# US 2016/0354510 A1 · Absorbable Medical Devices Based on Novel Films and Foams Made From Semi-Crystalline, Segmented Copolymers of Lactide and Epsilon-Caprolactone Exhibiting Long Term Absorption Characteristics > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2016/0354510 A1 - Document ID: US20160354510A1 - Status: Published application - Kind: A1 - Application number: 14/728,177 - Filed: 2015-06-02 - Published: 2016-12-08 - Earliest claimed: 2015-06-02 - Assignees: Ethicon, Inc. - Applicants: Ethicon, Inc. - Inventors: Sasa Andjelic; Dennis D. Jamiolkowski; Jackie Donners; Mark Timmer - Web page: https://patentgrep.com/patent/US20160354510A1 ## CPC - A61L 24/046: {obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds (A61L24/043 takes precedence)} - A61L 24/001: {Use of materials characterised by their function or physical properties} - A61L 24/0036: {Porous materials, e.g. foams or sponges} - A61L 27/18: obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds - A61L 27/56: Porous materials, {e.g. foams or sponges} - A61L 27/58: Materials at least partially resorbable by the body - A61L 31/06: obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds {(A61L31/041 takes precedence)} - A61L 31/146: {Porous materials, e.g. foams or sponges} - A61L 31/148: {Materials at least partially resorbable by the body} - C08G 63/08: Lactones or lactides - C08J 5/18: Manufacture of films or sheets - C08J 9/04: using blowing gases generated by a previously added blowing agent - C08J 9/26: by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out - C08L 67/04: Polyesters derived from hydroxycarboxylic acids, e.g. lactones (C08L67/06 takes precedence) - C08G 2101/00: Manufacture of cellular products - C08J 2201/03: Extrusion of the foamable blend - C08J 2201/0482: the liquid phase being organic - C08J 2205/02: the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition - C08J 2300/16: Biodegradable polymers - C08J 2367/04: Polyesters derived from hydroxy carboxylic acids, e.g. lactones (C08J2367/06 takes precedence) - 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 (preservation of bodies or disinfecting characterised by the agents employed A01N; preserving, e.g. sterilising, food or foodstuffs A23; preparations for medical, dental or toiletry purposes A61K) - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) ## Abstract Absorbable medical devices based on novel foams and films made from semi-crystalline, segmented copolymers of lactide and epsilon-caprolactone exhibiting long term absorption characteristics are disclosed. Also disclosed are methods of producing said foams and films, and useful polymer solutions. ## Claims ### Claim 1 An absorbable foam, comprising a semicrystalline absorbable segmented copolymer, said copolymer comprising repeating units of polymerized lactide and polymerized epsilon-caprolactone, wherein the mole ratio of polymerized lactide to polymerized epsilon-caprolactone is between about 60:40 to about 75:25, said copolymer having a first heat Tg, as determined by differential scanning calorimetry at a scan rate of 10° C. per minute, equal to or less than 0° C., and a crystallinity level of about 20 percent to about 50 percent, as measured by wide angle X-ray diffraction. ### Claim 2 (depends on 1) The foam of claim 1 in which the solids content is between about 3 weight percent to about 30 weight percent. ### Claim 3 (depends on 2) The foam of claim 2 having a solid content between 5 weight percent and 20 weight percent. ### Claim 4 (depends on 1) The foam of claim 1 having a thickness between about 20 mils to about 500 mils. ### Claim 5 (depends on 4) The foam of claim 4 having a thickness between about 40 mils and about 200 mils. ### Claim 6 (depends on 1) The foam of claim 1 having mechanical integrity at least 40 days post-implantation or having mechanical integrity after at least 40 days of incubation in a buffer of pH 7.27 at 37° C. ### Claim 7 (depends on 1) The foam of claim 1 having mechanical integrity at least 64 days post-implantation or having mechanical integrity after at least 64 days of incubation in a buffer of pH 7.27 at 37° C. ### Claim 8 (depends on 1) The foam of claim 1 having a crystallinity level great than about 25 percent. ### Claim 9 (depends on 1) The foam of claim 1, wherein the copolymer has an inherent viscosity at least about 0.5 dL/g, as measured in a 0.1 g/dl solution of HFIP at 25° C. ### Claim 10 A method of making an absorbable foam by a melt process, comprising the steps of: A. providing an absorbable polymer comprising a semicrystalline absorbable segmented copolymer, said copolymer comprising repeating units of polymerized lactide and polymerized