CA2296642C - Silicon-containing chain extenders - Google Patents
Silicon-containing chain extenders Download PDFInfo
- Publication number
- CA2296642C CA2296642C CA002296642A CA2296642A CA2296642C CA 2296642 C CA2296642 C CA 2296642C CA 002296642 A CA002296642 A CA 002296642A CA 2296642 A CA2296642 A CA 2296642A CA 2296642 C CA2296642 C CA 2296642C
- Authority
- CA
- Canada
- Prior art keywords
- polyurethane
- radicals
- macrodiol
- composition
- unsaturated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000004970 Chain extender Substances 0.000 title claims abstract description 64
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 15
- 239000010703 silicon Substances 0.000 title claims abstract description 15
- 150000002009 diols Chemical class 0.000 claims abstract description 22
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 18
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 10
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 9
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims abstract description 9
- 125000005647 linker group Chemical group 0.000 claims abstract description 5
- -1 heterocyclic radical Chemical class 0.000 claims description 223
- 239000000203 mixture Substances 0.000 claims description 105
- 239000004814 polyurethane Substances 0.000 claims description 102
- 229920002635 polyurethane Polymers 0.000 claims description 96
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 claims description 30
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 27
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 24
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 23
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 23
- 239000007943 implant Substances 0.000 claims description 23
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 23
- 230000015556 catabolic process Effects 0.000 claims description 22
- 238000006731 degradation reaction Methods 0.000 claims description 22
- 229920000570 polyether Polymers 0.000 claims description 22
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- 125000002911 monocyclic heterocycle group Chemical group 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 125000000623 heterocyclic group Chemical group 0.000 claims description 17
- 125000005442 diisocyanate group Chemical group 0.000 claims description 15
- 229920001296 polysiloxane Polymers 0.000 claims description 15
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 11
- 150000003254 radicals Chemical class 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000002950 monocyclic group Chemical group 0.000 claims description 8
- 125000003367 polycyclic group Polymers 0.000 claims description 8
- 125000000304 alkynyl group Chemical group 0.000 claims description 7
- 230000000747 cardiac effect Effects 0.000 claims description 7
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Chemical group 0.000 claims description 6
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000005864 Sulphur Chemical group 0.000 claims description 5
- 125000004450 alkenylene group Chemical group 0.000 claims description 5
- 125000004419 alkynylene group Chemical group 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000012620 biological material Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000001301 oxygen Chemical group 0.000 claims description 5
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 4
- OWJKJLOCIDNNGJ-UHFFFAOYSA-N 4-[[4-hydroxybutyl(dimethyl)silyl]oxy-dimethylsilyl]butan-1-ol Chemical compound OCCCC[Si](C)(C)O[Si](C)(C)CCCCO OWJKJLOCIDNNGJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 claims description 4
- 210000003709 heart valve Anatomy 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- 230000002792 vascular Effects 0.000 claims description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 3
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 claims description 3
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 claims description 2
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 claims description 2
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 claims description 2
- 125000006039 1-hexenyl group Chemical group 0.000 claims description 2
- PAUHLEIGHAUFAK-UHFFFAOYSA-N 1-isocyanato-1-[(1-isocyanatocyclohexyl)methyl]cyclohexane Chemical compound C1CCCCC1(N=C=O)CC1(N=C=O)CCCCC1 PAUHLEIGHAUFAK-UHFFFAOYSA-N 0.000 claims description 2
- 125000006023 1-pentenyl group Chemical group 0.000 claims description 2
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 claims description 2
- 125000003562 2,2-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 claims description 2
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 claims description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000004336 3,3-dimethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000006041 3-hexenyl group Chemical group 0.000 claims description 2
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- JRQLZCFSWYQHPI-UHFFFAOYSA-N 4,5-dichloro-2-cyclohexyl-1,2-thiazol-3-one Chemical compound O=C1C(Cl)=C(Cl)SN1C1CCCCC1 JRQLZCFSWYQHPI-UHFFFAOYSA-N 0.000 claims description 2
- 101100331550 Antirrhinum majus DICH gene Proteins 0.000 claims description 2
- 241001631457 Cannula Species 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000004442 acylamino group Chemical group 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000005035 acylthio group Chemical group 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000006323 alkenyl amino group Chemical group 0.000 claims description 2
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003282 alkyl amino group Chemical group 0.000 claims description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 2
- 125000004656 alkyl sulfonylamino group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000006319 alkynyl amino group Chemical group 0.000 claims description 2
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000005251 aryl acyl group Chemical group 0.000 claims description 2
- 125000001769 aryl amino group Chemical group 0.000 claims description 2
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims description 2
- 125000005279 aryl sulfonyloxy group Chemical group 0.000 claims description 2
- 125000005110 aryl thio group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000000440 benzylamino group Chemical group [H]N(*)C([H])([H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 239000008280 blood Substances 0.000 claims description 2
- 210000004369 blood Anatomy 0.000 claims description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 claims description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000012377 drug delivery Methods 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 125000000262 haloalkenyl group Chemical group 0.000 claims description 2
- 125000005291 haloalkenyloxy group Chemical group 0.000 claims description 2
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 125000000232 haloalkynyl group Chemical group 0.000 claims description 2
- 125000005292 haloalkynyloxy group Chemical group 0.000 claims description 2
- 125000003106 haloaryl group Chemical group 0.000 claims description 2
- 125000004996 haloaryloxy group Chemical group 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 239000002649 leather substitute Substances 0.000 claims description 2
- 238000005065 mining Methods 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004971 nitroalkyl group Chemical group 0.000 claims description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 210000000056 organ Anatomy 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000000565 sealant Substances 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 210000004872 soft tissue Anatomy 0.000 claims description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000002966 varnish Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
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- 150000005840 aryl radicals Chemical class 0.000 claims 3
- 239000000306 component Substances 0.000 claims 2
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 claims 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims 1
- 125000005278 alkyl sulfonyloxy group Chemical group 0.000 claims 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims 1
- 125000004999 nitroaryl group Chemical group 0.000 claims 1
- 125000004585 polycyclic heterocycle group Polymers 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 description 25
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- 229920002379 silicone rubber Polymers 0.000 description 12
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- RYECOJGRJDOGPP-UHFFFAOYSA-N Ethylurea Chemical compound CCNC(N)=O RYECOJGRJDOGPP-UHFFFAOYSA-N 0.000 description 10
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- 239000003054 catalyst Substances 0.000 description 9
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- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000009864 tensile test Methods 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920005903 polyol mixture Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
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- 238000003786 synthesis reaction Methods 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
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- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 210000001519 tissue Anatomy 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000001113 thiadiazolyl group Chemical group 0.000 description 2
- 239000011995 wilkinson's catalyst Substances 0.000 description 2
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
- 125000000196 1,4-pentadienyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])=C([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- IOSZAJFVMXYBPJ-UHFFFAOYSA-N 6-[[6-hydroxyhexyl(dimethyl)silyl]oxy-dimethylsilyl]hexan-1-ol Chemical compound OCCCCCC[Si](C)(C)O[Si](C)(C)CCCCCCO IOSZAJFVMXYBPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000005874 benzothiadiazolyl group Chemical group 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000003406 indolizinyl group Chemical group C=1(C=CN2C=CC=CC12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- AMLJWLYRONUCKO-UHFFFAOYSA-N n-(6-amino-5-iodopyridin-2-yl)acetamide Chemical compound CC(=O)NC1=CC=C(I)C(N)=N1 AMLJWLYRONUCKO-UHFFFAOYSA-N 0.000 description 1
- 238000010915 one-step procedure Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- UHHKSVZZTYJVEG-UHFFFAOYSA-N oxepane Chemical compound C1CCCOCC1 UHHKSVZZTYJVEG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 206010033675 panniculitis Diseases 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920003224 poly(trimethylene oxide) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 210000004003 subcutaneous fat Anatomy 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—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
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/04—Macromolecular materials
- A61L29/06—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
- A61L31/04—Macromolecular materials
- A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4858—Polyethers containing oxyalkylene groups having more than four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
Abstract
A chain extender including a silicon-containing diol of formula (I) wherein R1, R2, R3, R4, R5, and R6 are the same or different and selected from an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical; R7 is a divalent linking group or an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical; and n is 0 or greater, preferably 2 or less.
Description
SILICON-CONTAINING CHAIN EXTENDERS
The present invention generally relates to silicon-containing chain extenders and their use in the preparation of polyurethane elastomeric compositions having improved properties. These polyurethane compositions are useful for a variety S of applications, in particular the manufacture of medical devices, articles or implants which contact living tissues or bodily fluids.
Polyurethane elastomers are amongst the best performing synthetic polymers in medical implant applications. Their excellent mechanical properties coupled with relatively good biostability make them the choice materials for a number of medical implants including cardiac pacemakers, catheters, implantable prostheses, cardiac assist devices, heart valves and vascular grafts. The excellent mechanical properties of polyurethane elastomers are attributed to their two phase morphology resulting from microphase separation of soft and hard segments. In polyurethanes used for medical implants, the soft segment is 1 S typically formed from a polyether macrodiol such as poly(tetramethylene oxide) (PTMO) while the hard segment is derived from a diisocyanate such as 4,4'-methylenediphenyl diisocyanate (MDI) and a diol chain extender such as 1,4-butanediol (BDO).
The diol chain extender which is used to link up diisocyanates is a relatively small difunctional molecule of molecular weight between about 60 and 350.
The structure of the chain extender makes a significant contribution to the physical properties of the polyurethane elastomers. The most commonly used ' diol chain extender is 1,4-butanediol.
Despite the long term use of polyurethane elastomers for applications such as cardiac pacemakers, in some cases the polyurethanes biodegrade causing surface or deep cracking, stiffening, erosion or the deterioration of mechanical properties such as flexural strength'. Elastomers with high flexibility and low Shore A Durometer hardness in particular degrade faster than the harder and more rigid grades. It is generally hypothesized that the degradation is primarily an in vivo oxidation process involving the polyether soft segment. The currently used medical polyurethanes are polyether-based and the most vulnerable site for degradation is the methylene group alpha to the ether oxygenz of the soft segment. Polyurethanes prepared with a lower amount of polyether component generally exhibit improved degradation resistance. However, such materials typically have high elastic modulus and are difficult to process making them less desirable for many implant applications. Pinchuk has recently reviewed the biostability of polyurethanes3.
Non-PTMO basedpolyurethane formulations which show significantly improved in vivo degradation resistance as demonstrated by animal implant experiments have also recently been disclosed in the patent literature. These include polyurethane formulations based on polycarbonate macrodiols disclosed in US
5,133,742 (Pinchuk) and US 5,254,662 (Szycher) and polyether macrodiols with fewer ether linkages in US 4,875,308 (Meijs et al). The aforementioned patents do not disclose polyurethane formulations which provide materials having flexural modulus, hardness and biostability comparable to those of silicon rubber while retaining high tensile strength, abrasion resistance and tear strength of typical polyurethane elastomers. Although the compositions disclosed in US
5,254,662 provide materials with low elastic modulus and high tensile strength, since those compositions are based on polycarbonate macrodiols and aliphatic diisocyanates, their degradation resistance under in vivo conditions is questionable. Hergenrother et al4 have demonstrated by animal implant experiments that aliphatic diisocyanate based polyurethanes degrade more than the aromatic diisocyanate based polyurethanes. There are also no examples provided in US 5,254,662 to demonstrate the biostability of the disclosed low modulus elastomer compositions.
The present invention generally relates to silicon-containing chain extenders and their use in the preparation of polyurethane elastomeric compositions having improved properties. These polyurethane compositions are useful for a variety S of applications, in particular the manufacture of medical devices, articles or implants which contact living tissues or bodily fluids.
Polyurethane elastomers are amongst the best performing synthetic polymers in medical implant applications. Their excellent mechanical properties coupled with relatively good biostability make them the choice materials for a number of medical implants including cardiac pacemakers, catheters, implantable prostheses, cardiac assist devices, heart valves and vascular grafts. The excellent mechanical properties of polyurethane elastomers are attributed to their two phase morphology resulting from microphase separation of soft and hard segments. In polyurethanes used for medical implants, the soft segment is 1 S typically formed from a polyether macrodiol such as poly(tetramethylene oxide) (PTMO) while the hard segment is derived from a diisocyanate such as 4,4'-methylenediphenyl diisocyanate (MDI) and a diol chain extender such as 1,4-butanediol (BDO).
The diol chain extender which is used to link up diisocyanates is a relatively small difunctional molecule of molecular weight between about 60 and 350.
The structure of the chain extender makes a significant contribution to the physical properties of the polyurethane elastomers. The most commonly used ' diol chain extender is 1,4-butanediol.
Despite the long term use of polyurethane elastomers for applications such as cardiac pacemakers, in some cases the polyurethanes biodegrade causing surface or deep cracking, stiffening, erosion or the deterioration of mechanical properties such as flexural strength'. Elastomers with high flexibility and low Shore A Durometer hardness in particular degrade faster than the harder and more rigid grades. It is generally hypothesized that the degradation is primarily an in vivo oxidation process involving the polyether soft segment. The currently used medical polyurethanes are polyether-based and the most vulnerable site for degradation is the methylene group alpha to the ether oxygenz of the soft segment. Polyurethanes prepared with a lower amount of polyether component generally exhibit improved degradation resistance. However, such materials typically have high elastic modulus and are difficult to process making them less desirable for many implant applications. Pinchuk has recently reviewed the biostability of polyurethanes3.
Non-PTMO basedpolyurethane formulations which show significantly improved in vivo degradation resistance as demonstrated by animal implant experiments have also recently been disclosed in the patent literature. These include polyurethane formulations based on polycarbonate macrodiols disclosed in US
5,133,742 (Pinchuk) and US 5,254,662 (Szycher) and polyether macrodiols with fewer ether linkages in US 4,875,308 (Meijs et al). The aforementioned patents do not disclose polyurethane formulations which provide materials having flexural modulus, hardness and biostability comparable to those of silicon rubber while retaining high tensile strength, abrasion resistance and tear strength of typical polyurethane elastomers. Although the compositions disclosed in US
5,254,662 provide materials with low elastic modulus and high tensile strength, since those compositions are based on polycarbonate macrodiols and aliphatic diisocyanates, their degradation resistance under in vivo conditions is questionable. Hergenrother et al4 have demonstrated by animal implant experiments that aliphatic diisocyanate based polyurethanes degrade more than the aromatic diisocyanate based polyurethanes. There are also no examples provided in US 5,254,662 to demonstrate the biostability of the disclosed low modulus elastomer compositions.
