Tunable segmented polyacetal

• US 9,120,919 B2
• Filed: 12/22/2004
• Issued: 09/01/2015
• Est. Priority Date: 12/23/2003
• Status: Expired due to Fees

• Current Assignee: Smith & Nephew Incorporated (Smith & Nephew PLC)
• Original Assignee: Smith & Nephew Incorporated (Smith & Nephew PLC)
• Inventors: Brown, Malcolm
• Primary Examiner(s): PEPITONE, MICHAEL F
• Application Number:
  US10/584,115
• Publication Number:
  US 20070299156A1
• Time in Patent Office: 3,905 Days
• Field of Search: 523/114, 525/469, 525/79, 528/392
• US Class Current: 1/1
• CPC Class Codes: A61L 2400/06 Flowable or injectable implant compositions
• CPC Class Codes: A61L 27/18 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: A61L 27/58 Materials at least partially resorbable by the body
• CPC Class Codes: C08G 2261/126 block
• CPC Class Codes: C08G 63/664 derived from hydroxy carboxylic acids
• CPC Class Codes: C08G 63/668 derived from polycarboxylic acids and polyhydroxy compounds
• CPC Class Codes: C08G 81/024 Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
• CPC Class Codes: C08G 81/027 containing polyester or polycarbonate sequences
• CPC Class Codes: C08G 81/028 containing polyamide sequences
• CPC Class Codes: C08K 3/32 Phosphorus-containing compounds
• CPC Class Codes: C08L 101/16 the macromolecular compounds being biodegradable
• CPC Class Codes: C08L 59/00 Compositions of polyacetals; Compositions of derivatives of polyacetals of polyvinyl acetals C08L29/14

Abstract

The present invention relates to polymer compositions namely biodegradable segmented block copolymers comprising polyol residues having a number average molecular weight of at least 4000 Daltons and in that the polyols are connected by actual linkages.

Claims

1. A biodegradable segmented block copolymer comprising strength blocks each comprising repeat units, each repeat unit comprising a polymer polyol residue, wherein the polymer polyol residues each have a molecular weight of at least 4000 Daltons, wherein the strength blocks are connected by acetal linkages, wherein the polymer polyol residues are selected from the group consisting of polyesters, degradable carbonates, and polyamides, and wherein the biodegradable segmented block copolymer is insoluble in physiological conditions.

2. The biodegradable segmented block copolymer of claim 1, wherein the acetal linkages comprise polyacetal residues.

3. The biodegradable segmented block copolymer of claim 2, wherein the polyacetal residues comprise enzyme degradable polyacetal/diamino acid ester blocks.

4. The biodegradable segmented block copolymer of claim 2, wherein the polyacetal residues comprise an incorporated bioactive diol.

5. The biodegradable segmented block copolymer of claim 2, wherein the polyacetal residues comprise enzyme degradable polyacetal/diamino acid ester blocks and incorporated bioactive agent.

6. The biodegradable segmented block copolymer of claim 1, wherein the segmented block copolymer is blended with at least one agent selected from the group consisting of other polymeric, ceramic, and glass material.

7. The biodegradable segmented block copolymer of claim 1, wherein the polymer polyol residues have a molecular weight of at least 5000 Daltons.

8. The biodegradable segmented block copolymer of claim 1, wherein the polymer polyol residues have a molecular weight between 4000 and 20000 Daltons.

9. The biodegradable segmented block copolymer of claim 1, wherein the polymer polyol residues comprise a polyester.

10. The biodegradable segmented block copolymer of claim 9, wherein the polyester is selected from the group consisting of homo-polymers and co-polymers of polycaprolactone (PCL), polylactic acid (PLA, L and D forms), polyglycolic acid (PGA), polydioxanone, aliphatic esters and aromatic esters.

11. The biodegradable segmented block copolymer of claim 1, wherein the polymer polyol residues comprise a degradable carbonate.

12. The biodegradable segmented block copolymer of claim 1, wherein the polymer polyol residues comprise a polyamide.

13. The biodegradable segmented block copolymer of claim 1, wherein the biodegradable segmented block copolymer further comprises a polymer selected from the group consisting of polyglycolic acid (PGA), polycaprolactone (PCL) and polylactic acid (PLA).

14. The biodegradable segmented block copolymer of claim 1, wherein the biodegradable segmented block copolymer further comprises a biocompatible inorganic material.

15. The biodegradable segmented block copolymer of claim 14, wherein the biocompatible inorganic material is selected from the group consisting of calcium carbonate, hydroxyapatite (RA), and tricalcium phosphate (TCP).

16. The biodegradable segmented block copolymer of claim 1, wherein a stabilizer and/or accelerator is blended into and/or polymerized into the biodegradable segmented block copolymer.

17. The biodegradable segmented block copolymer of claim 1, further comprising a biological active agent blended in and/or reacted with the segmented block copolymer.

18. The biodegradable segmented block copolymer of claim 17, wherein said biological active agent is selected from the group consisting of a growth factor, an antibiotic, a strontium salt, a fluoride salt, a magnesium salt, a sodium salt, a bone morphogenetic factor, a chemotherapeutic agent, a pain killer, a bisphosphonate, a bone growth agent, an angiogenic factor, and any combination thereof.

19. The biodegradable segmented block copolymer of claim 18, wherein said biological agent comprises a growth factor and wherein said growth factor is selected from the group consisting of platelet derived growth factor (PDGF), transforming growth factor beta (TGF-beta), insulin-related growth factor-I (IGF-I), insulin-related growth factor-II (IGF-II), fibroblast growth factor (FGF), beta-2-microglobulin (BDGF II), bone morphogenetic protein (BMP), and any combination thereof.

20. The biodegradable segmented block copolymer of claim 18, wherein said biological agent comprises an antibiotic and wherein said antibiotic is selected from the group consisting of tetracycline hydrochloride, vancomycin, cephalosporins, and aminoglycosides such as tobramycin, gentacin, and any combination thereof.

21. The biodegradable segmented block copolymer of claim 18, wherein said biological agent comprises a bone growth agent and wherein said bone growth agent is selected from the group consisting of proteins of demineralised bone, demineralised bone matrix (DBM), bone protein (BO), bone morphogenetic protein (BMP), osteonectin, osteocalcin, osteogenin, and any combination thereof.

22. The biodegradable segmented block copolymer of claim 18, wherein said biological agent comprises a chemotherapeutic agent and wherein said chemotherapeutic agent is selected from the group consisting of cisplatinum, ifosfamide, methotrexate, doxorubicin hydrochloride, and any combination thereof.

23. The biodegradable segmented block copolymer of claim 18, wherein said biological agent comprises a pain killer and wherein said pain killer is selected from the group consisting of lidocaine hydrochloride, bipivacain hydrochloride, non-steroidal anti-inflammatory drugs including ketorolac tromethamine, and any combination thereof.

24. The biodegradable segmented block copolymer of claim 1, wherein the biodegradable segmented block copolymer further comprises a reinforcing material.

25. The biodegradable segmented block copolymer of claim 24, wherein the reinforcing material comprises a polymer filler particulate.

26. The biodegradable segmented block copolymer of claim 24, wherein the reinforcing material comprises a fiber.

27. The biodegradable segmented block copolymer of claim 1, wherein the biodegradable segmented block copolymer forms in whole, or part, a medical device.

28. A medical device comprising the biodegradable segmented block copolymer of claim 1.

29. A method of manufacture of a medical device comprising forming in situ the biodegradable segmented block copolymer of claim 1.

30. The medical device of claim 28, wherein the biodegradable segmented block copolymer comprises a coating on the medical device.