epsilon-caprolactone, wherein the mole ratio of polymerized lactide to polymerized epsilon-caprolactone is between about 60:40 to about 75:25, said copolymer having a first heat Tg, as determined by differential scanning calorimetry at a scan rate of 10° C. per minute, equal to or less than 0° C., and a crystallinity level of about 20 to about 50 percent, as measured by wide angle X-ray diffraction, said copolymer having a melt temperature; B. heating the copolymer above the melt temperature to form a melt; C. introducing a suitable blowing agent (chemical or physical) into the melt; and D. enabling the gas produced from the blowing agent to expand within the melt to form an absorbable foam. ### Claim 11 A method of making an absorbable foam by a melt process, comprising the steps of: A. providing an absorbable polymer comprising a semicrystalline absorbable segmented copolymer, said copolymer comprising repeating units of polymerized lactide and polymerized epsilon-caprolactone, wherein the mole ratio of polymerized lactide to polymerized epsilon-caprolactone is between about 60:40 to about 75:25, said copolymer having a first heat Tg, as determined by differential scanning calorimetry at a scan rate of 10° C. per minute, equal to or less than 0° C., and a crystallinity level of about 20 to about 50 percent, as measured by wide angle X-ray diffraction, said copolymer having a melt temperature; B. transferring the said absorbable polymer to the hopper of a melt extruder outfitted with a profile die, with a barrel outfitted with a gas injection port, and die heated to a temperature within the range of about 10° C. above the melt temperature of said absorbable polymer to about 270° C. to form a melt; C. extruding said absorbable polymer through said profile die, while injecting into the melt through the gas injection port a gas selected from the group of carbon dioxide, nitrogen, helium, and argon, resulting in a foam; and, D. collecting said foam at a rate to result in a foam thickness between about 0.1 mils and 50 mils. ### Claim 12 A method of making an absorbable foam by a melt process, comprising the steps of: A. providing an absorbable polymer comprising a semicrystalline absorbable segmented copolymer, said copolymer comprising repeating units of polymerized lactide and polymerized epsilon-caprolactone, wherein the mole ratio of polymerized lactide to polymerized epsilon-caprolactone is between about 60:40 to about 75:25, said copolymer having a first heat Tg, as determined by differential scanning calorimetry at a scan rate of 10° C. per minute, equal to or less than 0° C., and a crystallinity level of about 20 to about 50 percent, as measured by wide angle X-ray diffraction, said copolymer having a melt temperature; B. transferring the said absorbable polymer in combination with a solid blowing agent to the hopper of a melt extruder outfitted with a profile die, and die heated to a temperature within the range of about 10° C. above the melt temperature of said absorbable polymer to about 270° C.; C. extruding said absorbable polymer through said profile die, resulting in a foam; and, D. collecting said foam at a rate to result in a foam thickness between about 0.1 mils and 50 mils. ### Claim 13 A method of making an absorbable foam by a lyophilization process, comprising the steps of: A. providing an absorbable polymer comprising a semicrystalline absorbable segmented copolymer, said copolymer comprising repeating units of polymerized lactide and polymerized epsilon-caprolactone, wherein the mole ratio of polymerized lactide to polymerized epsilon-caprolactone is between about 60:40 to about 75:25, said copolymer having a first heat Tg, as determined by differential scanning calorimetry at a scan rate of 10° C. per minute, equal to or less than 0° C., and a crystallinity level of about 20 to about 50 percent, as measured by wide angle X-ray diffraction; B. dissolving a sufficient quantity of the copolymer in a suitable solvent to form a lyophilizing solution; C. pouring at least a part of the solution into a suitable mold; and, D. subjecting the solution in the mold to a lyophilizing process to form an absorbable foam. ### Claim 14 (depends on 13) The method of claim 13 wherein the solvent is selected from the group consisting of 1,4-dioxane, trioxane, a mixture of at least 90 weight percent 1,4-dioxane and no more than 10 weight percent water, and a mixture of at least 90 weight percent 1,4-dioxane and no more than 10 weight percent of an organic alcohol having a molecular weight of less than 1500 Daltons. ### Claim 15 (depends on 13) The method of claim 13 wherein the dissolved absorbable polymer is between about 3 to about 30 percent by