The conventional method of preparing polyurethane elastomers with low hardness and modulus is by formulation changes so as to have a relatively higher percentage of the soft segment component. However, the materials made . this way generally have very poor mechanical properties and biostability.
For S example, it is reported2~3 that Pellethane 2363-80A (Registered Trade Mark) which has a higher percentage of soft segment than that in the harder grade Pellethane 2363-SSD (Registered Trade Mark), is significantly more prone to stress cracking in the biological environment. However, these reports do not disclose methods for formulating polyurethanes with hardness lower than 80 A
while retaining good biostability and mechanical properties. Despite the good stability of silicone rubber in biological environments, its use in the medical implant area is limited by poor properties such as low abrasion resistance and low tensile and tear strengths.
Although the aforementioned non-PTMO based polyurethane elastomers address the issue of biostability, they do not provide methods of formulating polyurethanes having properties such as flexibility and biostability comparable to those of silicone rubber. The formulations disclosed in the above patents (except US 5,254,662) typically have hardness in excess of Shore 80 A.
A requirement accordingly exists to develop polyurethanes having properties such as low durometer hardness, low flexural modulus, good processability and high resistance to degradation, without the disadvantages of silicone rubber such as poor tensile strength, abrasion resistance and tear strength. Such polyurethanes should also preferably have a good biostability for applications ' such as pacemaker leads, vascular grafts, heart valves and the like.
According to one aspect of the present invention there is provided a chain extender including a silicon-containing diol of the formula (I):
For S example, it is reported2~3 that Pellethane 2363-80A (Registered Trade Mark) which has a higher percentage of soft segment than that in the harder grade Pellethane 2363-SSD (Registered Trade Mark), is significantly more prone to stress cracking in the biological environment. However, these reports do not disclose methods for formulating polyurethanes with hardness lower than 80 A
while retaining good biostability and mechanical properties. Despite the good stability of silicone rubber in biological environments, its use in the medical implant area is limited by poor properties such as low abrasion resistance and low tensile and tear strengths.
Although the aforementioned non-PTMO based polyurethane elastomers address the issue of biostability, they do not provide methods of formulating polyurethanes having properties such as flexibility and biostability comparable to those of silicone rubber. The formulations disclosed in the above patents (except US 5,254,662) typically have hardness in excess of Shore 80 A.
A requirement accordingly exists to develop polyurethanes having properties such as low durometer hardness, low flexural modulus, good processability and high resistance to degradation, without the disadvantages of silicone rubber such as poor tensile strength, abrasion resistance and tear strength. Such polyurethanes should also preferably have a good biostability for applications ' such as pacemaker leads, vascular grafts, heart valves and the like.
According to one aspect of the present invention there is provided a chain extender including a silicon-containing diol of the formula (I):
Rl R2 HO-RS- ii - R~- ii -R6-OH
R4 n (I) wherein R,, R2, R3, R4, R5, and R6 are the same or different and selected from an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical;
R~ is a divalent linking group or an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical; and n is 0 or greater, preferably 2 or less.
The present invention also provides use of the diol of the formula (I) defined above as a chain extender.
The present invention further provides the diol of the formula (I) as defined above when used as a chain extender.
The hydrocarbon radical for substituents R,, RZ, R3 and R4 may include alkyl, alkenyl, alkynyl, aryl or heterocyclyl radicals. It will be appreciated that the equivalent radicals may be used for substituents R5, R6 and R~ except that the reference to alkyl, alkenyl and alkynyl should be to alkylene, alkenylene and alkynylene, respectively. In order to avoid repetition, only detailed definitions of alkyl, alkenyl and alkynyi are provided hereinafter.
The term "alkyl" denotes straight chain, branched or mono- or poly-cyclic alkyl, preferably C ,_,2 alkyl or cycloalkyl. Examples of straight chain and branched alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, amyl, isoamyl, sec-amyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, pentyl, hexyl, 4-methylpentyl, 1-methylperltyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2-. trimethylpropyl, heptyl, 5-methylhexyl, 1-methylhexyl, 2,2-dimethylpentyl, 5 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, octyl, 6-methylheptyl, 1-methylheptyl, 1,1,3,3-tetramethylbutyl, nonyl, 1-, 2-, 3-, 4-, 5-, G- or 7-methyloctyl, 1-, 2-, 3-, or 5-ethylheptyl, 1-, 2- or 3-propylhexyl, decyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-and 8-methylnonyl, 1-, 2-, 3-, 4-, 5- or 6-ethyloctyl, 1-, 2-, 3- or 4-propylheptyl, undecyl 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-methyldecyl, 1-, 2-, 3-, 4-, 5-, 6-or 7-ethylnonyl, 1-, 2-, 3-, 4- or 5-propyloctyl, 1-, 2- or 3-butylheptyl, 1-pentylhexyl, dodecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-methylundecyl, 1-, 2-, 3-, 4-, S-, G-, 7- or 8-ethyldecyl, 1-, 2-, 3-, 4-, 5- or 6-propylnonyl, 1-, 2-, 3- or 4-butyloctyl, 1,2-pentylheptyl and the like. Examples of cyclic alkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like.
The term "alkenyl" denotes groups formed from straight chain, branched or mono- or poly-cyclic alkenes including ethylenically mono- or poly-unsaturated alkyl or cycloalkyl groups as defined above, preferably C2_,2 alkenyl. Examples of alkenyl include vinyl, allyl, 1-methylvinyl, butenyl, iso-butenyl, 3-methyl-2-butenyl, 1-pentenyl, cyclopentenyl, 1-methyl-cyclopentenyl, 1-hexenyl, 3-hexenyl, cyclohexenyl, 1-heptenyl, 3 heptenyl, 1-octenyl, cyclooctenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 3-decenyl, 1,3-butadienyl, 1,4-pentadienyl, 1,3-cyclopentadienyl, 1,3-hexadienyl, 1,4-hexadienyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, 1,3-cycloheptadienyl, 1,3,5-cycloheptatrienyl, 1,3,5,7-cycloocta-tetraenyl and the like.
R4 n (I) wherein R,, R2, R3, R4, R5, and R6 are the same or different and selected from an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical;
R~ is a divalent linking group or an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical; and n is 0 or greater, preferably 2 or less.
The present invention also provides use of the diol of the formula (I) defined above as a chain extender.
The present invention further provides the diol of the formula (I) as defined above when used as a chain extender.
The hydrocarbon radical for substituents R,, RZ, R3 and R4 may include alkyl, alkenyl, alkynyl, aryl or heterocyclyl radicals. It will be appreciated that the equivalent radicals may be used for substituents R5, R6 and R~ except that the reference to alkyl, alkenyl and alkynyl should be to alkylene, alkenylene and alkynylene, respectively. In order to avoid repetition, only detailed definitions of alkyl, alkenyl and alkynyi are provided hereinafter.
The term "alkyl" denotes straight chain, branched or mono- or poly-cyclic alkyl, preferably C ,_,2 alkyl or cycloalkyl. Examples of straight chain and branched alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, amyl, isoamyl, sec-amyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, pentyl, hexyl, 4-methylpentyl, 1-methylperltyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2-. trimethylpropyl, heptyl, 5-methylhexyl, 1-methylhexyl, 2,2-dimethylpentyl, 5 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, octyl, 6-methylheptyl, 1-methylheptyl, 1,1,3,3-tetramethylbutyl, nonyl, 1-, 2-, 3-, 4-, 5-, G- or 7-methyloctyl, 1-, 2-, 3-, or 5-ethylheptyl, 1-, 2- or 3-propylhexyl, decyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-and 8-methylnonyl, 1-, 2-, 3-, 4-, 5- or 6-ethyloctyl, 1-, 2-, 3- or 4-propylheptyl, undecyl 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-methyldecyl, 1-, 2-, 3-, 4-, 5-, 6-or 7-ethylnonyl, 1-, 2-, 3-, 4- or 5-propyloctyl, 1-, 2- or 3-butylheptyl, 1-pentylhexyl, dodecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-methylundecyl, 1-, 2-, 3-, 4-, S-, G-, 7- or 8-ethyldecyl, 1-, 2-, 3-, 4-, 5- or 6-propylnonyl, 1-, 2-, 3- or 4-butyloctyl, 1,2-pentylheptyl and the like. Examples of cyclic alkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like.
The term "alkenyl" denotes groups formed from straight chain, branched or mono- or poly-cyclic alkenes including ethylenically mono- or poly-unsaturated alkyl or cycloalkyl groups as defined above, preferably C2_,2 alkenyl. Examples of alkenyl include vinyl, allyl, 1-methylvinyl, butenyl, iso-butenyl, 3-methyl-2-butenyl, 1-pentenyl, cyclopentenyl, 1-methyl-cyclopentenyl, 1-hexenyl, 3-hexenyl, cyclohexenyl, 1-heptenyl, 3 heptenyl, 1-octenyl, cyclooctenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 3-decenyl, 1,3-butadienyl, 1,4-pentadienyl, 1,3-cyclopentadienyl, 1,3-hexadienyl, 1,4-hexadienyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, 1,3-cycloheptadienyl, 1,3,5-cycloheptatrienyl, 1,3,5,7-cycloocta-tetraenyl and the like.
The term "alkynyl" denotes groups formed from straight chain, branched, or mono- or poly-cyclic alkynes. Examples of alkynyl include ethynyl, 1-propynyl, 1- and 2-butynyl, 2-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 10-undecynyl, 4-ethyl-1-octyn-3-yl, 7-dodecynyl, 9-dodecynyl, 10-dodecynyl, 3-methyl-1-dodecyn-3-yl, 2-tridecynyl, 11-tridecynyl, 3-tetradecynyl, 7-hexadecynyl, 3-octadecynyl and the like.
The term "aryl" denotes single, polynuclear, conjugated and fused residues of aromatic hydrocarbons. Examples of aryl include phenyl, biphenyl, terphenyl, quaterphenyl, phenoxyphenyi, naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl, benzanthracenyl, dibenzanthracenyl, phenanthrenyl and the like.
The term "heterocyclyl" denotes mono- or poly-cyclic heterocyclyl groups containing at least one heteroatom selected from nitrogen, sulphur and oxygen. Suitable heterocyclyl groups include N-containing heterocyclic groups, such as, unsaturated 3 to 6 membered heteromonocyclic groups containing 1 to 4 nitrogen atoms, for example, pyrrolyI, pyrrolinyl, imidazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazolyl or tetrazolyl; saturated 3 to 6-mernbered heteromonocyclic groups containing 1 to 4 nitrogen atoms, such as pyrrolidinyl, imidazolidinyl, piperidino or piperazinyl; unsaturated condensed heterocyclic groups containing 1 to 5 nitrogen atoms, such as, indolyl, isoindolyl, indolizinyl, benzimidazolyl, quinolyl, isoquinolyl, indazolyl, benzotriazolyl or tetrazolopyridazinyl;
unsaturated 3 to 6-membered heteromonocyclic group containing an oxygen atom, such as, pyranyl or furyl; unsaturated 3 to 6-membered hetermonocyclic group containing 1 to 2 sulphur atoms, such as, thienyl;
unsaturated 3 to 6-membered heteromonocyclic group containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, such as, oxazolyl, isoazolyl or oxadiazolyl; saturated 3 to 6-membered heteromonocyclic group containing 1 .. to 2 oxygen atoms and 1 to 3 nitrogen atoms, such as, morpholinyl;
' unsaturated condensed heterocyclic group containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, such as, benzoxazoiyl or benzoxadiazolyl;
unsaturated 3 to 6-membered heteromonocyclic group containing 1 to 2 sulphur atoms and 1 to 3 nitrogen atoms, such as thiazolyl or thiadiazolyl;
saturated 3 to 6-membered heteromonocyclic group containing 1 to 2 sulphur atoms and 1 to 3 nitrogen atoms, such as, thiadiazolyl; and unsaturated condensed heterocyclic group containing 1 to 2 sulphur atoms and 1 to 3 nitrogen atoms, such as benzothiazolyl or benzothiadiazolyl.
In this specification, "optionally substituted" means that a group may or may not be further substituted with one or more groups selected from oxygen, nitrogen, sulphur, alkyl, alkenyl, alkynyl, aryl, halo, haloalkyl, haloalkenyl, haloalkynyl,_ haloaryl, hydroxy, alkoxy, alkenyloxy, alkynyloxy, aryloxy, carboxy, benzyloxy, haloalkoxy, haloalkenyloxy, haloalkynyloxy, haloaryloxy, vitro, nitroalkyl, nitroalkenyl~ nitroalkynyl, nitFOaryl, nitroheterocyclyl, azido, amino, ~alkylamino, alkenylamino, alkynylamino, arylamino, benzylamino, acyl, alkenylacyl, alkynylacyl, arylacyl, acylamino, acyloxy, aldehydo, alkylsulphonyl, arylsulphonyl, alkylsulphonylamino, arylsulphonylamino, alltylsulphonyloxy, arylsulphonyloxy, hetemcyclyl, .
hetervcycloxy, heterocyclylamino, haIoheterocyclyl, alkylsulphenyl, arylsulphenyl, carboalkoxy, carboaryloxy, mercapto, alkylthio, arylthio, acylthio and the like.
The term "halo" denotes fluoro, chloro, bromo or iodo, prefei'ably fluoro.
Examples of suitable fluoro radicals include trifluoropropyl, pentafluorobutyl and heptafluropropyl.
Suitable divalent linking groups for R~ include 0, S and NR wherein R is hydrogen or an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical.
Preferred silicon-containing diols are 1,3-bis(4-hydroxybutyl)tetramethyl PCT/AU98/00~~6 Received 12 March 1999 __ disiloxane (compound of formula (I) wherein R1, R2, R3 and R4 are methyl, RS
and R6 are butyl and R~ is O), 1,4-bis(3-hydroxypropyl)tetramethyl disilylethylene (compound of formula (I) wherein Rl, R2, R3 and R4 are methyl, RS and R6 are propyl and R~ is ethylene) and 1,4-bis(3 hydroxypropyl)tetramethyl disiloxane.
The silicon-containing diol chain extenders can be conveniently prepared by methods reported in the literature6. Some of these compounds such as 1,3-bis(3-hydroxypropyl)tetramethyl disilylethylene (BPTD) and 1,3-bis(4-hydroxybutyl) tetramethyl disiloxane (BHTD) are available commercially. Others can be prepared by using hydrosilylation reaction of the appropriate hydroxy alkene and 1,1,3,3,-tetramethyldisiloxane using a catalyst such as Wilkinson's catalyst.
