AU776330B2 - Shape memory polyurethane or polyurethane-urea polymers - Google Patents
Shape memory polyurethane or polyurethane-urea polymers Download PDFInfo
- Publication number
- AU776330B2 AU776330B2 AU57974/00A AU5797400A AU776330B2 AU 776330 B2 AU776330 B2 AU 776330B2 AU 57974/00 A AU57974/00 A AU 57974/00A AU 5797400 A AU5797400 A AU 5797400A AU 776330 B2 AU776330 B2 AU 776330B2
- Authority
- AU
- Australia
- Prior art keywords
- shape memory
- polymer
- glass transition
- diisocyanate
- memory polymer
- 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.)
- Ceased
Links
- 229920000642 polymer Polymers 0.000 title claims description 91
- 229920002635 polyurethane Polymers 0.000 title claims description 64
- 239000004814 polyurethane Substances 0.000 title claims description 64
- 229920003226 polyurethane urea Polymers 0.000 title claims description 13
- -1 polysiloxane Polymers 0.000 claims description 124
- 239000000203 mixture Substances 0.000 claims description 88
- 230000009477 glass transition Effects 0.000 claims description 53
- 229920000431 shape-memory polymer Polymers 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 30
- 239000004970 Chain extender Substances 0.000 claims description 28
- 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 22
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- 239000010703 silicon Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 125000005442 diisocyanate group Chemical group 0.000 claims description 18
- 229920000570 polyether Polymers 0.000 claims description 18
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 17
- 230000015556 catabolic process Effects 0.000 claims description 16
- 238000006731 degradation reaction Methods 0.000 claims description 16
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- 239000007943 implant Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 150000003254 radicals Chemical class 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 239000012620 biological material Substances 0.000 claims description 7
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 7
- 150000002009 diols Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 6
- 125000004427 diamine group Chemical group 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000002792 vascular Effects 0.000 claims description 5
- 210000003462 vein Anatomy 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
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 238000003780 insertion Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000001356 surgical procedure Methods 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
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-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 3
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 3
- 210000000988 bone and bone Anatomy 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 238000001727 in vivo Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 claims description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 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
- 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
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 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
- ILCGTNBULCHWOE-UHFFFAOYSA-N 4-[[4-aminobutyl(dimethyl)silyl]oxy-dimethylsilyl]butan-1-amine Chemical compound NCCCC[Si](C)(C)O[Si](C)(C)CCCCN ILCGTNBULCHWOE-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004606 Fillers/Extenders Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 206010052664 Vascular shunt Diseases 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
- 238000005299 abrasion Methods 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 238000002399 angioplasty Methods 0.000 claims description 2
- 239000008280 blood Substances 0.000 claims description 2
- 210000004369 blood Anatomy 0.000 claims description 2
- 230000000747 cardiac effect Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000013267 controlled drug release Methods 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 2
- 230000007831 electrophysiology Effects 0.000 claims description 2
- 238000002001 electrophysiology Methods 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims description 2
- 230000002255 enzymatic effect Effects 0.000 claims description 2
- 230000001815 facial effect Effects 0.000 claims description 2
- 210000003709 heart valve Anatomy 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
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-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
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 230000037431 insertion Effects 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005304 joining Methods 0.000 claims description 2
- 125000005647 linker group Chemical group 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 125000006233 propoxy propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000008439 repair process Effects 0.000 claims description 2
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 2
- 230000002861 ventricular Effects 0.000 claims description 2
- 101100278987 Arabidopsis thaliana ECH2 gene Proteins 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 238000005452 bending Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 125000000623 heterocyclic group Chemical group 0.000 description 8
- 125000002911 monocyclic heterocycle group Chemical group 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 125000000304 alkynyl group Chemical group 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 125000003367 polycyclic group Polymers 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000036760 body temperature Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 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 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RYECOJGRJDOGPP-UHFFFAOYSA-N Ethylurea Chemical compound CCNC(N)=O RYECOJGRJDOGPP-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 210000001124 body fluid Anatomy 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000001301 oxygen Chemical group 0.000 description 2
- 229910052760 oxygen Chemical group 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 238000000807 solvent casting Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000001113 thiadiazolyl group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000005919 1,2,2-trimethylpropyl group Chemical group 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- 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 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-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
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- 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 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 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 description 1
- 125000006041 3-hexenyl group Chemical group 0.000 description 1
- 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 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 101100331550 Antirrhinum majus DICH gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000005035 acylthio group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000006323 alkenyl amino group Chemical group 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000006319 alkynyl amino group Chemical group 0.000 description 1
- 125000004419 alkynylene group Chemical group 0.000 description 1
- 125000005133 alkynyloxy group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005251 aryl acyl group Chemical group 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000008901 benefit Effects 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
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000000440 benzylamino group Chemical group [H]N(*)C([H])([H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000008512 biological response Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 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 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 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 description 1
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 1
- 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 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 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 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000262 haloalkenyl group Chemical group 0.000 description 1
- 125000005291 haloalkenyloxy group Chemical group 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000000232 haloalkynyl group Chemical group 0.000 description 1
- 125000005292 haloalkynyloxy group Chemical group 0.000 description 1
- 125000003106 haloaryl group Chemical group 0.000 description 1
- 125000004996 haloaryloxy group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 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 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 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 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000002513 implantation Methods 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
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- 125000004999 nitroaryl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 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 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 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 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Description
WO 01/07499 PCT/AU00/00863 1 SHAPE MEMORY POLYURETHANE OR POLYURETHANE-UREA POLYMERS The present invention relates to polyurethane and polyurethane-urea polymers which have shape memory characteristics. The polymers respond to their shape memory when heated in a temperature range of about 20 0 C to about 100°C and are suitable for manufacturing articles, devices and implants requiring shape memory properties. The polymers are particularly useful in biomedical applications.
A shape memory polymer as a cast, moulded, foamed or extruded shape is capable of remembering a basic shape such as plane configuration and dead folds and taking on a second shape when the basic shape is modified. The basic shape can be modified by changing the plane configuration and adding further folds, twists, kinks, bends and/or other three dimensional configurations at a temperature higher than the glass transition point of the polymer, but lower than the moulding temperature. The modified shape is typically set when the polymer is cooled in the modified state to a temperature lower than the glass transition temperature. The method of utilising the shape memory is by heating the modified shape to a temperature higher than the glass transition temperature thereby restoring the original shape. Polymers with such characteristics combined with biostability would find many applications in the fabrication of various medical devices. The device shape can be optimised depending on the location site, for example, the shape could be modified by coiling or collapsing and subsequent cooling to a temperature below the glass transition temperature to freeze the modified shape. Thermally triggered shape memory could then occur thereby returning the device to its original shape to enable fixing or anchoring to the location site. Medical devices which would benefit from such shape memory characteristics include bone suture anchors, vascular, esophageal and bilial stents and cochlear implantations.
