A/en not_active Application Discontinuation
- 1991-07-04 CA CA002046192A patent/CA2046192C/en not_active Expired - Lifetime
- 1991-07-05 NO NO91912635A patent/NO912635L/en unknown
- 1991-07-05 ZA ZA915229A patent/ZA915229B/en unknown
- 1991-07-05 AU AU80220/91A patent/AU652761B2/en not_active Ceased
- 1991-07-05 BR BR919102855A patent/BR9102855A/en not_active Application Discontinuation
- 1991-07-05 KR KR1019910011408A patent/KR0173469B1/en not_active IP Right Cessation
- 1991-07-05 TW TW080105226A patent/TW205501B/zh active
- 1991-07-05 FI FI913284A patent/FI913284A/en not_active Application Discontinuation
-
1992
- 1992-01-13 US US07/821,731 patent/US5376102A/en not_active Expired - Lifetime
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1994
- 1994-12-09 AU AU80347/94A patent/AU680060B2/en not_active Ceased
-
1998
- 1998-01-09 US US09/005,143 patent/US6130271A/en not_active Expired - Lifetime
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| AU652761B2 (en) | 1994-09-08 |
| DK0460439T3 (en) | 2002-11-04 |
| EP0460439A2 (en) | 1991-12-11 |
| KR0173469B1 (en) | 1999-03-20 |
| EP0460439A3 (en) | 1992-03-25 |
| FI913284A (en) | 1992-01-07 |
| BR9102855A (en) | 1992-02-04 |
| US5376102A (en) | 1994-12-27 |
| NO912635D0 (en) | 1991-07-05 |
| ES2177519T3 (en) | 2002-12-16 |
| DE69133073T2 (en) | 2002-11-14 |
| AU680060B2 (en) | 1997-07-17 |
| ZA915229B (en) | 1992-04-29 |
| PT98204A (en) | 1993-08-31 |
| MX166882B (en) | 1993-02-10 |
| US6130271A (en) | 2000-10-10 |
| KR920002101A (en) | 1992-02-28 |
| TW205501B (en) | 1993-05-11 |
| CA2046192A1 (en) | 1992-01-07 |
| NO912635L (en) | 1992-01-07 |
| DE69133073D1 (en) | 2002-08-29 |
| US5080665A (en) | 1992-01-14 |
| AU8022091A (en) | 1992-01-09 |
| FI913284A0 (en) | 1991-07-05 |
| IL98146A (en) | 1996-01-31 |
| EP0460439B1 (en) | 2002-07-24 |
| JPH04231963A (en) | 1992-08-20 |
| IL98146A0 (en) | 1992-06-21 |
| AU8034794A (en) | 1995-02-16 |
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