Some of the diols of formula (I) are novel per se. Thus, the present invention also provides a silicon-containing diol of the formula (I) defined above wherein R~ is ethylene.
In a preferred embodiment, the diol of the formula (I) defined above is combined with a chain extender known in the art of polyurethane manufacture.
According to another aspect of the present invention provides a chain extender composition including a silicone-containing diol of the formula (I) defined above and a chain extender known in the art of polyurethane manufacture.
The present invention also provides use of the composition defined above as a chain extender.
AMENDED SHEET (Article 34) (IPEA/AUl WO 99/03863 ~ PCTlAU98/00546 The present invention further provides the composition defined above when used as a chain extender.
The chain extender known in the art of polyurethane manufacture is preferably selected from 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyelohexanedimethanol, p-xylene glycol and 1,4-bis(2-hydroxyethoxy) benzene. 1,4 butanediol is particularly preferred.
The silicon chain extender and the known chain extender can be used in a range of molar proportions with decreasing tensile properties as the molar percentage of the silicon chain extender increases in the mixture. A
preferred molar percentage of silicon chain extender is about 1 to about 50%, more preferably about 40%.
Although the preferred chain extender composition contains one known chain extender and one silicon-containing diol, it will be understood that mixtures containing more than one known chain extender and diol may be used in the chain extender composition.
The chain extender and chain extender composition of the present invention are particularly useful in preparing polyurethane elastomeric compositions.
According to a still further aspect of the present invention there is provided a polyurethane elastomeric composition which includes a segment derived from the chain extender or chain extender composition defined above.
The polyurethane elastomeric compositions of the present invention may be prepared by any suitable known technique. A preferred method involves mixing the chain extender or chain extender composition with a soft segment macrodiol and then reacting this mixture with a diisocyanate. The initial ingredients are preferably mixed at a temperature in the range of about 45 to about 100°C, more preferably about 60 to about 80°C. If desired, a catalyst such as dibutyl tin dilaurate at a level of about 0.00 i to about 0.5 wt 5 based on the total ingredients may be added to the initial mixture. The mixing may occur in conventional apparatus or within the conf nes of a reactive extruder or continuous reactive injection molding machine.
Alternatively, the polyurethanes may be prepared by the prepolymer method which involves reacting a diisocyanate with the soft segment macrodiol to 10 form a prepolymer having terminal reactive diisocyanate groups. The prepolymer is then reacted with the chain extender or chain extender composition.
Thus, the polyurethane elastomeric composition of the present invention may be further defined as comprising a reaction product of (i) a soft segment macrodiol;
(ii) a diisocyanate; and (iii) the chain extender or chain extender composition defined above.
The soft segment macrodiol may be of any suitable type known in the art of polyurethane manufacture. Examples include polyethers, polyesters, polysiloxanes, polycarbonates or mixtures thereof. Preferably, the soft segment is derived from a polysiloxane macrodiol and a polyether macrodiol.
A suitable polysiloxane is polydimethyl siloxane (PDMS). The polysiloxane macrodiols may be obtained as commercially available products such as X-22-160AS from Shin Etsu or prepared according to known procedures'. The preferred molecular weight range of the polysiloxane macrodiol is about 200 i wp 9gI03863 ~ PCT/AU98/00546 to about 5000, Preferably about 300 to about 3000.
Suitable polyether macrodiols include those represented by the formula (II) HO-~(CH2)M-O~~-H
(n) wherein m is an integer of 4 or more, preferably 5 to 18; and n is an integer of 2 to 50.
Although conventional polyether macrodiols such as PTMO can be used, the more preferred macrodiols and their preparation are described in Gunatillake et ah and US 5403912. Polyethers such as PHMO described-in these references are more hydrophobic than PTMO and' are more compatible with polysiloxane macrodiols. The preferred molecular weight range of the polyether macrodiol is about 200 to about 5000, more-preferably about 200 to about 1200.
Preferably; the diisocyanate is selected from one or more of 4,4'-methylenediphenyi diisocyanate (MDI), methylene bis (cyclohexyl} diisocyanate (H12MDI), p-phenylene diisocyanate (p-PDI), trans-cyclohexane-1, 4-diisocyanate (CHDI) or a mixture of the cis and trans isomers, 1,6-hexamethylene diisocyanate (DICH), 2,4-toluene diisocyanate (2,4-TDI) or its isomers or mixtures thereof, p-tetramethylxylene diisocyanate (p-TMXDI} and m-tetramethylxylene diisocyanate (m-TMXDI). MDI is particularly preferred.
A particularly preferred polyurethane elastomeric composition of the present invention comprises a reaction product of (i) macrodiols including:
(a) polysiloxanc macrodiol; and {b) polyether macrodiol;
(ii) MDI; and (iii) chain extender composition including 1,4-butanediol and a silicon chain extender selected from 1,3-bis(4-hydroxybutyl)tetramethyl disiloxane and 1,4-bis(3-hydroxypropyl)tetramethyl disilylethylene and 1-4-bis(3-hydroxypropyl)tetramethyl disiloxane..
Preferably, the silicon chain extender is present in an amount of about 40 moI % of the chain extender composition.
The methods described above do not cause premature phase separation and yield polymers that are compositionally homogeneous and transparent having high molecular weights. These methods also have the advantage of not requiring the use of any solvent to ensure that the soft and hard segments are compatible during synthesis.
The polyurethane may be processed by conventional methods such as extrusion, injection and compression moulding without the need of added processing waxes. If desired, however, conventional polyurethane processing additives such as catalysts, antioxidants, stablisers; lubricants, dyes, pigments, inorganic and/or organic fillers and reinforcing materials can be incorporated into the polyurethane during preparation. Such additives are preferably added to the soft segment macrodiol.
The soft segment macrodiol, diisocyanate and the chain extender or chain extender composition may be present in certain preferred proportions. The preferred level of hard segment (i.e. diisocyanate and chain extender) in the composition is about 40 to about 60 wt%. The weight ratio of polysiloxane to polyether in the preferred soft segment may be in the range of from 1:99 to 99:I. A particularly preferred ratio of polysiloxane to polyether which provides increased degradation resistance, stability and clarity is 80:20.
The polyurethane elastomeric composition of the present invention is particularly useful in preparing materials having good mechanical properties, in particular biomaterials.
According to another aspect of the present invention there is provided a material having improved mechanical properties, clarity, processability and/or degradation resistance comprising a polyurethane elastomeric composition which includes a chain extender or chain extender composition defined above.
The present invention also provides use of the polyurethane elastomeric composition defined above as a material having improved mechanical properties, clarity, processability and/or degradation resistance.
The present invention further provides the polyurethane elastomeric 1 S composition defined above when used as a material having improved mechanical properties, clarity, processability and/or degradation resistance.
The mechanical properties which are improved include tensile strength, tear strength, abrasion resistance, Durometer hardness, flexural modulus and related measures of flexibility or elasticity.
The improved resistance to degradation includes resistance to free radical, oxidative, enzymatic and/or hydrolytic processes and to degradation when implanted as a biomaterial.
The improved processability includes ease of processing by casting such as solvent casting and by thermal means such as extrusion and injection molding, for example, low tackiness after extrusion and relative freedom from gels.
There is also provided a degradation resistant material which comprises the polyurethane elastomeric composition defined above.
The polyurethane elastomeric composition of the present invention shows good elastomeric properties. It should also have a good compatibility and stability in biological environments, particularly when implanted in vivo for extended periods of time.
According to another aspect of the present invention there is provided an in vivo degradation resistant material which comprises the polyurethane elastomeric composition defined above.
The polyurethane elastomeric composition may also be used as a biomaterial.
The term "biomaterial" is used herein in its broadest sense and refers to a 1 S material which is used in situations where it comes into contact with the cells and/or bodily fluids of living animals or humans.
The polyurethane elastomeric composition is therefore useful in manufacturing medical devices, articles or implants.
Thus, the present invention still further provides medical devices, articles or implants which are composed wholly or partly of the polyurethane elastomeric composition defined above.
The medical devices, articles or implants may include cardiac pacemakers, defibrillators and other electromedical devices, catheters, cannulas, ~yp.99/03g~ PCT/AU98I00546 implantable prostheses, cardiac assist devices, heart valves, vascular grafts, extra-corporeal devices, artificial organs, pacemaker leads, defibrillator leads, blood pumps, balloon pumps, A-V shunts, biosensors, membranes for cell ._ encapsulation, drug delivery devices, wound dressings, artificial joints, 5 orthopaedic implants ~ soft tissue replacements, intraocular lenses, optical devices, tissue engineering products and ENT implants.
It will be appreciated that polyurethane elastomeric compositions having properties optimised for use in the construction of various medical devices, articles or implants will also have other non-medical applications. Such applications may include their use in the manufacture of artificial Leather, 10 shoe soles; cable sheathing; varnishes and coatings; structural components for pumps, vehicles, etc; mining ore screens and conveyor belts; laminating compounds, for example in glazing; textiles; separation membranes; sealants or as components of adhesives.
Thus, the present invention extends to the use of the polyurethane 15 elastomeric composition defined above in the manufacture- of devices or articles.
The present invention also provides devices or articles which are composed wholly or partly of the polyurethane elastomeric composition defined above.
The invention will now be described with reference to the following examples. These examples are not to be construed as Limiting the invention in any way.
In the examples, reference will be made to the accompanying drawings in which:
Figures- la and lb are two photomicrographs of a polyurethane composition in Example 1 explanted after three months; and Figures 2a and 2b are two micrographs of a commercial Pellethane 2363-55D
explanted after three months.
Example 1 A polyurethane composition based on a mixture of PDMS/PHMO, a mixture of BDO and BHTD, and MDI was prepared by a one-step bulk polymerisation procedure.
a,,c~-bis (6-hydroxyethoxypropyl)polydimethylsiloxane (Shin Etsu product x-22-160AS, MW 940.27) (PDMS) containing 0.1 wt% of tris(nonyltriphenyl)phosphine (TNPP) was dried at 105°C for 15 h under vacuum (0.1 torr). Poly(hexamethylene oxide) (PHMO), prepared according to a method described by Gunatillake et alb and US 5403912, was dried at 130°C with 0.1 wt% TNPP {based on PHMO weight) under vacuum (0.1 ton) for 4 h. The molecular weight of the PHMO was 851.54. BHTD was degassed under vacuum (0.1 ton) at ambient temperature immediately before use to remove the cyclic impurities.
A mixture of dried PDMS (260.0 g), PHMO (65.00 g), 1,4-butanediol (16.14 g), dibutyl tin dilaurate catalyst (0.054 g), Irgawax (0.81 g) and Irganox 1010 (0.54 g) was placed into a 1L flask and degassed at 80°C for 2 h under vacuum (0.2 torr). Separately degassed BHTD (33.256 g) was added to the flask containing the macrodiol mixture. This mixture (370.00 g) was weighed into a 1L polypropylene beaker and allowed to cool to 70°C
under nitrogen. Molten MDI ( 164.67 g) at 60°C was weighed in a fume hood into 250 ml polypropylene beaker. The MDI was then quickly added with rapid stirring using a stainless steel spatula. The mixture, which was initially cloudy, turned clear with mixing after about 10 sec. The viscous mixture was rapidly poured onto a teflon coated metal tray and cured in an oven under nitrogen at 100°C. Heating was discontinued after 4 h and the sheet of polyurethane was allowed to cool to ambient temperature over a period of about 15 h.
A sample of the polymer after drying for 15 h at 45°C under vacuum (0.1 torr) was compression moulded at 180°C to a 1 mm thick flat sheet for tensile testing. Dumbbells punched from the sheet were tensile tested using an Instron Model 4032 Universal Testing Machine.
The degradation resistance of the polyurethane composition described in example 1 was examined by a three month ovine implant experiment.
Polyurethane in example 1, Pellethane 2363-80A (Registered Trade Mark) and 2363-SSD were compression moulded into sheets of 0.5 mm thickness.
Specimens shaped as dumbbells were cut from the sheets and stretched over poly(methyl methacrylate) holders. This caused the central section to be 1 S strained to 250% of its original length. A polypropylene suture was firmly tied around the centre of each specimen. This caused a localised increase in stress in the specimen. The specimens attached to their holders were sterilised with ethylene oxide and implanted into the subcutaneous adipose tissue in the dorsal thoraco-lumbar region of adult crossbred wether sheep.
This test method provides a means of assessing the resistance to biodegradation by environmental stress cracking.
After a period of three months the polyurethanes were retrieved. Attached tissue was carefully dissected away and the specimens were washed by soaking in O.1M sodium hydroxide for 2 days at ambient temperature followed by rinsing in deionised water. The specimens were then dried in air and examined by scanning electron microscopy (SEM) for signs of pitting or cracking. The polyurethane sample showed no sign of stress cracking and while Pellethane 80A showed severe degradation. Since Pellethane 80A
showed severe degradation visible to the naked eye, those samples were not examined by SEM. Representative scanning photomicrographs of the new polyurethane composition and Pellethane SSD are shown in Figures 1 and 2, respectively.
The mechanical properties of the material prepared in example 1 were examined and the results are shown in Table 1 with those of Pellethane 2363-80A (Registered Trade Mark) for comparison.
Table 1 Property Polyurethane Prior art soft -example 1 Polyurethane (Pellethane - 2363A
80A)+
Shore Hardness 70A 82A
Ultimate Tensile (MPa) 28 33.7 Elongation at break 420 430 Young's Modulus (MPa) 9.6 13 Tear Strength (N.mrri 51 72 ~) Flexural Modulus (MPa) 14 26 + Results from testing of a commercial sample of Pellethane 2363-80A
The thermal processability of the polyurethane elastomer prepared according to the procedure in example 1 was evaluated by extrusion into a thin film (0.5 mm) using a single screw Brabender extruder. The polyurethane was dried at 45°C under vacuum {0.1 ton) for 48 h prior to the extrusion.
The material extruded easily into a clear and transparent film with no imperfections and the post extrusion tackiness was minimal with easy handling.
Example 2 A polyurethane composition based on a mixture of PDMS/PHMO, a mixture of BDO and BHTD, and MDI was prepared by a two-step bulk polymerisation procedure without the use of the catalyst or other conventional additives used in example 1. The composition was based on an isocyanate index ([NCO/[OH]) of 1.03 and a hard segment weight percentage of 40.
PDMS (Shin Etsu product X-22-160AS, MW 937.83) was dried at 105°C
for 15h under vacuum (0.1 torr). PHMO (MW 696.06) was dried at 130°C
under vacuum (0.1 torr) for 4 h prior to polymerisation.