WO 01/07499 PCT/AUOO/00863 2 Segmented copolymers such as thermoplastic polyurethanes usually exhibit shape memory characteristics if formulated such that the glass transition temperature of one segment falls within a useful temperature range of about 25°C to about 60 0 C. Such polyurethanes are generally prepared from polyester or polyether macrodiols, aromatic diisocyanates and chain extenders' 2 3 The shape memory polyurethane compositions disclosed in United States Patent Nos. 5,049,591 and 5,139,832 are formulated with conventional reagents used in the art of polyurethane manufacture and hence are prone to degradation, particularly under the oxidative and hydrolytic conditions present in biological environments.
The stability of such compositions in long term implant applications is expected to be very poor since commercial polyurethanes such as Estane are based on degradation-prone' 5 polytetramethylene oxide (PTMO), 4,4'diphenylmethane diisocyanate and 1,4 butanediol.
Similarly, polycarbonate macrodiol based shape memory polyurethanes are expected to have very poor hydrolytic resistance and be unsuitable for long term medical implants 6 These commercial polyurethanes often also contain small amounts of low molecular weight residues and additives that leach out of the polyurethane and cause undesirable biological responses.
United States Patent No. 5814705 discloses shape memory compositions based on blends of commercial polyurethanes such as Estane with other block copolymers.
The compatibility of the component polymers may not be sufficient to have a homogeneous shape memory polymer composition. Such compositions, particularly in long term use, may lead to poor performance due to a phase separation of the component polymers.
A range of biostable polyurethanes are disclosed in International Patent Publication Nos. W098/13405 and W099/03863 and United States Patent No. 5,393,858. We have found that by proper choice of components and the relative 3 amounts of the hard and soft segments that biostable polyurethanes can be formulated to have one glass transition temperature in a temperature range of about 20 0
C
to about 100 0 C. Such polyurethanes therefore possess both the properties of biostability, compatibility and shape memory which enable them to be used in the manufacture of medical articles, devices and implants.
According to the present invention there is provided a biostable shape memory polyurethane or polyurethane-urea polymer comprising a reaction product of and as set out under below or a reaction product of and as set out under below: a silicon-based macrodiol; a polyether of formula below; or a silicon-based macrodiol and a polyether of formula A- (CH) n(CH 2 )mn-(CH2)-A' (I) wherein 20 A and A' are endcapping groups; m is an integer of 6 or more; and n is an integer of 1 or greater, wherein the molecular weight range of the silicon-based macrodiol in component is 300 25 to 700; a diisocyanate; and .o a chain extender; or a diisocyanate; 60% by weight of a diol or diamine chain 30 extender based on the total weight of chain extender; and 40% by weight of a silicon-containing chain extender based on the total weight of chain extender, said polymer having a glass transition temperature which enables the polymer to be transformed from its original shape into a first shape at a temperature higher than the H:u7AnmetWXecp\SpecMY7974-0. I SPECIdoc 24AO04 4 glass transition temperature and maintained in said first shape when the polymer is cooled to a temperature lower than the glass transition temperature, said polymer then being capable of resuming its original shape on heating to a temperature higher than the glass transition temperature.
The term "endcapping group" is used herein in its broadest sense and includes reactive functional groups or groups containing reactive functional groups. Suitable examples of reactive functional groups are alcohols, carboxylic acids, aldehydes, ketones, esters, acid halides, acid anhydrides, amines, imines, thio, thioesters, sulphonic acid and expoxides. Preferably the reactive functional group is an alcohol or an amine, more preferably an alcohol.
Further according to the present invention there is provided a biostable shape memory composition which comprises: a blend of two or more biostable shape memory polymers comprising a reaction product of and 20 as set out under below or a reaction product i°-o of and as set out under below: a silicon-based macrodiol; the polyether of formula as defined above; or a silicon-based macrodiol and the 25 polyether of formula as defined above; a diisocyanate; and a chain extender; or a diisocyanate; and a chain extender, 30 said polymers having glass transition temperatures which enable the polymers to be transformed from their original shape into a first shape at a temperature higher than the glass transition temperature and maintained in said first shape when the polymers are cooled to a temperature lower than the glass transition temperature, said polymers then being capable of resuming their original shape on heating to a temperature higher H:\suanctU(mepLSp57974-.1 SPECIdoc I 67/04 5 than the glass transition temperature; or (ii) a blend of at least one biostable shape memory polymer as defined above in combination with a polymeric material.
Component preferably has greater than about silicon-based macrodiol, in particular greater than about 70% as such polymers possess good biostability.
The silicon-based macrodiol or macrodiamine may be a polysiloxane.
The polysiloxane may be represented by the formula (III):
HO-R
5 i- Si -R 6
-OH
R3 R4
P
(III)
wherein 15 A and A' are as defined above;
R
1
R
2
R
3 and R 4 are the same or different and selected from hydrogen or an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical; 20 R 5 and R 6 are the same or different and selected from a divalent optionally substituted straight chain, Sbranched or cyclic, saturated or unsaturated hydrocarbon radical; and p is an integer of 1 or greater.
25 The hydrocarbon radical for substituents R, R 1
R
2
R
3 and R 4 may include alkyl, alkenyl, alkynyl, aryl or heterocyclyl radicals. It will be appreciated that the equivalent radicals may be used for substituents Rs, R 6 and
R
7 except that the reference to alkyl, alkenyl and alkynyl should be to alkylene, alkenylene and alkynylene, respectively. In order to avoid repetition, only detailed H:\sutmnnetUep\SppecN7 7974-0I SPECIldoc 24A06A4 Sa definitions of alkyl, alkenyl and alkynyl are provided hereinafter.
The term "alkyl", denotes straight chain, branched or mono- or poly-cyclic alkyl, pref erably CI-.
12 alkyl or cycloalkyl. Examples of straight chain and branched alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, amiyl, isoamyl, sec-amyl, 1,2-dimethylpropyl, 1, l-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, 1,2,2trimethylpropyl, 1,1, 2-trimethylpropyl, heptyl, 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, 1methylheptyl, 1,1,3,3-tetramethylbutyl, nonyl, 3-, 6- or 7-methyloctyl, 4- or 20 ethylheptyl, 2- or 3-propylhexyl, decyl, 3-, 7- and 8-methylnonyl, 5- or 6-ethyloctyl, 3- or 4-propylheptyl, undecyl, 1-, 8- or 9-methyldecyl, 3-, 6- or 7-ethylnonyl, 4- or 5-propyloctyl, 2- or 3-butylheptyl, 1-pentylhexyl, dodecyl, 9- or H:\sunrKccp\Spci\57974-). I SPECIdoc 24AW04 WO 01/07499 PCT/AUOO/00863 7- or 8-ethyldecyl, 5- or 6-propylnonyl, 2-, 3- or 4-butyloctyl, 1,2-pentyiheptyl and the like.