weight of the solution. ### Claim 16 (depends on 13) The method of claim 13 wherein the resulting foam has a thickness between about 20 to about 500 mils. ### Claim 17 A lyophilizing solution, comprising: A. a solvent selected from the group consisting of 1,4-dioxane, trioxane, a mixture of at least 90 weight percent 1,4-dioxane and no more than 10 weight percent water, and a mixture of at least 90 weight percent 1,4-dioxane and no more than 10 weight percent of an organic alcohol having a molecular weight of less than 1500 Daltons; and, B. about 3 wt. % to about 30 wt. % of a polymer comprising a semicrystalline absorbable segmented copolymer, the copolymer comprising repeating units of polymerized lactide and polymerized epsilon-caprolactone, wherein the mole ratio of polymerized lactide to polymerized epsilon-caprolactone is between about 60:40 to about 75:25, said copolymer having a first heat Tg, as determined by differential scanning calorimetry at a scan rate of 10° C. per minute, equal to or less than 0° C., and a crystallinity level of about 20 to about 50 percent, as measured by wide angle X-ray diffraction. ### Claim 18 (depends on 17) The lyophilizing solution of claim 17 wherein said solution remains non-gelling at 20° C. for at least 18 hours. ### Claim 19 (depends on 17) The lyophilizing solution of claim 17 wherein said solution remains non-gelling at 20° C. for at least 168 hours. ### Claim 20 An absorbable film comprising a semicrystalline absorbable segmented copolymer, the copolymer comprising repeating units of polymerized lactide and polymerized epsilon-caprolactone, wherein the mole ratio of polymerized lactide to polymerized epsilon-caprolactone is between about 60:40 to about 75:25, said copolymer having a first heat Tg, as determined by differential scanning calorimetry at a scan rate of 10° C. per minute, equal to or less than 0° C., and a crystallinity level of about 20 to about 50 percent, as measured by wide angle X-ray diffraction. ### Claim 21 (depends on 20) The film of claim 20 having a thickness between about 0.1 mil to about 50 mil. ### Claim 22 (depends on 20) The film of claim 20 having mechanical integrity at least 40 days post-implantation or having mechanical integrity after at least 40 days of incubation in a buffer of pH 7.27 at 37° C. ### Claim 23 (depends on 20) The film of claim 20 having mechanical integrity at least 64 days post-implantation or having mechanical integrity after at least 64 days of incubation in a buffer of pH 7.27 at 37° C. ### Claim 24 A method of making an absorbable film by melt processing, comprising the steps of: A. providing an absorbable polymer comprising a semicrystalline absorbable segmented copolymer, the copolymer comprising repeating units of polymerized lactide and polymerized epsilon-caprolactone, wherein the mole ratio of polymerized lactide to polymerized epsilon-caprolactone is between about 60:40 to about 75:25, said copolymer having a first heat Tg, as determined by differential scanning calorimetry at a scan rate of 10° C. per minute, equal to or less than 0° C., and a crystallinity level of about 20 to about 50 percent, as measured by wide angle X-ray diffraction, said copolymer having a melt temperature; B. transferring the said absorbable polymer to the hopper of a melt extruder outfitted with a slit die, with a barrel and die temperature within the range of about 10° C. above the melt temperature of the said absorbable polymer to about 270° C.; C. extruding said absorbable polymer through said slit die, resulting in a film; and, D. drawing said film to a draw ratio between about 0.8× to about 10× to form a film having a thickness between about 0.1 mils and 50 mils. ### Claim 25 A method of making an absorbable film by a solution process, comprising the steps of: A. providing an absorbable polymer comprising a semicrystalline absorbable segmented copolymer, said copolymer comprising repeating units of polymerized lactide and polymerized epsilon-caprolactone, wherein the mole ratio of polymerized lactide to polymerized epsilon-caprolactone is between about 60:40 to about 75:25, said copolymer having a first heat Tg, as determined by differential scanning calorimetry at a scan rate of 10° C. per minute, equal to or less than 0° C., and a crystallinity level of about 20 to about 50 percent, as measured by wide angle X-ray diffraction; B. dissolving a sufficient quantity of the copolymer in a suitable solvent to form a polymer solution; C. pouring at least a part of the solution into a suitable mold or dispensing the polymer solution onto a conveying surface; and, D. allowing the solvent to be removed from the polymer solution to form an absorbable film.