Molten MDI ( 195.0 g) was weighed into a 2 L three necked round bottom S flask fitted with an additional funnel, nitrogen inlet and a mechanical stirrer.
The dried polyol mixture (240.0 g PDMS and 60.0 g PHMO) was weighed into the additional funnel and then added to MDI in the flask over a period of 30 min with stirring. During this time the reaction temperature was maintained at 70°C. The reaction was continued for further 2 h at 80°C with 10 stirring to form the prepolymer. The prepolymer (537.1 g) was then weighed into a 2 L polypropylene beaker and thoroughly mixed with the chain extenders BDO { 16.82 g) for 2 min. The polymer was poured into a teflon coated pan and cured at 100°C for 4 h in an oven under nitrogen.
The cured polyurethane after drying at 45°C under vacuum (0.1 torr) was 15 compression moulded at 180°C into 2 mm thick flat sheets for testing tensile properties and flexural modulus, and 2 mm thick, 10.5 cm diameter discs for abrasion resistance. Tensile properties and flexural strength were tested on an Instron Model 4032 Universal Testing Machine while the abrasion resistance was tested on a Taber Model 503 Abraser using Calibrade H-22 20 abrading wheels and 1000 g wheel loading. The tensile test specimens were 10 cm long dumbbells with a 6 mm wide narrow section. The test results are summarised in Table 2 along with corresponding properties for a commercial sample of silicon rubber. Some properties of high tear strength silicon rubber as reported in the literatures are shown in Table 3 for comparison.
The clarity of the polyurethane composition in example 2 and commercial silicone rubber was measured on a Gardner Hazemeter Model UX10, using 2 mm thick films.
Table 2 Property Polyurethane of exampleSilicon Rubber-Durometer Hardness 70 65 (Shore A) Tensile Strength (MPa)20 9.0 Elongation at Break 890 410 (%) Young's Modulus (MPa) 4.4 5.0 Tear Strength (n/mm) 57 45 Flexural Modulus (MPa)14 17 Abrasion (depth 0.06 0.09 (mm)/3000 revolutions) ~ Results from testing of a commercial sample of Silicon Rubber Table 3 Property Silicon Rubber Durometer Hardness (Shore A) 50 50 50 Tensile Strength (MPa) 6.90 10.34 9.66 Tear Strength (N/mm) (ASTM 17.50 33.25 35.00 54, Disc B) Abrasion (Rev/0.254 cm) (ASTM 155 300 1600 D1630 61) Table 4 Sample Hazemeter Reading (% absorption) Polyurethane of Example 2 7 Commercial silicon rubber 65 Clear glass (microscope slide)1.5 Parafilm 50 The results in Tables 2, 3 and 4 clearly demonstrate that the composition of the present invention are superior to silicon rubber with respect to tensile strength, tear strength and abrasion resistance as well as film clarity.
Example 3 1,4-bis(3-hydroxypropyl)-1,1,4,4-tetramethyl disilylethylene (HTDE) was prepared by a hydrosilylation procedure.
1,1,4,4,-Tetramethyldisilylethylene (50.0 g) and tris(triphenylphosphine) rhodium chloride (Wilkinson's catalyst, 0.005 g) were placed in a 500 ml 1 S round bottom flask fitted with a nitrogen inlet, addition funnel, a drying tube and a condenser. The flask was placed in an oil bath at 40°C and allylalcohol (80.00 g) was added to the reaction mixture over a period of 30 min. After the addition was completed, the oil bath temperature was raised to 80°C and continued reaction for 2 h. A sample of the reaction was analysed by IR spectroscopy. The absence of an Si-H band at 2160 cm 1 was taken as the completion of the reaction. The product mixture was dissolved in CH2C12 and treated with charcoal to remove the catalyst. The product was purified by vacuum distillation and the fraction distilled at 135-137°C/0.1 ton was used for the preparation of polyurethane.
PDMS and PHMO were purified according to the procedures described in Example 1. PDMS (28.00 g), PHMO (7.00 g), BDO (2.433 g), HTDE
(2.363 g) and dibutyl tin dilauarate (0.006 g) were weighed into a 100 ml polypropylene) beaker and degassed at 80°C for 2 h under vacuum (2 torr).
Molten MDI (18.57 g) was quickly added to the contents in the beaker and stirred rapidly. The polymer was cured in the beaker at 100°C for 4 h in an oven under nitrogen.
A sample of the polymer after drying for 15 h at 45°C under vacuum (0.1 torr) was compression moulded at 180°C to a 1 mm thick flat sheet for tensile testing. Dumbbells punched from the sheet were tensile tested on an Instron Model 4032 Universal Testing Machine: fail stress 17 MPa, fail strain 460%, Young's modulus 17.6 MPa, Shore hardness 79A and tear strength 51 N/mm.
Example 4 1,3-bis(S-hydroxypentyl)-1,1,3,3-tetramethyldisiloxane (BHPD) and 1,3-bis(6-hydroxyhexyl)-1,1,3,3-tetramethyldisiloxane (BHHD) were prepared using procedures similar to that described in example 3.
Two polyurethanes were prepared using a one step procedure similar to that described in example 1. The polyurethane based on BHPD was prepared from PDMS (20.0 g), PHMO (5.0 g}, MDI (12.72 g), BDO (1.209 g), BHPD
(2.742 g) and catalyst dibutyl tin dilaurate {0.004 g). Likewise, a polyurethane based on BHHD was prepared from PDMS (20.0 g), PHMO
(5.0 g), MDI ( 12.57 g), BDO ( 1.178 g), BHHD (2.914 g) and dibutyl tin dilaurate (0.004 g).
Samples of the two polymers after drying for 15 h at 45°C under vacuum (0.1 torr) were compression moulded at 180°C to a 1 mm thick flat sheet for testing tensile properties. Dumbbells punched from the sheets were tested on an Instron Model 4032 Universal Testing Machine. The polyurethane based on BHPD showed fail stress 19.5 MPa, fail strain 300%, stress at 100%
elongation 7.2 MPa, Shore Hardness 67A and Young's modulus 11.2 MPa.
Similarly, the polyurethane based on BHHD showed fail stress 22.2 MPa, fail strain 290%, Shore Hardness 60A and Young's modulus 12.7 MPa.
Example 5 PDMS and PHMO were purified according to the procedures described in Example 1. PDMS (5.00 g), PHMO (20.0 g), BDO (2.04 g), BHTD (4.203 g) and dibutyl tin dilaurate (0.005 g) were weighed into a 100 ml polypropylene) beaker and degassed at 80°C for 2 h under vacuum (2 torr).
Hydrogenated MDI (Aldrich, 18.76 g) was quickly added to the contents in the beaker and stirred rapidly. The polymer was cured in the beaker at 100°C for 4 h in an oven under nitrogen.
The polymer after curing was colourless and transparent. A 1 mm thick sheet of the polymer was prepared by compression moulding at 180°C.
Dumbbells punched from the sheet were tested for tensile properties on an Instron Model 4032 Universal Testing Machine: fail stress 18 MPa, fail strain 410%, stress at 100% elongation 2.3 MPa, Young's modulus 10 MPa and Shore hardness 60A.
Example 6 This example illustrates the synthesis of a polyurethane composition using a PDMS macrodiol with a molecular weight of 1913.3 according to a two-step polymerisation procedure.
WO 99/03863 PCT/AU98l00546 MDI (23.85g) was weighed into a 250mL three necked round bottom flask fitted with a dry nitrogcn inlet, a mechanical stirrer and an addition funnel.
The reaction flask was placed in an oil bath at 70°C and the polyol mixture (40.008, PDMS molecular weight 1913.3 and 10.OOg PHMO, molecular 5 weight 700.16) was slowly added to MDI from the addition funnel over a period of 15 min. After completion of the addition, the oil bath temperature was raised to 80°C and reacted for 2 hours with stirring- under a slow flow of nitrogen to complete the reaction. The prepolymer was then dissolved in anhydrous N,N-dimethyformamide (DMF) (440mL), to make a 15% solution.
10 The chain extender mixture, 1,4-butanediol (3.0998) and l,3bis(4-hydroxybutyl)tetramethyl disiloxane (6.3878), was added to the prepolymer solution and reacted at 90°C for 4h with stirring.
A 0.5mm thick film was cast from the DMF solution of the polymer onto a Petrie dish and dried at 45°C in an aver for 48h to remove the solvent. The I S cast film was clear and transparent. Test specimens were punched from the film for. testing tensile properties and tear strength.
The polyurethanc exhibitcd 22 MPa fail stress, 440% fail strain, I S MPa Young's modulus, and 7 MPa stress at 100% elongation. The tear strength of the polyurethane was 60 N/mm.
CA 02296642 2003-12-24 , s 25a Example 7 This example illustrates that by varying the relative amounts of the silicon chain extender BHTD and the conventional chain extender BDO, polyurethanes with a .range of mechanical properties could be synthesised. Eight polyurethanes were prepared by varying the chain extender composition (BHTD/BDO molar ratio) using a two-step polymerisation procedure similar to that described in Example 2: .
Bishydroxyethoxypropylpolydimethylsiloxane (PDMS) (Shin-Etsu) and poly (hexamethylene oxide) (PIilViO) werc dried and degassed using a thin-filin evaporator. 4,4'-methylenediphenyl diisocyanate (11~I, ICI Australia), 1,4-butanediol (BDO,GAF) and BHTD (Silar Laboratories) were used as received.
.'Phe hard segment (lVmI-based) was 40 wt % while the soft segment was based on an 80120 wt °/ mixture of PDMS (MW 966) and PHMO (MW 715), respectively.
Table 5 below Iists the formulation details of tech polyurethane prepared.
Polyurethanes are designated as PU-XX where XX denotes the molar percentage of BHTD in the chain extender mixture.
Table 5 Sample (PDMSlPHMO: MDI (g) BDO (g) BHTD (g) code 80120) (g) PU-0 300.0 170.4 29.61 0 PU 10 300.0 166.0 25.28 8.68 PU-20 ~ 300.0 162.1 21.37 16.51 PU-30 300.0 158.55 17.83 23.62 PU-40 300.0 155.3 14.60 30.09 PU-60 300.0 149.7 8.94 41.44.
PU-80 300.0 144.79 4.13 51.08 PU-100 300.0 140.64 0 59.36 DAB:FPH:#2J036additexamp 10 Janwry 2000 . .. ...... . . ............ ..................,. .. ............ ~ 02296642 25b Flat sheets of PU . were prepared using compression moulding. Tensile test specimens punched from PU sheets were annealed at 100°C for. lOh and allowed to condition to ambient temperature for one week before testing tensile properties.
Tensile testing was conducted using an Instron Model 4032 Universal testing machine with a 1kN load cell at a cross-head speed of 500 mm/min. The tensile properties of the polyuret~ianes are shown in Table ~6 below.
Table 6 Sample Elong UTS ~ YM Tear S. FM . SH
Code % MPa MPa N/mm MPa (A) PU 0 3174 230.8 323 61f4 362 85 ~
PU 10 356116 2411.5 22f1 5812 2711.4 79 PU-20 38116 2410.9 1410.5 52f0.5 1613 75 PU-30 378118 2111.6 9.3f 44f3 I2f2 73 1.1 PU-40 3915 200.4 7.8f0.4 430.6 !010.5 70 PU 60 42010 161.3 7.411.1 3110.9 7.90.4 63 .
PU-80 48915 1310.8 7.3f1.2 23f0.4 9f0.1 64 . PU-100 54710 9.zf0.4 13f0.9 19f0.3 170.3 71 1 I ~ ~ ~
Example 8 S
This example illustrates the synthesis of a polyurethane based on a new silicon chain extender bis(6-hydroxyethoxypropyl) tetramethyldisiloxane (BETD) [formula (I) wherein RS and R5 = -CHzCH20CH2CHa CHI; RIO; and Ri, Ra, R3 and R4 =
CH3].
BETD was synthesised by reacting 1,1,3,3-tetramethyldisiloxane and hydroxyethoxypmpene in the presence of a hydmsilylation catalyst (Karstead's catalyst) using the procedure described in Example 3. A polyurethane based on a 60!40 molar composition of BDO and BETD was prepared using a two-step bulk polymerisation procedure.
DAH:FPFI:#Z3036~ddi~examp ~ 10 Jmmy 2000 25c N ~ "
Molten MDI (25.26 g) was weighed into a 250 mL three necked round bottom flask fitted with an addition ftmnel, nitrogen inlet and a mechanical stirrer. The dried polyol mixture (40.0 g PDMS and 10.0 g PHMO) was weighed into the addition funnel and then added to MDI in the flask over a period of 30 min with stirring.
During this time the reaction temperature was maintained at 70° C. The reaction was continued for further 2 h at 80°C with stirring to form the prepolymer. The ~
prepolymer (70.00 g) was then weighed into a 250 mL polypropylene beaker and thoroughly mixed with chain extenders BDO (2.14 g) and BHTD (5.38 g) for Z
min.
The polymer was poured into a teflon-coated pan and cured at 100°C for 4 h in an ~ r- j oven under nitrogen.
A sample of the polyurethane after drying for 15 h at 45°C under vacuum (O.I tort) vcwas compression moulded at 180°C to a lmm thick flat sheet for tensile testing.
Dumbbells punched from the sheet were tensile tested on an Instcon Model 4032 Universal Testing Machine: fail stress 13 MPa, fail strain 4I5%, Young's modules 7.5 MPa, Shore hardness 69, flexural modules 9.5 MPa and tear strength 4'1 N/mm.
Example 9 This example illustrates the synthesis of a polyurethane composition using a PDMS
,, raacrodiol with a molecular weight of 2955 according to a two-step procedure.
, MDI (23.10 g) was weighed into a 250 mI. three necked round bottom flask fitted with a dry nitrogen inlet, a mechanical stizrer and an addition funnel. The reaction flask was placed in an oil bath at 70°C and the polyol mixture (40.00 g PDMS
molecular weight 2955.7 and 10.00 g PHMO, molecular weight 700.2) was slowly .
added to MDI from tlae addition funnel over a period of 15 min. After completion of the addition, the oil bath temperature was raised to 80°C and reacted far 2 hours with stirring under a slow flow of nitrogen to complete the reaction. The prepolymer was dissolved in anhydrous N,N'-dimethylac~tamide (DMAc) (330 mL) to make a 20 wt-% solution. The chain extender mixture, i,4-butanediol (3.34 DAH:FPH:#23036addibxamp , 101anwry 2000 _ _... . .. .... ... .... . . ... ...... .. .._............... ....._ .....,.