Examples of cyclic alkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like.
The term "alkenyla 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 C 2 _1 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, 1,3cyclopentadienyl, 1, 3-hexadienyl, 1, 4-hexadienyl, 1, 3-cyclohexadienyl, 1,4-cyclohexadienyl, 1, 3-cycloheptadienyl, 1,3, 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-pezitynyl, 4-pentynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 1O-undecynyl, 4-ethyl-1-octyn-3-yl, 7-dodecynyl, 9-dodecynyl, lO-dodecynyl, 3-methyl-l-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, phenoxyphenyl, naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl, benzanthracenyl, dibenzanthracenyl, phenanthrenyl and the like.
The term "heterocyclyl" denotes mono- or poly-cyclic heterocyclyl groups containing at least one WO 01/07499 PCT/AU0/00863 7 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, pyrrolyl, pyrrolinyl, imidazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazolyl or tetrazolyl; saturated 3 to 6 membered heteromonocyclic groups containing 1 to 4 nitrogen atoms, such as pyrrolidinyl, imidazolidinyl, piperidino or piperazinyl; unsaturated condensed heterocyclic groups containing 1 to 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 heteromonocyclic 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, benzoxazolyl 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, 8alkenyloxy, 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, aldehydo, alkylsuiphonyl, arylsuiphonyl, alkylsuiphonylamino, arylsuiphonylamino, alkylsuiphonyloxy, arylsuiphonyloxy, heterocyclyl, heterocycloxy, heterocyclylamino, haloheterocyclyl, alkylsuiphenyl, arylsuiphenyl, carboalkoxy, carboaryloxy, mercapto, alkylthio, arylthio, acylthio and the like.
A preferred polysiloxane is PDMS which is a compound of formula (III) wherein R, to R4 are methyl and R and R 6 are as def ined above. Preferably R 5 and R 6 are the same or different and selected from propylene, butylene, pentylene, hexylene, ethoxypropyl (-CH 2
CH
2
OCH
2
CH
2
CH
2 propoxypropyl and butoxypropyl.
The polysiloxane macrodiols may be obtained as commercially available products such as X-22-160AS from Shin Etsu in Japan or prepared according to known procedures. The preferred molecular weight range of the :polysiloxane macrodiol is 500 to about 700.
Suitable polyethers include polyether macrodiols represented by the formula H0 L(CH2)M-Oj -H
M
~.wherein m is as defined in formula above, preferably 6 to 18; and n is as defined in formula above, preferably 1 to Polyether macrodiols of formula wherein m is 6 or higher such as poly(hexamethyleneoxide) (PHNO), poly(heptamethyleneoxide), poly(octamethylene oxide) (POMO) fi:su7nneW~cp\r~m\5774-0I SPECIAdoc 24/(W04 9 and poly(decamethylene oxide) (PDMO) are preferred over the conventional PTMO. PHMO and PDMO are particularly preferred due to their relatively high glass transition temperatures.
The polyether macrodiols may be prepared by the procedure described by Gunatillake et a1 6 The molecular weight range of the polyether macrodiol is about 300 to about 2000, more preferably about 300 to about 700.
The diisocyanates may be aliphatic or aromatic diisocyanates such as, for example 4,4'-diphenylmethane diisocyanate (MDI), methylene biscyclohexyl diisocyanate
(H
12 MDI), p-phenylene diisocyanate (p-PDI), trans-cyclohexane-1,4-diisocyanate (CHDI), 1,6-diisocyanatohexane (DICH), (NDI), para-tetramethylxylenediisocyanate (p-TMXDI), meta-tetramethylxylene diisocyanate (m-TMXDI), 2,4-toluene diisocyanate (2,4-TDI) isomers or mixtures thereof or isophorone diisocyanate (IPDI). MDI is particularly preferred.
The chain extender may be selected from diol or diamine chain extenders. Examples of diol chain extenders include 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1, 10-decanediol, 1,12-dodecanediol,1,4cyclohexanediol, 1,4-cyclohexanedimethanol, p-xyleneglycol, 1,3-bis(4-hydroxybutyl) tetramethyldisiloxane, 25 1,3-bis(6-hydroxyethoxypropyl)tetramethyldisiloxane and 1,4-bis(2-hydroxyethoxy)benzene. Suitable diamine chain %6 6extenders include 1,2-ethylenediamine, 1,3-propanediamine,1,4-butanediamine, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane and 1,6-hexanediamine.
The chain extender may also be a silicon-containing chain extender of the type described in our International Patent Publication No. W099/03863, the entire contents of which are incorporated herein by reference. Such chain extenders include a silicon-containing diol of the formula (VI): H:'6uiannetLKccpSpcdN37974-X). I SPECI.doc 24/0/(1
R
1 2
HO-R
5 -Si- -R 7 -Si- -R 6
-OH
R3 R4 q
(VI)
wherein
R
1
R
2
R
3
R
4 Rs and R 6 are as defined in formula (III) above;
R
7 is a divalent linking group or a divalent optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical; and q is 0 or greater, preferably 2 or less.
Component of the polymer generally forms the soft segment of the polyurethane or polyurethane-urea and provides the low glass transition temperature. The high glass transition temperature is provided by the hard 0** segment components and 15 Preferably, the amount of hard segment in the polymer of the present invention is about 30 to about Gee 100 wt%, more preferably about 50 to about 80 wt%, most preferably about 60 to about 70 wt%. However, it will be appreciated that this amount is dependent on the type of *ee
G
a0 0 H:\urnnc\Kccp\Spc57974-X). I SPECIdoc 24A(W04 11 THIS AND THE FOLLOWING PAGE ARE INTENTIONALLY BLANK THE NEXT PAGE IS PAGE 13 HAsu72nwtiU,=p Spccil57974-SX) I SPECIAOc 24106104 13 soft segment polymer used, in particular the molecular weight of this polymer. For example, when the molecular weight of the soft segment polymer is about 500, then a to 60 wt% hard segment is preferred.
For most applications, it is preferred that the shore hardness of the polymer below the glass transition temperature is in the range of about 82D to about while the hardness above the glass transition temperature is in the range of about 20D to about 30D. The glass transition temperatures of the polymers and compositions of the present invention are generally in the range of about 0 C to about 100 0 C, preferably about 20 to about 60 0
C.
However, in some applications such as biotechnological applications, it may be advantageous for the glass transition temperature to be sub ambient below about 0
C.