. _ ~ 02296642 2003-12-24 , _- ~ 2 5 d g) aad I,3-bis(4-hydroxybutyl) tetramethyldisiioxane (6.887 g) was added to the prepolymer solution and reacted at 90°C for 4h with stirring. ' ' 'A 0.5 mm thick film was cast from the 17MF solution of the prepolymer onto a Petrie dish and dried at 45°C in an oven for 48 h to remove the solvent. The cast film was clear and transparent. Test specimens were punched from the film for testing tensile pmperbies and tear strength.
The polyurethane exhibited 21 MPa fail stress,.168% elongation at break, 62.64.
Young's modulus and 55 N/mm tear strength.
DAB:FPH:#Z5036additexamp ~ l0 January 2000 WO 99/03863 PCTlAU98/00546 References 1. M. Szycher, J. Biomat. Appl., Vol 3, pp 297-402, (1988).
2. M. Szycher and W.A. McArthur, Surface Fissuring of Polyurethanes w Following In Vivo Exposure, In A.C. Fraker and C.D. Griffin, ~Eds.
Corrosion and Degradation of Implant Materials, Fhiladelphia, PA, ASTM STP 859, pp 308-321, (1985).
3. L. Pinchuk, J. Biomater. Sci. Edn, Vol 3 (3), pp 225-267, (1994).
4' :R.W. Hergenrother and S.L. Cooper, Mat. Res. Soc. Symp. Proc., Vol 252, pp 257-263, ( 1992).
5. K.E. Polmanteer, Advances in Silicon Rubber Technology in Handbook of Elastomers, A.K. Bhowmick and H.L. Stephens, Eds Ma~cel Dekker, Inc., pp 551-615, (1988). , 6. F. Braun, L. Willner, M. Hess and R. Kosfeld, d.Organomet. Chem., Vol 332, pp 63-68, (1987).
7. I. Yilgor, J.S. Riffle, W.P. Steckle, Jr., A.K. Banthia and J.E.
McGrath, Polym. Mater. Sci & Eng., Vol 50, pp 518-522, (1984).
The term "aryl" denotes single, polynuclear, conjugated and fused residues of aromatic hydrocarbons. Examples of aryl include phenyl, biphenyl, terphenyl, quaterphenyl, phenoxyphenyi, naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl, benzanthracenyl, dibenzanthracenyl, phenanthrenyl and the like.
The term "heterocyclyl" denotes mono- or poly-cyclic heterocyclyl groups containing at least one heteroatom selected from nitrogen, sulphur and oxygen. Suitable heterocyclyl groups include N-containing heterocyclic groups, such as, unsaturated 3 to 6 membered heteromonocyclic groups containing 1 to 4 nitrogen atoms, for example, pyrrolyI, pyrrolinyl, imidazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazolyl or tetrazolyl; saturated 3 to 6-mernbered heteromonocyclic groups containing 1 to 4 nitrogen atoms, such as pyrrolidinyl, imidazolidinyl, piperidino or piperazinyl; unsaturated condensed heterocyclic groups containing 1 to 5 nitrogen atoms, such as, indolyl, isoindolyl, indolizinyl, benzimidazolyl, quinolyl, isoquinolyl, indazolyl, benzotriazolyl or tetrazolopyridazinyl;
unsaturated 3 to 6-membered heteromonocyclic group containing an oxygen atom, such as, pyranyl or furyl; unsaturated 3 to 6-membered hetermonocyclic group containing 1 to 2 sulphur atoms, such as, thienyl;
unsaturated 3 to 6-membered heteromonocyclic group containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, such as, oxazolyl, isoazolyl or oxadiazolyl; saturated 3 to 6-membered heteromonocyclic group containing 1 .. to 2 oxygen atoms and 1 to 3 nitrogen atoms, such as, morpholinyl;
' unsaturated condensed heterocyclic group containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, such as, benzoxazoiyl or benzoxadiazolyl;
unsaturated 3 to 6-membered heteromonocyclic group containing 1 to 2 sulphur atoms and 1 to 3 nitrogen atoms, such as thiazolyl or thiadiazolyl;
saturated 3 to 6-membered heteromonocyclic group containing 1 to 2 sulphur atoms and 1 to 3 nitrogen atoms, such as, thiadiazolyl; and unsaturated condensed heterocyclic group containing 1 to 2 sulphur atoms and 1 to 3 nitrogen atoms, such as benzothiazolyl or benzothiadiazolyl.
In this specification, "optionally substituted" means that a group may or may not be further substituted with one or more groups selected from oxygen, nitrogen, sulphur, alkyl, alkenyl, alkynyl, aryl, halo, haloalkyl, haloalkenyl, haloalkynyl,_ haloaryl, hydroxy, alkoxy, alkenyloxy, alkynyloxy, aryloxy, carboxy, benzyloxy, haloalkoxy, haloalkenyloxy, haloalkynyloxy, haloaryloxy, vitro, nitroalkyl, nitroalkenyl~ nitroalkynyl, nitFOaryl, nitroheterocyclyl, azido, amino, ~alkylamino, alkenylamino, alkynylamino, arylamino, benzylamino, acyl, alkenylacyl, alkynylacyl, arylacyl, acylamino, acyloxy, aldehydo, alkylsulphonyl, arylsulphonyl, alkylsulphonylamino, arylsulphonylamino, alltylsulphonyloxy, arylsulphonyloxy, hetemcyclyl, .
hetervcycloxy, heterocyclylamino, haIoheterocyclyl, alkylsulphenyl, arylsulphenyl, carboalkoxy, carboaryloxy, mercapto, alkylthio, arylthio, acylthio and the like.
The term "halo" denotes fluoro, chloro, bromo or iodo, prefei'ably fluoro.
Examples of suitable fluoro radicals include trifluoropropyl, pentafluorobutyl and heptafluropropyl.
Suitable divalent linking groups for R~ include 0, S and NR wherein R is hydrogen or an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical.
Preferred silicon-containing diols are 1,3-bis(4-hydroxybutyl)tetramethyl PCT/AU98/00~~6 Received 12 March 1999 __ disiloxane (compound of formula (I) wherein R1, R2, R3 and R4 are methyl, RS
and R6 are butyl and R~ is O), 1,4-bis(3-hydroxypropyl)tetramethyl disilylethylene (compound of formula (I) wherein Rl, R2, R3 and R4 are methyl, RS and R6 are propyl and R~ is ethylene) and 1,4-bis(3 hydroxypropyl)tetramethyl disiloxane.
The silicon-containing diol chain extenders can be conveniently prepared by methods reported in the literature6. Some of these compounds such as 1,3-bis(3-hydroxypropyl)tetramethyl disilylethylene (BPTD) and 1,3-bis(4-hydroxybutyl) tetramethyl disiloxane (BHTD) are available commercially. Others can be prepared by using hydrosilylation reaction of the appropriate hydroxy alkene and 1,1,3,3,-tetramethyldisiloxane using a catalyst such as Wilkinson's catalyst.
Some of the diols of formula (I) are novel per se. Thus, the present invention also provides a silicon-containing diol of the formula (I) defined above wherein R~ is ethylene.
In a preferred embodiment, the diol of the formula (I) defined above is combined with a chain extender known in the art of polyurethane manufacture.
According to another aspect of the present invention provides a chain extender composition including a silicone-containing diol of the formula (I) defined above and a chain extender known in the art of polyurethane manufacture.
The present invention also provides use of the composition defined above as a chain extender.
AMENDED SHEET (Article 34) (IPEA/AUl WO 99/03863 ~ PCTlAU98/00546 The present invention further provides the composition defined above when used as a chain extender.
The chain extender known in the art of polyurethane manufacture is preferably selected from 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyelohexanedimethanol, p-xylene glycol and 1,4-bis(2-hydroxyethoxy) benzene. 1,4 butanediol is particularly preferred.
The silicon chain extender and the known chain extender can be used in a range of molar proportions with decreasing tensile properties as the molar percentage of the silicon chain extender increases in the mixture. A
preferred molar percentage of silicon chain extender is about 1 to about 50%, more preferably about 40%.
Although the preferred chain extender composition contains one known chain extender and one silicon-containing diol, it will be understood that mixtures containing more than one known chain extender and diol may be used in the chain extender composition.
The chain extender and chain extender composition of the present invention are particularly useful in preparing polyurethane elastomeric compositions.
According to a still further aspect of the present invention there is provided a polyurethane elastomeric composition which includes a segment derived from the chain extender or chain extender composition defined above.
The polyurethane elastomeric compositions of the present invention may be prepared by any suitable known technique. A preferred method involves mixing the chain extender or chain extender composition with a soft segment macrodiol and then reacting this mixture with a diisocyanate. The initial ingredients are preferably mixed at a temperature in the range of about 45 to about 100°C, more preferably about 60 to about 80°C. If desired, a catalyst such as dibutyl tin dilaurate at a level of about 0.00 i to about 0.5 wt 5 based on the total ingredients may be added to the initial mixture. The mixing may occur in conventional apparatus or within the conf nes of a reactive extruder or continuous reactive injection molding machine.
Alternatively, the polyurethanes may be prepared by the prepolymer method which involves reacting a diisocyanate with the soft segment macrodiol to 10 form a prepolymer having terminal reactive diisocyanate groups. The prepolymer is then reacted with the chain extender or chain extender composition.
Thus, the polyurethane elastomeric composition of the present invention may be further defined as comprising a reaction product of (i) a soft segment macrodiol;
(ii) a diisocyanate; and (iii) the chain extender or chain extender composition defined above.
The soft segment macrodiol may be of any suitable type known in the art of polyurethane manufacture. Examples include polyethers, polyesters, polysiloxanes, polycarbonates or mixtures thereof. Preferably, the soft segment is derived from a polysiloxane macrodiol and a polyether macrodiol.
A suitable polysiloxane is polydimethyl siloxane (PDMS). The polysiloxane macrodiols may be obtained as commercially available products such as X-22-160AS from Shin Etsu or prepared according to known procedures'. The preferred molecular weight range of the polysiloxane macrodiol is about 200 i wp 9gI03863 ~ PCT/AU98/00546 to about 5000, Preferably about 300 to about 3000.
Suitable polyether macrodiols include those represented by the formula (II) HO-~(CH2)M-O~~-H
(n) wherein m is an integer of 4 or more, preferably 5 to 18; and n is an integer of 2 to 50.
Although conventional polyether macrodiols such as PTMO can be used, the more preferred macrodiols and their preparation are described in Gunatillake et ah and US 5403912. Polyethers such as PHMO described-in these references are more hydrophobic than PTMO and' are more compatible with polysiloxane macrodiols. The preferred molecular weight range of the polyether macrodiol is about 200 to about 5000, more-preferably about 200 to about 1200.
Preferably; the diisocyanate is selected from one or more of 4,4'-methylenediphenyi diisocyanate (MDI), methylene bis (cyclohexyl} diisocyanate (H12MDI), p-phenylene diisocyanate (p-PDI), trans-cyclohexane-1, 4-diisocyanate (CHDI) or a mixture of the cis and trans isomers, 1,6-hexamethylene diisocyanate (DICH), 2,4-toluene diisocyanate (2,4-TDI) or its isomers or mixtures thereof, p-tetramethylxylene diisocyanate (p-TMXDI} and m-tetramethylxylene diisocyanate (m-TMXDI). MDI is particularly preferred.
A particularly preferred polyurethane elastomeric composition of the present invention comprises a reaction product of (i) macrodiols including:
(a) polysiloxanc macrodiol; and {b) polyether macrodiol;
(ii) MDI; and (iii) chain extender composition including 1,4-butanediol and a silicon chain extender selected from 1,3-bis(4-hydroxybutyl)tetramethyl disiloxane and 1,4-bis(3-hydroxypropyl)tetramethyl disilylethylene and 1-4-bis(3-hydroxypropyl)tetramethyl disiloxane..
Preferably, the silicon chain extender is present in an amount of about 40 moI % of the chain extender composition.
The methods described above do not cause premature phase separation and yield polymers that are compositionally homogeneous and transparent having high molecular weights. These methods also have the advantage of not requiring the use of any solvent to ensure that the soft and hard segments are compatible during synthesis.
The polyurethane may be processed by conventional methods such as extrusion, injection and compression moulding without the need of added processing waxes. If desired, however, conventional polyurethane processing additives such as catalysts, antioxidants, stablisers; lubricants, dyes, pigments, inorganic and/or organic fillers and reinforcing materials can be incorporated into the polyurethane during preparation. Such additives are preferably added to the soft segment macrodiol.
The soft segment macrodiol, diisocyanate and the chain extender or chain extender composition may be present in certain preferred proportions. The preferred level of hard segment (i.e. diisocyanate and chain extender) in the composition is about 40 to about 60 wt%. The weight ratio of polysiloxane to polyether in the preferred soft segment may be in the range of from 1:99 to 99:I. A particularly preferred ratio of polysiloxane to polyether which provides increased degradation resistance, stability and clarity is 80:20.
The polyurethane elastomeric composition of the present invention is particularly useful in preparing materials having good mechanical properties, in particular biomaterials.
According to another aspect of the present invention there is provided a material having improved mechanical properties, clarity, processability and/or degradation resistance comprising a polyurethane elastomeric composition which includes a chain extender or chain extender composition defined above.
The present invention also provides use of the polyurethane elastomeric composition defined above as a material having improved mechanical properties, clarity, processability and/or degradation resistance.
The present invention further provides the polyurethane elastomeric 1 S composition defined above when used as a material having improved mechanical properties, clarity, processability and/or degradation resistance.
The mechanical properties which are improved include tensile strength, tear strength, abrasion resistance, Durometer hardness, flexural modulus and related measures of flexibility or elasticity.
The improved resistance to degradation includes resistance to free radical, oxidative, enzymatic and/or hydrolytic processes and to degradation when implanted as a biomaterial.
The improved processability includes ease of processing by casting such as solvent casting and by thermal means such as extrusion and injection molding, for example, low tackiness after extrusion and relative freedom from gels.
There is also provided a degradation resistant material which comprises the polyurethane elastomeric composition defined above.
The polyurethane elastomeric composition of the present invention shows good elastomeric properties. It should also have a good compatibility and stability in biological environments, particularly when implanted in vivo for extended periods of time.
According to another aspect of the present invention there is provided an in vivo degradation resistant material which comprises the polyurethane elastomeric composition defined above.
The polyurethane elastomeric composition may also be used as a biomaterial.
The term "biomaterial" is used herein in its broadest sense and refers to a 1 S material which is used in situations where it comes into contact with the cells and/or bodily fluids of living animals or humans.
The polyurethane elastomeric composition is therefore useful in manufacturing medical devices, articles or implants.
Thus, the present invention still further provides medical devices, articles or implants which are composed wholly or partly of the polyurethane elastomeric composition defined above.
The medical devices, articles or implants may include cardiac pacemakers, defibrillators and other electromedical devices, catheters, cannulas, ~yp.99/03g~ PCT/AU98I00546 implantable prostheses, cardiac assist devices, heart valves, vascular grafts, extra-corporeal devices, artificial organs, pacemaker leads, defibrillator leads, blood pumps, balloon pumps, A-V shunts, biosensors, membranes for cell ._ encapsulation, drug delivery devices, wound dressings, artificial joints, 5 orthopaedic implants ~ soft tissue replacements, intraocular lenses, optical devices, tissue engineering products and ENT implants.
It will be appreciated that polyurethane elastomeric compositions having properties optimised for use in the construction of various medical devices, articles or implants will also have other non-medical applications. Such applications may include their use in the manufacture of artificial Leather, 10 shoe soles; cable sheathing; varnishes and coatings; structural components for pumps, vehicles, etc; mining ore screens and conveyor belts; laminating compounds, for example in glazing; textiles; separation membranes; sealants or as components of adhesives.
Thus, the present invention extends to the use of the polyurethane 15 elastomeric composition defined above in the manufacture- of devices or articles.
The present invention also provides devices or articles which are composed wholly or partly of the polyurethane elastomeric composition defined above.
The invention will now be described with reference to the following examples. These examples are not to be construed as Limiting the invention in any way.
In the examples, reference will be made to the accompanying drawings in which:
Figures- la and lb are two photomicrographs of a polyurethane composition in Example 1 explanted after three months; and Figures 2a and 2b are two micrographs of a commercial Pellethane 2363-55D
explanted after three months.
Example 1 A polyurethane composition based on a mixture of PDMS/PHMO, a mixture of BDO and BHTD, and MDI was prepared by a one-step bulk polymerisation procedure.
a,,c~-bis (6-hydroxyethoxypropyl)polydimethylsiloxane (Shin Etsu product x-22-160AS, MW 940.27) (PDMS) containing 0.1 wt% of tris(nonyltriphenyl)phosphine (TNPP) was dried at 105°C for 15 h under vacuum (0.1 torr). Poly(hexamethylene oxide) (PHMO), prepared according to a method described by Gunatillake et alb and US 5403912, was dried at 130°C with 0.1 wt% TNPP {based on PHMO weight) under vacuum (0.1 ton) for 4 h. The molecular weight of the PHMO was 851.54. BHTD was degassed under vacuum (0.1 ton) at ambient temperature immediately before use to remove the cyclic impurities.
A mixture of dried PDMS (260.0 g), PHMO (65.00 g), 1,4-butanediol (16.14 g), dibutyl tin dilaurate catalyst (0.054 g), Irgawax (0.81 g) and Irganox 1010 (0.54 g) was placed into a 1L flask and degassed at 80°C for 2 h under vacuum (0.2 torr). Separately degassed BHTD (33.256 g) was added to the flask containing the macrodiol mixture. This mixture (370.00 g) was weighed into a 1L polypropylene beaker and allowed to cool to 70°C
under nitrogen. Molten MDI ( 164.67 g) at 60°C was weighed in a fume hood into 250 ml polypropylene beaker. The MDI was then quickly added with rapid stirring using a stainless steel spatula. The mixture, which was initially cloudy, turned clear with mixing after about 10 sec. The viscous mixture was rapidly poured onto a teflon coated metal tray and cured in an oven under nitrogen at 100°C. Heating was discontinued after 4 h and the sheet of polyurethane was allowed to cool to ambient temperature over a period of about 15 h.
A sample of the polymer after drying for 15 h at 45°C under vacuum (0.1 torr) was compression moulded at 180°C to a 1 mm thick flat sheet for tensile testing. Dumbbells punched from the sheet were tensile tested using an Instron Model 4032 Universal Testing Machine.
The degradation resistance of the polyurethane composition described in example 1 was examined by a three month ovine implant experiment.
Polyurethane in example 1, Pellethane 2363-80A (Registered Trade Mark) and 2363-SSD were compression moulded into sheets of 0.5 mm thickness.
Specimens shaped as dumbbells were cut from the sheets and stretched over poly(methyl methacrylate) holders. This caused the central section to be 1 S strained to 250% of its original length. A polypropylene suture was firmly tied around the centre of each specimen. This caused a localised increase in stress in the specimen. The specimens attached to their holders were sterilised with ethylene oxide and implanted into the subcutaneous adipose tissue in the dorsal thoraco-lumbar region of adult crossbred wether sheep.
This test method provides a means of assessing the resistance to biodegradation by environmental stress cracking.
After a period of three months the polyurethanes were retrieved. Attached tissue was carefully dissected away and the specimens were washed by soaking in O.1M sodium hydroxide for 2 days at ambient temperature followed by rinsing in deionised water. The specimens were then dried in air and examined by scanning electron microscopy (SEM) for signs of pitting or cracking. The polyurethane sample showed no sign of stress cracking and while Pellethane 80A showed severe degradation. Since Pellethane 80A
showed severe degradation visible to the naked eye, those samples were not examined by SEM. Representative scanning photomicrographs of the new polyurethane composition and Pellethane SSD are shown in Figures 1 and 2, respectively.
The mechanical properties of the material prepared in example 1 were examined and the results are shown in Table 1 with those of Pellethane 2363-80A (Registered Trade Mark) for comparison.
Table 1 Property Polyurethane Prior art soft -example 1 Polyurethane (Pellethane - 2363A
80A)+
Shore Hardness 70A 82A
Ultimate Tensile (MPa) 28 33.7 Elongation at break 420 430 Young's Modulus (MPa) 9.6 13 Tear Strength (N.mrri 51 72 ~) Flexural Modulus (MPa) 14 26 + Results from testing of a commercial sample of Pellethane 2363-80A
The thermal processability of the polyurethane elastomer prepared according to the procedure in example 1 was evaluated by extrusion into a thin film (0.5 mm) using a single screw Brabender extruder. The polyurethane was dried at 45°C under vacuum {0.1 ton) for 48 h prior to the extrusion.
The material extruded easily into a clear and transparent film with no imperfections and the post extrusion tackiness was minimal with easy handling.
Example 2 A polyurethane composition based on a mixture of PDMS/PHMO, a mixture of BDO and BHTD, and MDI was prepared by a two-step bulk polymerisation procedure without the use of the catalyst or other conventional additives used in example 1. The composition was based on an isocyanate index ([NCO/[OH]) of 1.03 and a hard segment weight percentage of 40.
PDMS (Shin Etsu product X-22-160AS, MW 937.83) was dried at 105°C
for 15h under vacuum (0.1 torr). PHMO (MW 696.06) was dried at 130°C
under vacuum (0.1 torr) for 4 h prior to polymerisation.
Molten MDI ( 195.0 g) was weighed into a 2 L three necked round bottom S flask fitted with an additional funnel, nitrogen inlet and a mechanical stirrer.
The dried polyol mixture (240.0 g PDMS and 60.0 g PHMO) was weighed into the additional funnel and then added to MDI in the flask over a period of 30 min with stirring. During this time the reaction temperature was maintained at 70°C. The reaction was continued for further 2 h at 80°C with 10 stirring to form the prepolymer. The prepolymer (537.1 g) was then weighed into a 2 L polypropylene beaker and thoroughly mixed with the chain extenders BDO { 16.82 g) for 2 min. The polymer was poured into a teflon coated pan and cured at 100°C for 4 h in an oven under nitrogen.
The cured polyurethane after drying at 45°C under vacuum (0.1 torr) was 15 compression moulded at 180°C into 2 mm thick flat sheets for testing tensile properties and flexural modulus, and 2 mm thick, 10.5 cm diameter discs for abrasion resistance. Tensile properties and flexural strength were tested on an Instron Model 4032 Universal Testing Machine while the abrasion resistance was tested on a Taber Model 503 Abraser using Calibrade H-22 20 abrading wheels and 1000 g wheel loading. The tensile test specimens were 10 cm long dumbbells with a 6 mm wide narrow section. The test results are summarised in Table 2 along with corresponding properties for a commercial sample of silicon rubber. Some properties of high tear strength silicon rubber as reported in the literatures are shown in Table 3 for comparison.
The clarity of the polyurethane composition in example 2 and commercial silicone rubber was measured on a Gardner Hazemeter Model UX10, using 2 mm thick films.
Table 2 Property Polyurethane of exampleSilicon Rubber-Durometer Hardness 70 65 (Shore A) Tensile Strength (MPa)20 9.0 Elongation at Break 890 410 (%) Young's Modulus (MPa) 4.4 5.0 Tear Strength (n/mm) 57 45 Flexural Modulus (MPa)14 17 Abrasion (depth 0.06 0.09 (mm)/3000 revolutions) ~ Results from testing of a commercial sample of Silicon Rubber Table 3 Property Silicon Rubber Durometer Hardness (Shore A) 50 50 50 Tensile Strength (MPa) 6.90 10.34 9.66 Tear Strength (N/mm) (ASTM 17.50 33.25 35.00 54, Disc B) Abrasion (Rev/0.254 cm) (ASTM 155 300 1600 D1630 61) Table 4 Sample Hazemeter Reading (% absorption) Polyurethane of Example 2 7 Commercial silicon rubber 65 Clear glass (microscope slide)1.5 Parafilm 50 The results in Tables 2, 3 and 4 clearly demonstrate that the composition of the present invention are superior to silicon rubber with respect to tensile strength, tear strength and abrasion resistance as well as film clarity.
Example 3 1,4-bis(3-hydroxypropyl)-1,1,4,4-tetramethyl disilylethylene (HTDE) was prepared by a hydrosilylation procedure.
1,1,4,4,-Tetramethyldisilylethylene (50.0 g) and tris(triphenylphosphine) rhodium chloride (Wilkinson's catalyst, 0.005 g) were placed in a 500 ml 1 S round bottom flask fitted with a nitrogen inlet, addition funnel, a drying tube and a condenser. The flask was placed in an oil bath at 40°C and allylalcohol (80.00 g) was added to the reaction mixture over a period of 30 min. After the addition was completed, the oil bath temperature was raised to 80°C and continued reaction for 2 h. A sample of the reaction was analysed by IR spectroscopy. The absence of an Si-H band at 2160 cm 1 was taken as the completion of the reaction. The product mixture was dissolved in CH2C12 and treated with charcoal to remove the catalyst. The product was purified by vacuum distillation and the fraction distilled at 135-137°C/0.1 ton was used for the preparation of polyurethane.
PDMS and PHMO were purified according to the procedures described in Example 1. PDMS (28.00 g), PHMO (7.00 g), BDO (2.433 g), HTDE
(2.363 g) and dibutyl tin dilauarate (0.006 g) were weighed into a 100 ml polypropylene) beaker and degassed at 80°C for 2 h under vacuum (2 torr).
Molten MDI (18.57 g) was quickly added to the contents in the beaker and stirred rapidly. The polymer was cured in the beaker at 100°C for 4 h in an oven under nitrogen.
A sample of the polymer after drying for 15 h at 45°C under vacuum (0.1 torr) was compression moulded at 180°C to a 1 mm thick flat sheet for tensile testing. Dumbbells punched from the sheet were tensile tested on an Instron Model 4032 Universal Testing Machine: fail stress 17 MPa, fail strain 460%, Young's modulus 17.6 MPa, Shore hardness 79A and tear strength 51 N/mm.
Example 4 1,3-bis(S-hydroxypentyl)-1,1,3,3-tetramethyldisiloxane (BHPD) and 1,3-bis(6-hydroxyhexyl)-1,1,3,3-tetramethyldisiloxane (BHHD) were prepared using procedures similar to that described in example 3.
Two polyurethanes were prepared using a one step procedure similar to that described in example 1. The polyurethane based on BHPD was prepared from PDMS (20.0 g), PHMO (5.0 g}, MDI (12.72 g), BDO (1.209 g), BHPD
(2.742 g) and catalyst dibutyl tin dilaurate {0.004 g). Likewise, a polyurethane based on BHHD was prepared from PDMS (20.0 g), PHMO
(5.0 g), MDI ( 12.57 g), BDO ( 1.178 g), BHHD (2.914 g) and dibutyl tin dilaurate (0.004 g).
Samples of the two polymers after drying for 15 h at 45°C under vacuum (0.1 torr) were compression moulded at 180°C to a 1 mm thick flat sheet for testing tensile properties. Dumbbells punched from the sheets were tested on an Instron Model 4032 Universal Testing Machine. The polyurethane based on BHPD showed fail stress 19.5 MPa, fail strain 300%, stress at 100%
elongation 7.2 MPa, Shore Hardness 67A and Young's modulus 11.2 MPa.
Similarly, the polyurethane based on BHHD showed fail stress 22.2 MPa, fail strain 290%, Shore Hardness 60A and Young's modulus 12.7 MPa.
Example 5 PDMS and PHMO were purified according to the procedures described in Example 1. PDMS (5.00 g), PHMO (20.0 g), BDO (2.04 g), BHTD (4.203 g) and dibutyl tin dilaurate (0.005 g) were weighed into a 100 ml polypropylene) beaker and degassed at 80°C for 2 h under vacuum (2 torr).
Hydrogenated MDI (Aldrich, 18.76 g) was quickly added to the contents in the beaker and stirred rapidly. The polymer was cured in the beaker at 100°C for 4 h in an oven under nitrogen.
The polymer after curing was colourless and transparent. A 1 mm thick sheet of the polymer was prepared by compression moulding at 180°C.
Dumbbells punched from the sheet were tested for tensile properties on an Instron Model 4032 Universal Testing Machine: fail stress 18 MPa, fail strain 410%, stress at 100% elongation 2.3 MPa, Young's modulus 10 MPa and Shore hardness 60A.
Example 6 This example illustrates the synthesis of a polyurethane composition using a PDMS macrodiol with a molecular weight of 1913.3 according to a two-step polymerisation procedure.
WO 99/03863 PCT/AU98l00546 MDI (23.85g) was weighed into a 250mL three necked round bottom flask fitted with a dry nitrogcn inlet, a mechanical stirrer and an addition funnel.
The reaction flask was placed in an oil bath at 70°C and the polyol mixture (40.008, PDMS molecular weight 1913.3 and 10.OOg PHMO, molecular 5 weight 700.16) was slowly added to MDI from the addition funnel over a period of 15 min. After completion of the addition, the oil bath temperature was raised to 80°C and reacted for 2 hours with stirring- under a slow flow of nitrogen to complete the reaction. The prepolymer was then dissolved in anhydrous N,N-dimethyformamide (DMF) (440mL), to make a 15% solution.