It will be appreciated that the shape memory compositions of the present invention may include a blend of two or more of the shape memory polyurethane or polyurethane-urea polymers defined above or at least one shape memory polyurethane or polyurethane-urea polymer defined above in combination with another material. The o.o other material will preferably be of any suitable known S* type which does not substantially effect the shape memory and/or biostability properties of the polymers of the present invention and may include polymeric and nonpolymeric materials.
Examples of polymeric materials include S: conventional polyurethanes such as PELETHANE
TM
ESTANE
TM
CARBOTHANE
T
CORETHANE
T and CHRONOFLEX
T
m; shape memory polyurethanes such as those disclosed in United States Patent Nos. 5,145,935 and 5,135,786 and available from Mitsubishi Heavy Industries Ltd (distributed by Memry Corporation in the United States of America; polyolefins such as polyethylene, polypropylene, ethylene propylene H:suanrtccp SpciA57974-(X. I SPECIdoc I 1103/04 WO 01/07499 PCT/AU00/00863 14 copolymers, metallocene polymers, ethylene vinylacetate copolymers and polyvinyl chloride; polyamides; and liquid crystalline polymers such as those available from Eastman Kodak (XG7), Mitsubishi Chemical Industry (Novaculates) and Idemitsu Petrochemical Industry (Idemitsu LCP and Unitika (Lodrum LC). Such polymeric materials generally blend well with the shape memory polymers of the present invention which usually contain high levels of polysiloxane segments.
Each of the polymers forming the shape memory composition preferably have different glass transition temperatures and/or different amounts of hard segment component. Suitable compositions may include a first polymer with a low glass transition temperature, preferably below about ambient temperature and a second polymer with a glass transition temperature above the ambient temperature, more preferably above about 50 0 C. The two polymers can be blended in proportions such that the final blend will have a glass transition temperature in the preferred range of about 20 0 C to about 60 0 C. Generally the glass transition temperature of the composition is intermediate to those of the two polymers.
Alternatively, the composition may include a first polymer having a high percentage of hard segment component, for example, above about 70 wt%, more preferably above about 90%. Particularly preferred examples of such polymers are the non-elastomeric polyurethane or polyurethane-urea polymers disclosed in International Patent Application No. PCT/AU99/00236. This first polymer can be blended with a second polymer having a lower percentage of hard segment, for example, about 30 to about wt%, more preferably about 40 to about 50 wt%. Examples of suitable polymeric blends include a combination of an elastomeric and a non-elastomeric polyurethane or polyurethane-urea polymer. The term "non-elastomeric" refers to polyurethanes having a elongation of up to about 200% generally up to about 100%. This technique allows a composition having a softening temperature 15 appropriate for the application to be prepared.
The shape memory polymers and compositions of the present invention may be prepared by any technique familiar to those skilled in the manufacture of polyurethanes. These include one or two-step bulk or solution polymerisation procedures. The polymerisation can be carried out in conventional apparatus or within the confines of a reactive extruder continuous injection moulding or mixing machines.
In a one-step bulk polymerisation procedure the appropriate amount of component is mixed with the chain extender first at temperatures in the range of about 45 to about 100 0 C, more preferably about 60 to about 80 0 C. If desired a catalyst such as stanneous octoate or dibutyltin dilaurate at a level of about 0.001 to about 0.5 wt based on the weight of the total ingredients may be added to the initial mixture. Molten diisocyanate is then added and mixed thoroughly to give a homogeneous polymer liquid and cured by pouring the liquid polymer into Teflon-coated trays and heating in an oven to about 100°C.
20 The shape memory polymers can also be prepared by a two-step method where a prepolymer is prepared by reacting component with a diisocyanate. The prepolymer is then reacted with a suitable chain extender.
The polymers and compositions of the present invention are particularly useful in preparing materials having good mechanical properties, more specifically biomaterials as a consequence of their biostability or improved resistance to degradation and their shape memory properties.
According to another aspect of the present invention there is provided a material having improved mechanical properties, clarity, processability, biostability and/or degradation resistance comprising the polymer or composition defined above.
The present invention also provides use of the polymer or composition defined above as a material having improved mechanical properties, clarity, processability, H:uanncil\KeepSpccM79744 SPECIdoc I 1/0304 16 biostability and/or degradation resistance.
The present invention further provides the polymer or composition defined above when used as a biostable material having improved mechanical properties, clarity, processability, biostability and/or degradation resistance.
The mechanical properties which are improved include tensile strength, tear strength, flex fatigue resistance, 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 20 from gels.
The term "biostability" is used herein in its broadest sense and refers to a stability when in contact with cells and/or bodily fluids of living animals or humans.
There is further provided a degradation resistant material which comprises the polymer or composition defined *0 above.
The polymer or composition of the present invention should also have a good compatibility and 30 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 or biostable material which comprises the polymer or composition defined above.
The polymer or composition may also be used as a HsnuannclUWtcp spi7974-. I SPECIAdoc 1103/04 WO 01/07499 PCT/AU00/00863 17 biomaterial. The term "biomaterial" is used herein in its broadest sense and refers to a material which is used in situations where it comes into contact with the cells and/or bodily fluids of living animals or humans.
The polymer or 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 polymer or composition defined above.
The medical devices, articles or implants may include catheters; stylets; bone suture anchors; vascular, oesophageal and bilial stents; cochlear implants; reconstructive facial surgery; controlled drug release devices; components in key hole surgery; biosensors; membranes for cell encapsulations; medical guidewires; medical guidepins; cannularizations; pacemakers, defibrillators and neurostimulators and their respective electrode leads; ventricular assist devices; orthopaedic joints or parts thereof including spinal discs and small joints; cranioplasty plates; intraoccular lenses; urological stents and other urological devices; stent/graft devices; device joining/extending/repair sleeves; heart valves; vein grafts; vascular access ports; vascular shunts; blood purification devices; casts for broken limbs; vein valve, angioplasty, electrophysiology and cardiac output catheters; and tools and accessories for insertion of medical devices, infusion and flow control devices.
As the polymers and compositions of the present invention may be designed so that they are rigid at ambient temperature but soften around the body temperature they have many applications in the construction of medical articles, devices and implants. For example, intravenous catheters made from such materials could be inserted initially in the vein due to the high flexural modulus of the material, but would then soften once inside the blood vessel. Furthermore, catheters may be modified to a WO 01/07499 PCT/AU00/00863 18 predetermined shape for ease of directing to a target area or modified in such a way to have sections with different softening temperatures, for ease of guidance of the device to a specific location.
It will be appreciated that polymers and compositions having properties optimised for use in the construction of various medical devices, articles or implants and possessing shape memory characteristics will also have other non-medical applications. Such applications may include toys and toy components, shape memory films, pipe couplings, electrical connectors, zero-insertion force connectors, Robotics, Aerospace actuators, dynamic displays, flow control devices, sporting goods and components thereof, body-conforming devices, temperature control devices, safety release devices and heat shrink insulation.
Thus, the present invention extends to the use of the polymer or 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 polymer or composition as defined above.
The invention will now be described with reference to the following non-limiting examples.
EXAMPLE 1 Poly(hexamethylene oxide) (PHMO) (MW 489.7) was prepared according to a method described by Gunatillake et a1 7 and United States Patent No. 5,403,912 and dried at 130°C under vacuum for 4 h. A shape memory polyurethane composition from PHMO was prepared according to a one-step bulk polymerisation as described below.
PHMO (35.00 g) and 1,4-butanediol (BDO) (12.06 g) were weighed in to a 500 mL polypropylene beaker and the contents warmed to 70 0 C. Molten MDI (52.93 g) was weighed into a 100 mL, wet-tared polypropylene beaker and added to the PHMO/BDO mixture quickly with stirring. The mixture was WO 01/07499 PCT/AU00/00863 19 stirred for about 30 sec and the contents poured onto a Teflon-coated metal pan. The polyurethane was cured at 100°C for 4 h under nitrogen. The resulting polyurethane was clear and transparent. The specimens for various tests were prepared by compression molding at a temperature of 200 0 C and injection moulding.
Dynamical Mechanical Thermal Analysis, DMTA (Rheometrics MkIIIe) was performed on 40 mm x 10 mm x 1 mm compression moulded samples in single cantilever bending mode at Htz over a temperature range of 30 0 C to 90 0 C at a ramp rate of 2 0 C/min. The onset of the change in the bending modulus was at 37 0 C (1100±50 MPa bending mod) and the endset of change in the bending modulus was 56 0 C (50±20 MPa bending modulus).
The shape memory characteristics of the polyurethane composition were demonstrated as follows. An injection moulded flat, 2.5 mm thick plaque of the polyurethane and a compression moulded flat thin film (0.1 mm thick) were folded 1800 at 55 0 C and cooled to 20 0 C so that the plaque and thin film were locked into a 1800 folded configuration. The folded plaque and the thin film were stored for 72 hours without any configurational change and then subsequently heated in water to 55 0 C at which point the folded thin film very quickly sec) returned to its original flat configuration and the thicker plaque returned also to its original flat configuration but more slowly (ca. 20 sees).
A reverse experiment was also performed whereby permanent 1800 folds were placed in the samples by compressing between flat plates heated to 150 0 C. The thick and thin samples were then heated to 55 0 C and the 1800 fold undone to 00, this unfolding being locked in by cooling to The samples were stored at ambient temperature for 72 hours in the modified (unfolded) shape with no observable configuration changes. The samples were subsequently heated in water at 55 0 C causing the original 1800 fold to reform in similar times to those observed in the previous WO 01/07499 PCT/AU00/00863 20 experiment.
EXAMPLE 2 A polyurethane based on PHMO with a molecular weight of 398.0 was prepared using a procedure similar to that described in Example 1. PHMO (32.00 g) and 1,4butanediol (12.67 g) was weighed into a 500 mL polypropylene beaker and the contents warmed to 70 0
C.
Molten MDI (55.33 g) was weighed into a 100 mL wet-tared polypropylene beaker and added to the PHMO quickly with stirring. The mixture was stirred for about 30 sec and the contents poured onto a Teflon-coated metal pan. The polyurethane was cured at 100 0 C for 4 h under nitrogen. The resulting polyurethane was clear and transparent. The test specimens for various tests were prepared by compression moulding at a temperature of 200 0 C and injection moulding.
The onset of the change in the bending modulus was at 46 0 C (1050±50 MPa bending mod) and the endset of change in the bending modulus was 60 0 C (50±20 MPa bending mod) as determined by DMTA analysis. The shape memory characteristics of the composition was similar to that of the composition of Example 1 EXAMPLE 3 This example illustrates the preparation of shape memory polyurethane compositions with desired glass transition temperatures in the 20 0 C to 100 0 C range by solvent blending of two polyurethane compositions, one with a low flexural modulus (approximately in the range of about 15 to about 100 MPa range) and the other with a high flexural modulus 500MPa).
The low modulus polyurethane composition was prepared by reacting bis(6-hydroxyethoxypropyl) polydimethylsiloxane (48.00 g, MW 940.3), poly(hexamethylene oxide) (12.00 g, MW 700.2), 1,4-butanediol (5.80 g) and MDI (34.19 g) according to a one-step polymerisation procedure. The flexural modulus of WO 01/07499 PCT/AUOO/00863 21 the polyurethane was 30 MPa.
The high modulus polyurethane composition was prepared by reacting 1,4-cyclohexanedimethanol (25.27g), 1, 3bis(4-hydroxybutyl)-1, ,3,3-tetramethyldisiloxane (16.27 g) and MDI (58.46 g) according to a one-step bulk polymerisation. The flexural modulus of the polyurethane was 1770 MPa.
Differential scanning calorimetry (at a ramp rate of 10°C/min) demonstrated the presence of glass transition change onset at 91.2°C and an endset at 106.7°C with a Cp of 0.28J.g- 1 .°C This high modulus composition exhibited shape memory characteristics. A compression moulded thin plaque (0.1 mm) was folded at 110°C and immediately cooled to ambient temperature to preserve the fold. It was subsequently heated to 110°C resulting in a reversal of the shape to the original.
The high modulus and low modulus polyurethanes were blended by mixing 7.5 g and 2.5 g, respectively and dissolving the blend in N,N-dimethylformamide to give a 20 wt% solution. A thin film of the blend was prepared by solvent casting. The polymer solution was poured onto a Petrie Dish to form a 5 mm thick layer and the solvent evaporated in a nitrogen circulating oven over a period of 48 h. DSC analysis of the dried film showed a glass transition onset temperature of 45.6°C and an end set at 49.5°C.
A thin film (0.3 mm) of the blend was folded by 180° by heating to a temperature above 50°C and the folded shape fixed by cooling to room temperature. The folded shape reverted to the original shape when it was heated to exhibiting the shape memory characteristics of the blended polyurethane.
EXAMPLE 4 A polyurethane composition based on 1, 3-bis(4-hydroxybutyl)tetramethyldisiloxane (BHTD) and MDI was prepared.
WO 01/07499 PCT/AU00/00863 22 BHTD (Silar Laboratories, 55.68 g) was added to molten (45 0 C) MDI (50.00g) and thoroughly mixed until a clear and homogenous solution was obtained. This required about 3 min of stirring. The viscous polymer was then poured onto a Teflon-coated metal tray and cured at 100 0
C
for 4 h in an oven under nitrogen. The resulting polymer was clear and transparent. The cured polyurethane was compression moulded at 200 0 C to a 1 mm thick plaque. The materials exhibited a shore hardness of 75D, ultimate tensile strength of 60 MPa, and flexural modulus of 1795 MPa.