10 The chain extender mixture, 1,4-butanediol (3.0998) and l,3bis(4-hydroxybutyl)tetramethyl disiloxane (6.3878), was added to the prepolymer solution and reacted at 90°C for 4h with stirring.
A 0.5mm thick film was cast from the DMF solution of the polymer onto a Petrie dish and dried at 45°C in an aver for 48h to remove the solvent. The I S cast film was clear and transparent. Test specimens were punched from the film for. testing tensile properties and tear strength.
The polyurethanc exhibitcd 22 MPa fail stress, 440% fail strain, I S MPa Young's modulus, and 7 MPa stress at 100% elongation. The tear strength of the polyurethane was 60 N/mm.
CA 02296642 2003-12-24 , s 25a Example 7 This example illustrates that by varying the relative amounts of the silicon chain extender BHTD and the conventional chain extender BDO, polyurethanes with a .range of mechanical properties could be synthesised. Eight polyurethanes were prepared by varying the chain extender composition (BHTD/BDO molar ratio) using a two-step polymerisation procedure similar to that described in Example 2: .
Bishydroxyethoxypropylpolydimethylsiloxane (PDMS) (Shin-Etsu) and poly (hexamethylene oxide) (PIilViO) werc dried and degassed using a thin-filin evaporator. 4,4'-methylenediphenyl diisocyanate (11~I, ICI Australia), 1,4-butanediol (BDO,GAF) and BHTD (Silar Laboratories) were used as received.
.'Phe hard segment (lVmI-based) was 40 wt % while the soft segment was based on an 80120 wt °/ mixture of PDMS (MW 966) and PHMO (MW 715), respectively.
Table 5 below Iists the formulation details of tech polyurethane prepared.
Polyurethanes are designated as PU-XX where XX denotes the molar percentage of BHTD in the chain extender mixture.
Table 5 Sample (PDMSlPHMO: MDI (g) BDO (g) BHTD (g) code 80120) (g) PU-0 300.0 170.4 29.61 0 PU 10 300.0 166.0 25.28 8.68 PU-20 ~ 300.0 162.1 21.37 16.51 PU-30 300.0 158.55 17.83 23.62 PU-40 300.0 155.3 14.60 30.09 PU-60 300.0 149.7 8.94 41.44.
PU-80 300.0 144.79 4.13 51.08 PU-100 300.0 140.64 0 59.36 DAB:FPH:#2J036additexamp 10 Janwry 2000 . .. ...... . . ............ ..................,. .. ............ ~ 02296642 25b Flat sheets of PU . were prepared using compression moulding. Tensile test specimens punched from PU sheets were annealed at 100°C for. lOh and allowed to condition to ambient temperature for one week before testing tensile properties.
Tensile testing was conducted using an Instron Model 4032 Universal testing machine with a 1kN load cell at a cross-head speed of 500 mm/min. The tensile properties of the polyuret~ianes are shown in Table ~6 below.
Table 6 Sample Elong UTS ~ YM Tear S. FM . SH
Code % MPa MPa N/mm MPa (A) PU 0 3174 230.8 323 61f4 362 85 ~
PU 10 356116 2411.5 22f1 5812 2711.4 79 PU-20 38116 2410.9 1410.5 52f0.5 1613 75 PU-30 378118 2111.6 9.3f 44f3 I2f2 73 1.1 PU-40 3915 200.4 7.8f0.4 430.6 !010.5 70 PU 60 42010 161.3 7.411.1 3110.9 7.90.4 63 .
PU-80 48915 1310.8 7.3f1.2 23f0.4 9f0.1 64 . PU-100 54710 9.zf0.4 13f0.9 19f0.3 170.3 71 1 I ~ ~ ~
Example 8 S
This example illustrates the synthesis of a polyurethane based on a new silicon chain extender bis(6-hydroxyethoxypropyl) tetramethyldisiloxane (BETD) [formula (I) wherein RS and R5 = -CHzCH20CH2CHa CHI; RIO; and Ri, Ra, R3 and R4 =
CH3].
BETD was synthesised by reacting 1,1,3,3-tetramethyldisiloxane and hydroxyethoxypmpene in the presence of a hydmsilylation catalyst (Karstead's catalyst) using the procedure described in Example 3. A polyurethane based on a 60!40 molar composition of BDO and BETD was prepared using a two-step bulk polymerisation procedure.
DAH:FPFI:#Z3036~ddi~examp ~ 10 Jmmy 2000 25c N ~ "
Molten MDI (25.26 g) was weighed into a 250 mL three necked round bottom flask fitted with an addition ftmnel, nitrogen inlet and a mechanical stirrer. The dried polyol mixture (40.0 g PDMS and 10.0 g PHMO) was weighed into the addition funnel and then added to MDI in the flask over a period of 30 min with stirring.
During this time the reaction temperature was maintained at 70° C. The reaction was continued for further 2 h at 80°C with stirring to form the prepolymer. The ~
prepolymer (70.00 g) was then weighed into a 250 mL polypropylene beaker and thoroughly mixed with chain extenders BDO (2.14 g) and BHTD (5.38 g) for Z
min.
The polymer was poured into a teflon-coated pan and cured at 100°C for 4 h in an ~ r- j oven under nitrogen.
A sample of the polyurethane after drying for 15 h at 45°C under vacuum (O.I tort) vcwas compression moulded at 180°C to a lmm thick flat sheet for tensile testing.
Dumbbells punched from the sheet were tensile tested on an Instcon Model 4032 Universal Testing Machine: fail stress 13 MPa, fail strain 4I5%, Young's modules 7.5 MPa, Shore hardness 69, flexural modules 9.5 MPa and tear strength 4'1 N/mm.
Example 9 This example illustrates the synthesis of a polyurethane composition using a PDMS
,, raacrodiol with a molecular weight of 2955 according to a two-step procedure.
, MDI (23.10 g) was weighed into a 250 mI. three necked round bottom flask fitted with a dry nitrogen inlet, a mechanical stizrer and an addition funnel. The reaction flask was placed in an oil bath at 70°C and the polyol mixture (40.00 g PDMS
molecular weight 2955.7 and 10.00 g PHMO, molecular weight 700.2) was slowly .
added to MDI from tlae addition funnel over a period of 15 min. After completion of the addition, the oil bath temperature was raised to 80°C and reacted far 2 hours with stirring under a slow flow of nitrogen to complete the reaction. The prepolymer was dissolved in anhydrous N,N'-dimethylac~tamide (DMAc) (330 mL) to make a 20 wt-% solution. The chain extender mixture, i,4-butanediol (3.34 DAH:FPH:#23036addibxamp , 101anwry 2000 _ _... . .. .... ... .... . . ... ...... .. .._............... ....._ .....,.
. _ ~ 02296642 2003-12-24 , _- ~ 2 5 d g) aad I,3-bis(4-hydroxybutyl) tetramethyldisiioxane (6.887 g) was added to the prepolymer solution and reacted at 90°C for 4h with stirring. ' ' 'A 0.5 mm thick film was cast from the 17MF solution of the prepolymer onto a Petrie dish and dried at 45°C in an oven for 48 h to remove the solvent. The cast film was clear and transparent. Test specimens were punched from the film for testing tensile pmperbies and tear strength.
The polyurethane exhibited 21 MPa fail stress,.168% elongation at break, 62.64.
Young's modulus and 55 N/mm tear strength.
DAB:FPH:#Z5036additexamp ~ l0 January 2000 WO 99/03863 PCTlAU98/00546 References 1. M. Szycher, J. Biomat. Appl., Vol 3, pp 297-402, (1988).
2. M. Szycher and W.A. McArthur, Surface Fissuring of Polyurethanes w Following In Vivo Exposure, In A.C. Fraker and C.D. Griffin, ~Eds.
Corrosion and Degradation of Implant Materials, Fhiladelphia, PA, ASTM STP 859, pp 308-321, (1985).
3. L. Pinchuk, J. Biomater. Sci. Edn, Vol 3 (3), pp 225-267, (1994).
4' :R.W. Hergenrother and S.L. Cooper, Mat. Res. Soc. Symp. Proc., Vol 252, pp 257-263, ( 1992).
5. K.E. Polmanteer, Advances in Silicon Rubber Technology in Handbook of Elastomers, A.K. Bhowmick and H.L. Stephens, Eds Ma~cel Dekker, Inc., pp 551-615, (1988). , 6. F. Braun, L. Willner, M. Hess and R. Kosfeld, d.Organomet. Chem., Vol 332, pp 63-68, (1987).
7. I. Yilgor, J.S. Riffle, W.P. Steckle, Jr., A.K. Banthia and J.E.
McGrath, Polym. Mater. Sci & Eng., Vol 50, pp 518-522, (1984).
8. P.A. Gunadllake, G.F. Meijs, R.C. Chatelier, D.M. McIntosh and E.
Rizzardo, Polym. Int., Vol 27, pp 275-283, (1992).
It will be appreciated that further modifications and alterations may be made to the embodiment described above without del.~arting from the scope or spirit of the present intention.
Rizzardo, Polym. Int., Vol 27, pp 275-283, (1992).
It will be appreciated that further modifications and alterations may be made to the embodiment described above without del.~arting from the scope or spirit of the present intention.
Claims (54)
1. Use as a chain extender of a silicon-containing diol of the formula (1):
wherein R1, R2, R3 and R4 are the same or different and selected from a substituted or unsubstituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical;
R5 and R6 are the same or different and selected from a substituted or unsubstituted straight chain, branched or cyclic alkylene, alkenylene, alkynylene or heterocyclic radical;
R7 is a divalent linking group or a substituted or unsubstituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical;
and n is 0, 1 or 2.
wherein R1, R2, R3 and R4 are the same or different and selected from a substituted or unsubstituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical;
R5 and R6 are the same or different and selected from a substituted or unsubstituted straight chain, branched or cyclic alkylene, alkenylene, alkynylene or heterocyclic radical;
R7 is a divalent linking group or a substituted or unsubstituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical;
and n is 0, 1 or 2.
2. Use as claimed in claim 1 wherein R1, R2, R3 and R4 are the same or different and are selected from alkyl, alkenyl, alkynyl, aryl or heterocycle radicals.
3. Use as claimed in claim 2 wherein said alkyl radicals comprise straight chain, branched or mono- or poly-cyclic alkyl radicals.
4. Use as claimed in claim 3 wherein said alkyl radicals are selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, amyl, isoamyl, sec-amyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, pentyl, hexyl, 4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl,1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1,2-trimethylpropyl, heptyl, 5-methylhexyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl,1,1,3-trimethylbutyl, octyl, 6-methylheptyl, 1-methylheptyl, 1,1,3,3-tetramethylbutyl, nonyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-methyloctyl,1-, 2-, 3;
4- or 5-ethylheptyl, 1-, 2- or 3-propylhexyl, decyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-and 8-methylnonyl, 1-, 2-, 3-, 4-, 5- or 6-ethyloctyl, 1-, 2-, 3- or 4-propylheptyl, undecyl 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-methyldecyl, 1-, 2-, 3-, 4-, 5-, 6-or 7-ethylnonyl,1-, 2-, 3-, 4- or 5-propyloctyl, 1-, 2- or 3- butylheptyl,1 pentylhexyl, dodecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-methylundecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-ethyldecyl, 1-, 2-, 3-, 4-, 5- or 6- propylnonyl, 1-, 2-, 3- or 4-butyloctyl, 1,2-pentylheptyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl.
4- or 5-ethylheptyl, 1-, 2- or 3-propylhexyl, decyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-and 8-methylnonyl, 1-, 2-, 3-, 4-, 5- or 6-ethyloctyl, 1-, 2-, 3- or 4-propylheptyl, undecyl 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-methyldecyl, 1-, 2-, 3-, 4-, 5-, 6-or 7-ethylnonyl,1-, 2-, 3-, 4- or 5-propyloctyl, 1-, 2- or 3- butylheptyl,1 pentylhexyl, dodecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-methylundecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-ethyldecyl, 1-, 2-, 3-, 4-, 5- or 6- propylnonyl, 1-, 2-, 3- or 4-butyloctyl, 1,2-pentylheptyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl.
5. Use as claimed in any one of claims 2 to 4 wherein said alkenyl radicals comprise groups formed from straight chain, branched or mono- or poly-cyclic alkenes.
6. Use as claimed in claim 5 wherein said alkenyl radicals comprise vinyl, allyl, 1-methylvinyl, butenyl, iso-butenyl, 3-methyl-2-butenyl, 1-pentenyl, cyclopentenyl, 1-methyl-cyclopentenyl, 1-hexenyl, 3-hexenyl, cyclohexenyl, 1-heptenyl, 3-heptenyl, 1-octenyl, cyclooctenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 1-decenyl, 3-decenyl, 1,3-butadienyl,1,4-pentadienyl, 1,3-cyclopentadienyl, 1,3-hexadienyl, 1,4-hexadienyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, 1,3-cycloheptadienyl, 1,3,5-cycloheptatrienyl and 1,3,5,7-cycloocta-tetraenyl.
7. Use as claimed in any one of claims 2 to 6 wherein said alkynyl radicals comprise groups formed from straight chain, branched or mono- or poly-cyclic alkynes.
8. Use as claimed in claim 7 wherein said alkynyl radicals comprise ethynyl, 1-propynyl, 1- and 2-butynyl, 2-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl,10-undecynyl, 4-ethyl-1-octyn-3-yl, 7-dodecynyl, 9-dodecynyl, 10-dodecynyl, 3-methyl-1-dodecyn-3-yl, 2-tridecynyl, 11-tridecynyl, 3-tetradecynyl, 7-hexadecynyl and 3-octadecynyl.
9. Use as claimed in any one of claims 2 to 8 wherein said aryl radicals comprise single, polynuclear, conjugated and fused residues of aromatic hydrocarbons.
10. Use as claimed in claim 9 wherein said aryl radicals comprise phenyl, biphenyl, terphenyl, quaterphenyl, phenoxyphenyl, naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl, benzanthracenyl, dibenzautbracenyl and phenanthrenyl.
11. Use as claimed in any one of claims 2 to 10 wherein said heterocycle radicals comprise mono- or poly-cyclic heterocycle groups containing at least one heteroatom selected from nitrogen, sulphur and oxygen.