The onset of glass transition temperature was 0 C and the polyurethane remained rigid below 30 0 C and softened at body temperature (37 0
C).
EXAMPLE This example illustrates the preparation of a polyurethane using a low molecular weight siloxane macrodiol such that the polyurethane composition has a glass transition temperature close to the body temperature.
The polyurethane was prepared by reacting 4,4'methylenediphenyl diisocyanate (MDI, Orica), a, 3-bis (6-hydroxyethoxypropyl)-polydimethylsiloxane (PDMS MW 595) and 1,4-cyclohexanedimethanol (Aldrich PDMS with a molecular weight of 595 was obtained by distilling Shin- Etsu product X-22-160AS (Lot No. 803037) using a wiped-film evaporator.
PDMS was degassed at ambient temperature under vacuum (0.1 torr) for 4 h prior to polymerisation and CHDM (Aldrich) was melted at 60 2 C and degassed under vacuum (0.1 torr) for 1 h.
Degassed PDMS (5.94g) was added to molten (50 0
C)
MDI (5.00g) in a polypropylene beaker and stirred rapidly until the solution turned clear followed by adding CHDM (1.44 After stirring the mixture for further 35 sec, the viscous polymer was poured onto a Teflon-coated pan and cured at 100eC for 6 h under nitrogen. Tensile properties WO 01/07499 PCT/AU00/00863 23 were measured on a compression moulded sheet. DSC analysis was carried out to determine the glass transition temperature of the polyurethane. The polyurethane exhibited an ultimate tensile strength of 23.3 MPa, elongation at break of 97 ±8 and a Young's modulus of 201±65. The DSC results showed the onset of glass transition to be 26 2
C,
mid point at 342C and end at 422C. The polyurethane showed shape memory properties when tested using the procedure described in Example 3.
EXAMPLE 6 This example illustrates the preparation of shape memory polyurethanes by blending commercial polyurethanes and a high modulus polyurethane with a glass transition temperature of about 1002C. PELLETHANEr 2363-80A and CORETHANE"M AW 80 were used as examples of commercial polyurethanes.
The high modulus polyurethane was prepared using the following procedure. Molten (50 2 C) MDI (500.00 g) was weighed into a 2 L polypropylene beaker. The chain extenders BHTD (139.11 g) and CHDM (216.08 g) were weighed separately into two wet-tared polypropylene beakers. BHTD was added to MDI and stirred for about 45 seconds followed by molten (80 2 C) CHDM. Stirring was continued for another to 25 sec and the viscous polymer was immediately stirred into a Teflon-coated tray. The tray containing the polymer was kept under nitrogen at ambient temperature for about 45 min and cured at 100 C for 4 h.
Two compositions were prepared by blending the high modulus polyurethane with CORETHANE T and PELLETHANE, respectively. Composition 1 was prepared by dissolving g of the high modulus polyurethane with 2.5 g of
CORETHANE
T
N in 40 mL of dimethyl acetamide. The mixture was cast into a thin film by pouring the solution into a Petrie dish and evaporating the solvent in a nitrogen circulating oven at 70 2C for 48 h. Similarly Composition-2 was 24 prepared by dissolving 2.5 g of PELLETHANE
T
N and 7.5 g of the high modulus polyurethane in dimethylacetamide and casting a thin film of the composition.
The tensile properties and glass transition temperature of the two compositions were determined and the results are summarised in Table 1 below. The two compositions showed shape memory properties when tested using the procedure described in Example 3.
TABLE 1. Tensile properties and glass transition temperatures of the polyurethane compositions prepared in Example 6.
Composition Elon. UTS YM Tg Mid Endpoint MPa MPa (°C)Onset point Composition 1 13 41.5 648 39.8 43.2 46.7 Composition 2 13 28.0 280 44.6 48.3 52.0 0%oo oooo 15 In the claims of this application and in the description of the invention, except where the context requires otherwise due to express language or necessary Soo implication, the words "comprise" or variations such as "comprises" or "comprising" are used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in •o various embodiments of the invention.
REFERENCES
1. J. R. Lin and L. W. Chen, J Appl. Polym. Sci., 69, 1563 (1998).
S. Hayashi, S. Kondo and K. Kawamura, 3 4 t h Annual Polyurethanes Technical Marketing Conf, p. 605 (1992).
3. T. Takahashi, N. Hayashi and S. Hayashi, J. Appl. Polym.
Sci., 60, 1061 (1996).
4. S. J. McCarthy, G. F. Meijs, N. Mitchell, P. A.
Gunatillake, G. Heath, A. Brandwood and K. Schindhelm, H:%annct\Kocp\Specj\57974-00.1I SPECI.doc I 1M3/04 24a Eiomaterials, 18, 1387 (1997).
L. Pinchuck, J. Eiomater. Sci. Edn. Vol 3 225 (1994).
6. Y. W. Tang, J. P. Santerre, R. S. Labow, I. Revenko and M. A. Sing, 25th Annual Meeting, Society for Biomaterials.
Rhode Island, USA, p 58 (1999).
7. P. A. Gunatillake, G. F. Mejs, R. C. Chatelier, D. M.
McIntosh, and E. Rizzardo Polya. Xnt. Vol 27, pp 275 (1992).
H:Nsu7znrLU~cepkSpc?\579744O I SPECIdoc I M0AM)
Claims (44)
1. A biostable shape memory polyurethane or polyurethane-urea polymer comprising a reaction product of and as set out under below or a reaction product of and as set out under below: a silicon-based macrodiol; a polyether of formula below; or a silicon-based macrodiol and a polyether of formula A- ECH2)m- O n-(CH 2 (I) wherein A and A' are endcapping groups; m is an integer of 6 or more; and n is an integer of 1 or greater, wherein the molecular weight range of the silicon-based macrodiol in component is 300 to 700; 20 a diisocyanate; and a chain extender; or a diisocyanate; S(c) 60% by weight of a diol or diamine chain extender based on the total weight of chain 25 extender; and 40% by weight of a silicon-containing chain extender based on the total weight of chain extender, said polymer having a glass transition temperature which 30 enables the polymer to be transformed from its original shape into a first shape at a temperature higher than the glass transition temperature and maintained in said first shape when the polymer is cooled to a temperature lower than the glass transition temperature, said polymer then being capable of resuming its original shape on heating to a temperature higher than the glass transition temperature. H:su/nnclUecpSpcciA579744)0 I SPECIdoc 24/06/04 26
2. A shape memory polymer according to claim 1, wherein component has greater than about 50% silicon- based macrodiol.
3. A shape memory polymer according to any one of the preceding claims, wherein component has greater than about 70% silicon based macrodiol.