12. Use as claimed in claim 11 wherein said heterocycle radicals comprise N-containing heterocyclic groups, saturated 3 to 6-membered heteromonocyclic groups containing 1 to 4 nitrogen atoms, unsaturated condensed heterocyclic groups containing 1 to 5 nitrogen atoms, unsaturated 3 to 5-membered heteromonocyclic group containing an oxygen atom, unsaturated 3 to 6-membered hetermonocyclic group containing 1 to 2 sulphur atoms, saturated 3 to 6-membered heteromonocyclic group containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, unsaturated condensed heterocyclic group containing 1 to oxygen atoms and 1 to 3 nitrogen atoms, unsaturated 3 to 6-membered heteromonocyclic group containing 1 to 2 sulphur atoms and 1 to 3 nitrogen atoms, saturated 3 to 6-membered heteromonocyclic group containing 1 to 2 sulphur atoms and 1 to 3 nitrogen atoms, and unsaturated condensed heterocyclic group containing 1 to 2 sulphur atoms and 1 to 3 nitrogen atoms.
13. Use as claimed in any one of claims 1 to 12 wherein said alkylene radicals of R5 and/or R6 are the alkylene equivalent of the alkyl radicals claimed in claim 3 or claim 4.
14. Use as claimed in any one of claims 1 to 12 wherein said alkenylene radicals of R5 and/or R6 are the alkenylene equivalent of the alkenyl radicals claimed in claim 5 or claim 6.
15. Use as claimed in any one of claims 1 to 12 wherein said alkynylene radicals of R5 and/or R6 are the alkynylene equivalent of the alkynyl radicals claimed in claim 7 or claim 8.
16. Use as claimed in any one of claims 1 to 12 wherein said heterocycle radicals of R5 and/or R6 comprise mono- or poly-cyclic heterocyclyl groups containing at least one heteroatom selected from nitrogen, sulphur and oxygen.
17. Use as claimed in claim 16 wherein said heterocycle radicals comprise N-containing heterocyclic groups, saturated 3 to 6-membered heteromonocyclic groups containing 1 to 4 nitrogen atoms, unsaturated condensed heterocyclic groups containing 1 to 5 nitrogen atoms, unsaturated 3 to 6-membered heteromonocyclic group containing an oxygen atom, unsaturated 3 to 6-membered hetermonocyclic group containing 1 to 2 sulphur atoms, unsaturated 3 to 6-membered heteromonocyclic group containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, saturated 3 to 6-membered heteromonocyclic group containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, unsaturated condensed heterocyclic group containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, unsaturated 3 to 6-membered heteromonocyclic group containing 1 to 2 sulphur atoms and 1 to 3 nitrogen atoms, saturated 3 to 6-membered heteromonocyclic group containing 1 to 2 sulphur atoms and 1 to 3 nitrogen atoms, and unsaturated condensed heterocyclic group containing 1 to 2 sulphur atoms and 1 to 3 nitrogen atoms.
18. Use as claimed in any one of claims 1 to 17 wherein R7 is selected from alkylene, alkenylene, alkynylene, aryl or heterocyclyl radicals.
19. Use as claimed in claim 18 wherein said aryl radicals comprise single, polynuclear, conjugated and fused residues of aromatic hydrocarbons.
20. Use as claimed in claim 19 wherein said aryl residues comprise phenyl, biphenyl, terphenyl, quaterphenyl, phenoxyphenyl, naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl, benzanthracenyl, dibenzanthracenyl and phenanthrenyl.
21. Use as claimed in any one of claims 1 to 20 wherein R7 is a divalent linking group selected from O, S, and NR wherein R is hydrogen or a substituted or unsubstituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical.
22. Use as claimed in any one of claims 1 to 21 wherein said substituted or unsubstituted radicals are substituted with one or more groups selected from oxygen, nitrogen, sulphur, alkyl, alkenyl, alkynyl, aryl, halo, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, hydroxy, alkoxy, alkenyloxy, alkynyloxy, aryloxy, carboxy, benzyloxy, haloalkoxy, haloalkenyloxy, haloalkynyloxy, haloaryloxy, nitro, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroaryl, nitroheterocyclyl, azido, amino, alkylamino, alkenylamino, alkynylamino, arylamino, benzylamino, acyl, alkenylacyl, alkynylacyl, arylacyl, acylamino, acyloxy, aldehydro, alkylsulphonyl, arylsulphonyl, alkylsulphonylamino, arylsulphonylamino, alkylsulphonyloxy, arylsulphonyloxy, heterocyclyl, heterocycloxy, heterocyclyamino, haloheterocyclyl, alkylsulphenyl, arylsulphenyl, carboalkoxy, carboaryloxy, mercapto, alkylthio, arylthio and acylthio.
23. Use as claimed in any one of claims 1 to 22 wherein said silicon-containing diol is 1,3-bis(4-hydroxybutyl)tetramethyl disiloxane or 1,4-bis(3-hydroxypropyl)tetramethyl disilylethylene and 1-4-bis(3-hydroxypropyl)tetramethyl disiloxane.
24. Use as claimed in any one of claims 1 to 23 wherein said silicon containing diol is used in combination with at least one other chain extender.
25. Use as claimed in claim 24 wherein the at least one other chain extender is selected from 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, p-xylene glycol and 1,4-bis(2-hydroxyethoxy) benzene.
26. Use as claimed in claim 24 or claim 25 wherein the silicon-containing diol is present in the chain extender in an amount of from 1 to 50 molar percent.
27. A silicon-containing diol of formula [I] having a molecular weight of 500 or less wherein R1, R2, R3, R4 are the same or different and selected from a substituted or unsubstituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical;
R5 and R6 are the same or different and selected from a substituted or unsubstituted straight chain, branched or cyclic alkylene, alkenylene, alkynylene or heterocyclic radical;
R7 is ethylene; and n is 0, 1 or 2.
R5 and R6 are the same or different and selected from a substituted or unsubstituted straight chain, branched or cyclic alkylene, alkenylene, alkynylene or heterocyclic radical;
R7 is ethylene; and n is 0, 1 or 2.
28. A polyurethane elastomeric composition comprising the combination of a silicon-containing diol and at least one other chain extender as defined in any one of claims 24 to 26.
29. A polyurethane composition comprising a reaction product of:
(i) a soft segment macrodiol;
(ii) a diisocyanate; and (iii) a silicon-containing diol of formula (1) as defined in claim 1.
(i) a soft segment macrodiol;
(ii) a diisocyanate; and (iii) a silicon-containing diol of formula (1) as defined in claim 1.
30. A polyurethane composition as claimed in claim 29 wherein said soft segment macrodiol is selected from polyethers, polyesters, polysiloxanes, polycarbonates or mixtures thereof.
31. A polyurethane composition as claimed in claim 30 wherein the soft segment macrodiol is derived from a polysiloxane macrodiol and a polyether macrodiol.
32. A polyurethane composition as claimed in claim 30 wherein the soft segment macrodiol comprises a polysiloxane macrodiol having a molecular weight in the range of 200 to 5000.
33. A polyurethane composition as claimed in claim 31 wherein the molecular weight of the macrodiol is in the range of 300 to 3000.
34. A polyurethane composition as claimed in claim 30, 32 or 33 wherein the soft segment macrodiol is derived from polydimethyl siloxane.
35. A polyurethane composition as claimed in claim 30 wherein the soft segment macrodiol comprises a polyether macrodiol of formula (II):
wherein m is an integer of 4 or more; and n is an integer of 2 to 50.
wherein m is an integer of 4 or more; and n is an integer of 2 to 50.
36. A polyurethane composition as claimed in claim 35 wherein m is from 5 to 18.
37. A polyurethane composition as claimed in claim 35 or claim 36 wherein the molecular weight of the polyether macrodiol is from about 200 to about 5000.
38. A polyurethane composition as claimed in claim 37 wherein the molecular weight of the polyether macrodiol is from about 200 to about 1200.
39. A polyurethane composition as claimed in any one of claims 29 to 30 wherein the diisocyanate is selected from one or more of 4,4'-methylenediphenyl diisocyanate (MDI), methylene bis(cyclohexyl) diisocyanate (H12MDI), p-phenylene diisocyanate (p-PDI), trans-cyclohexane-1,4-diisocyanate (CHDI) or a mixture of the cis and trans isomers, 1,6-hexamethylene diisocyanate (DICH), 2,4-toluene diisocyanate (2,4-TDI) or its isomers or mixtures thereof, p-tetramethylxylene diisocyanate (p-TMXDI) and m-tetramethylxylene diisocyanate (m- TMXDI).
40. A polyurethane elastomeric composition comprising a reaction product of:
(i) macrodiols comprising:
(a) polysiloxane macrodiol; and (b) polyether macrodiol;
(ii) MDI; and (iii) Chain extender composition comprising 1,4-butanediol and a silicon chain extender selected from the group consisting of 1,3-bis(4-hydroxybutyl) tetramethyl disiloxane; 1,4-bis(3-hydroxypropyl)tetramethyl disilylethylene;
1-4-bis(3-hydroxypropyl) tetramethyl disiloxane; and bis(6-hydroxyethoxypropyl)tetramethyldisiloxane.
(i) macrodiols comprising:
(a) polysiloxane macrodiol; and (b) polyether macrodiol;
(ii) MDI; and (iii) Chain extender composition comprising 1,4-butanediol and a silicon chain extender selected from the group consisting of 1,3-bis(4-hydroxybutyl) tetramethyl disiloxane; 1,4-bis(3-hydroxypropyl)tetramethyl disilylethylene;
1-4-bis(3-hydroxypropyl) tetramethyl disiloxane; and bis(6-hydroxyethoxypropyl)tetramethyldisiloxane.
41. A polyurethane composition as claimed in claim 40 wherein the silicon chain extender is present in an amount of about 40 mol% of the chain extender composition.
42. A polyurethane composition as claimed in any one of claims 29 to 41 wherein the weight percentage of (diisocyanate plus chain extender) in the composition is from 20 to 60 wt%.
43. A polyurethane composition as claimed in claim 40 wherein the weight ratio of polysiloxane to polyether is from 1:99 to 99:1.
44. A polyurethane composition as claimed in claim 43 wherein the weight ratio of polysiloxane is polyether is about 80:20.
45. A biomaterial comprising a polyurethane elastomeric composition as claimed in any one of claims 29 to 44.
46. A medical device, article or implant composed wholly or partly of the polyurethane elastomeric composition as claimed in any one of claims 29 to 44.
47. A medical device, article or implant as claimed in claim 46 wherein the medical device, article or implant is selected from cardiac pacemakers, defibrillators and other electromedical devices, catheters, cannulas, implantable prostheses, cardiac assist devices, heart valves, vascular grafts, stents, extra-corporeal devices, artificial organs, pacemaker leads, defibrillator leads, blood pumps, balloon pumps, A-V shunts, biosensors, membranes for cell encapsulation, drug delivery devices, wound dressings, artificial joints, orthopaedic implants and soft tissue replacements.
48. Use as claimed in any one of claims 1 to 22 wherein said optionally substituted radicals are substituted with one or more halo.
49. Use as claimed in claim 48 wherein the halo is fluoro.
50. A material having improved mechanical properties, clarity, processability and/or degradation resistance comprising a polyurethane elastomeric composition as claimed in any one of claims 29 to 44.
51. A degradation resistant material comprising a polyurethane elastomeric composition as claimed in any one of claims 29 to 44.
52. A degradation resistant material as claimed in claim 51 wherein the material is invivo degradation resistant.
53. A device, article or implant which is composed wholly or partly of a polyurethane elastomeric composition as claimed in any one of claims 29 to 44.
54. A device, article or implant as claimed in claim 53 wherein the device, article or implant is selected from artificial leather, shoe soles, cable sheathing, varnishes and coatings, structural components for pumps or vehicles, mining ore screens and conveyor belts, laminating compounds, textiles, separation membranes, sealants or components of adhesives.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPO7878 | 1997-07-14 | ||
| AUPO7878A AUPO787897A0 (en) | 1997-07-14 | 1997-07-14 | Silicon-containing chain extenders |
| PCT/AU1998/000546 WO1999003863A1 (en) | 1997-07-14 | 1998-07-14 | Silicon-containing chain extenders |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2296642A1 CA2296642A1 (en) | 1999-01-28 |
| CA2296642C true CA2296642C (en) | 2005-11-08 |
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ID=3802168
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002296642A Expired - Fee Related CA2296642C (en) | 1997-07-14 | 1998-07-14 | Silicon-containing chain extenders |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US6420452B1 (en) |
| EP (1) | EP1000070B1 (en) |
| JP (1) | JP2001510196A (en) |
| CN (1) | CN1267304A (en) |
| AT (1) | ATE249466T1 (en) |
| AU (2) | AUPO787897A0 (en) |
| BR (1) | BR9811689A (en) |
| CA (1) | CA2296642C (en) |
| DE (1) | DE69818063T2 (en) |
| WO (1) | WO1999003863A1 (en) |
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- 1997-07-14 AU AUPO7878A patent/AUPO787897A0/en not_active Abandoned
-
1998
- 1998-07-14 JP JP2000503086A patent/JP2001510196A/en active Pending
- 1998-07-14 AT AT98931847T patent/ATE249466T1/en not_active IP Right Cessation
- 1998-07-14 EP EP98931847A patent/EP1000070B1/en not_active Expired - Lifetime
- 1998-07-14 WO PCT/AU1998/000546 patent/WO1999003863A1/en active IP Right Grant
- 1998-07-14 CA CA002296642A patent/CA2296642C/en not_active Expired - Fee Related
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- 1998-07-14 DE DE69818063T patent/DE69818063T2/en not_active Expired - Fee Related
- 1998-07-14 BR BR9811689-4A patent/BR9811689A/en not_active Application Discontinuation
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2000
- 2000-01-14 US US09/483,165 patent/US6420452B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP1000070B1 (en) | 2003-09-10 |
| JP2001510196A (en) | 2001-07-31 |
| DE69818063D1 (en) | 2003-10-16 |
| AUPO787897A0 (en) | 1997-08-07 |
| AU748318B2 (en) | 2002-05-30 |
| EP1000070A1 (en) | 2000-05-17 |
| DE69818063T2 (en) | 2004-06-03 |
| CA2296642A1 (en) | 1999-01-28 |
| BR9811689A (en) | 2000-09-26 |
| AU8201398A (en) | 1999-02-10 |
| CN1267304A (en) | 2000-09-20 |
| EP1000070A4 (en) | 2000-06-07 |
| WO1999003863A1 (en) | 1999-01-28 |
| ATE249466T1 (en) | 2003-09-15 |
| US6420452B1 (en) | 2002-07-16 |
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