4. A shape memory polymer according to any one of the preceding claims, wherein the silicon-based macrodiol is a polysiloxane. A shape memory polymer according to claim 4, wherein the polysiloxane is represented by the formula (III): R, R 2 HO-Rs-Si- 0--Si- -R 6 OH I I R3 R4 (III) wherein A and A' are as defined in claim 1: R 1 R 2 R 3 and R 4 are the same or different and 20 selected from hydrogen or an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical; R 5 and R 6 are the same or different and selected from a divalent optionally substituted straight chain, 25 branched or cyclic, saturated or unsaturated hydrocarbon radical; and p is an integer of 1 or greater.
6. A shape memory polymer according to claim wherein the macrodiol is PDMS which is a compound of formula (III) wherein R 1 to R 4 are methyl and Rs and R 6 are H:\sunnc\Kcp\SpccM7974(X). I SPECdoc 24/W4 27 as defined in claim
7. A shape memory polymer according to claim 5 or claim 6, wherein R 5 and R 6 are the same or different and selected from propylene, butylene, pentylene, hexylene, ethoxypropyl (-CH 2 CH 2 OCH 2 CH 2 CH 2 propoxypropyl and butoxypropyl.
8. A shape memory polymer according to any one of the preceding claims, wherein the polyether is a polyether macrodiol represented by the formula HO- [(CH 2 )m-O n-H (V) wherein m is as defined in formula in claim 1; and n is as defined in formula in claim 1.
9. A shape memory polymer according to claim 8, S 20 wherein the polyether macrodiol is poly(hexamethylene oxide) (PHMO), poly(heptamethylene oxide), poly(octamethylene oxide) (POMO) or poly(decamethylene oxide) (PDMO). 25 10. A shape memory polymer according to claim 9, wherein the polyether of the formula is PHMO.
11. A shape memory polymer according to any one of the preceding claims, wherein the diisocyanate is an 30 aliphatic or aromatic diisocyanate. 0
12. A shape memory polymer according to any of the preceding claims, wherein the diisocyanate is 4,4'- diphenylmethane diisocyanate (MDI), methylene biscyclohexyl diisocyanate (H 12 MDI), p-phenylene diisocyanate (p-PDI), trans-cyclohexane-l,4-diisocyanate (CHDI), 1,6- diisocyanatohexane (DICH), H:%su/nnclUCcep\SpcecM7974-0 I SPECidAc 24A)MM 28 (NDI), para-tetramethyixylenediisocyanate (p-TMXDI), meta- tetramethyixylene diisocyanate (m-TMXDI), 2,4-toluene diisocyanate (2,4-TDI) isomers or mixtures thereof or isophorone diisocyanate (IPDI).
13. A shape memory polymer according to any one of the preceding claims, wherein the diisocyanate is MDI.
14. A shape memory polymer according to any one of the preceding claims, wherein the diol chain extender is 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, 1,9- nonanediol, 1, 10-decanediol, 1, 12-dodecanediol, 1,4- cyclohexanediol, 1, 4-cyclohexanedimethanol, p-xyleneglycol, 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane, 1, 3-bis(6- hydroxyethoxypropyl) tetramethyldisiloxane or 1, 4-bis (2- hydroxyethoxy) benzene. A shape memory polymer according to any one of the preceding claims, wherein the diamine chain extender is 20 1, 2-ethylenediamine, 1, 3-propanediamine, 1, 4-butanediaiine, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4- aminobutyl) tetramethyldisiloxane or 1, 6-hexanediamine.
16. A shape memory polymer according to any one of the preceding claims, wherein the silicon-containing chain extender includes a silicon-containing diol of the formula (VI): R, R2 HO-Rt-7iSi 7 6 -OH L Jq (VI) wherein R 1 R 2 R 3 R 4 R 5 and R 6 are as def ined in formula (III) in claim H: su/annctU~ccp .SpceMA7974-(X). I SPECIdoc 24/06/0)4 29 R 7 is a divalent linking group or a divalent optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical; and q is 0 or greater.
17. A shape memory polymer according to any one of the preceding claims, wherein component polymer forms the soft segment of the polyurethane or polyurethane-urea polymer.
18. A shape memory polymer according to any one of the preceding claims, wherein components and of the polymer form the hard segment of the polyurethane or polyurethane-urea polymer.
19. A shape memory polymer according to claim 18, wherein the amount of hard segment in the polymer is about to 100 wt%. 20 20. A shape memory polymer according to claim 18 or claim 19, wherein the amount of hard segment in the polymer about 50 to about 80 wt%.
21. A shape memory polymer according to any one of 25 claims 18 to 20, wherein the amount of hard segment in the polymer is about 60 to about 70 wt%.
22. A shape memory polymer according to any one of Sthe preceding claims, wherein the shore hardness of the 30 polymer below the glass transition temperature is in the range of about 82D to about 50D, while the hardness above the glass transition temperature is in the range of about to about
23. A shape memory polymer according to any one of the preceding claims, wherein the glass transition temperature is in the range of about 20 0 C to about 100 0 C. II:Vu/rn.wAKcpSpcc579744). I SPECIdc 24/0604 30
24. A shape memory polymer according to any one of the preceding claims, wherein the glass transition temperature is in the range of about 20 to about 60 0 C. A biostable shape memory composition which comprises: a blend of two or more biostable shape memory polymers comprising a reaction product of and as set out under below or a reaction product of and as set out under below: a silicon-based macrodiol; the polyether of formula as defined in claim 1; or a silicon-based macrodiol and the polyether of formula as defined in claim 1; a diisocyanate; and a chain extender; or a diisocyanate; and a chain extender, said polymers having glass transition temperatures which enable the polymers to be transformed from their original shape into a first shape at a 25 temperature higher than the glass transition temperature and maintained in said first shape when the polymers are cooled to a temperature lower than the glass transition temperature, said polymers then being capable of resuming their original shape on heating to a temperature higher than the glass transition temperature; or (ii) a blend of at least one biostable shape memory polymer as defined above in combination with a polymeric material.
26. A shape memory composition according to claim wherein the polymeric material is a conventional polyurethane, shape memory polyurethane, polyolefin, H:\s2nr\Kecp\SpeeM79744)0 I SPECIdoc 16&07/04 31 polyamide or a liquid crystalline polymer.
27. A shape memory composition according to claim or claim 26, wherein each of the polymers forming the shape memory composition have different glass transition temperatures and/or different amounts of hard segment component.
28. A shape memory composition according to claim 27, which comprises a first polymer with a low glass transition temperature of below about ambient temperature and a second polymer with a glass transition temperature above the ambient temperature.
29. A shape memory composition according to claim 28, wherein the second polymer has a glass transition temperature of about 50 0 C.
30. A shape memory composition according to any one S 20 of claims 27 to 29, wherein the two polymers can be blended in proportions such that the final blend will have a glass transition temperature in the range of about 20 0 C to about 60 0 C. 25 31. A shape memory composition according to claim 27, which comprises a first polymer having a high percentage of hard segment component of above about 70 wts and a second *5 g. polymer having a lower percentage of hard segment of about 30 to about
32. A shape memory composition according to any one of claims 28 to 31 which comprises a first polymer having a high flexural modulus above 500 MPa and a second polymer having a low flexural modulus of about 15 to about 100 MPa.
33. A shape memory composition according to claim 32, wherein the composition includes a combination of an H:\su/znri\Kccp\SpccM7974-.o I SPECIdoc 24/0((M4 32 elastomeric and a non-elastomeric polyurethane or polyurethane-urea polymer.
34. A process for preparing a shape memory polymer as defined in any one of claims 1 to 24 which is a reaction product of and as set out under comprising the steps of: mixing component and the chain extender and (ii) reacting the mixture with the diisocyanate A process according to claim 34, wherein step (i) is performed at a temperature in the range of about 45 0 C to about 100 0 C.
36. A process according to claim 34 or claim wherein step occurs in the presence of a catalyst.
37. A process for preparing a shape memory polymer as 20 defined in any one of claims 1 to 24 which is a reaction product of and as set out under comprising S• the steps of: reacting component with a diisocyanate to form a prepolymer; and (ii) reacting the prepolymer with the chain extender S38. A process for preparing a shape memory polymer as defined in any one of claims 1 to 24 which is a reaction *oo product of and as set out under comprising the step of reacting the diisocyanate with the chain extenders and
39. A biostable material having improved mechanical properties, clarity, processability, biostability and/or degradation resistance which comprises the shape memory polymer as defined in any one of claims 1 to 24 and/or the H:\sulannetKcp\Spcc579744X).1 SPECI.doc 24/0610 33 composition as defined in any one of claims 25 to 33. A material according to claim 39, wherein the improved mechanical properties are tensile strength, tear strength, flex fatigue resistance, abrasion resistance, Durometer hardness, flexural modulus and/or related measures of flexibility or elasticity.
41. A material according to claim 39 or claim wherein the improved resistance to degradation is resistance to free radical, oxidative, enzymatic and/or hydrolytic processes and/or to degradation when implanted as a biomaterial.
42. A material according to any one of claims 38 to wherein the improved processability is ease of processing by casting and/or thermal means.
43. A material according to any one of claims 38 to Si 20 42, which is a degradation resistant material.
44. A material according to any one of claims 38 to 43, which is an in vivo degradation resistant or biostable material.
45. A material according to any one of claims 38 to 44, which is a biomaterial.
46. Use of the shape memory polymer as defined in any one of claims 1 to 24 and/or composition as defined in any one of claims 25 to 33 as a material having improved mechanical properties, clarity, processability, biostability and/or degradation resistance.
47. The shape memory polymer as defined in any one of claims 1 to 24 and/or composition as defined in any one of claims 25 to 33 when used as a material having improved H:\suannciUrcepXSpcci'.57974-(X) I SPECISO 24106/04 34 mechanical properties, clarity, processability, biostability and for degradation resistance.
48. A device or article which is composed wholly or partly of the shape memory polymer as defined in any one of claims 1 to 24 and/or composition as defined in any one of claims 25 to 33.
49. A device or article according to claim 48, which is a medical device, article or implant. A device or article according to claim 49, which is a stylet; bone suture anchor; vascular, oesophageal or bilial stent; cochlear implant; reconstructive facial surgery; controlled drug release device; component in key- hole surgery; biosensor; membrane for cell encapsulation; medical guidewire; medical guidepin; cannularization; pacemaker, defibrillator or neurostimulator and their respective electrode leads; ventricular assist device; 20 orthopaedic joint or parts thereof; intraoccular lens; urological device; stent/graft device; device joining/extending/repair sleeves; heart valve; vein graft; vascular access port; vascular shunt; blood purification device; cast for a broken limb; vein valve, angioplasty, electrophysiology or cardiac output catheter; or tools for insertion of medical devices, infusion and flow control o*o devices.
51. A device or article according to claim 48, which 30 is a toy or component thereof, shape memory film, pipe coupling, electrical connector, zero-insertion force connector, robotic, aerospace actuator, dynamic display, flow control device, sporting goods and components thereof, body-conforming device, temperature control device, safety release device or heat shrink insulation.
52. Use of the shape memory polymer as defined in any H:suannc\Xecp)pcc\57974-0. I SPECIdoc 24A)M) 35 one of claims 1 to 24 and/or composition as defined in any one of claims 25 to 33 in the manufacture of a device or article.
53. A shape memory polymer as defined in any one of claims 1 to 24 and/or a composition as defined in any one of claims 25 to 33 when used in manufacture of a device or article.
54. Shape memory polymers or compositions, processes for their preparation, biostable materials, devices or articles containing them or uses involving them, substantially as hereinbefore described with reference to any one of examples 1 to 3, 5 and 6. Dated this 24th day of June 2004 AORTECH BIOMATERIALS PTY LTD By their Patent Attorneys 20 GRIFFITH HACK Fellows Institute of Patent and Trade Mark Attorneys of Australia S.o H:\sutannic\Kccp\Spece?57974-(X). I SPECIduc 24AW04
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU57974/00A AU776330B2 (en) | 1999-07-20 | 2000-07-18 | Shape memory polyurethane or polyurethane-urea polymers |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPQ1707 | 1999-07-20 | ||
| AUPQ1707A AUPQ170799A0 (en) | 1999-07-20 | 1999-07-20 | Shape memory polyurethane or polyurethane-urea polymers |
| AU57974/00A AU776330B2 (en) | 1999-07-20 | 2000-07-18 | Shape memory polyurethane or polyurethane-urea polymers |
| PCT/AU2000/000863 WO2001007499A1 (en) | 1999-07-20 | 2000-07-18 | Shape memory polyurethane or polyurethane-urea polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU5797400A AU5797400A (en) | 2001-02-13 |
| AU776330B2 true AU776330B2 (en) | 2004-09-02 |
Family
ID=25631861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU57974/00A Ceased AU776330B2 (en) | 1999-07-20 | 2000-07-18 | Shape memory polyurethane or polyurethane-urea polymers |
Country Status (1)
| Country | Link |
|---|---|
| AU (1) | AU776330B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114605646B (en) * | 2022-03-31 | 2023-03-10 | 四川大学 | A reusable thermosetting polyurethane modified polysiloxane material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5049591A (en) * | 1988-09-30 | 1991-09-17 | Mitsubishi Jukogyo Kabushiki Kaisha | Shape memory polymer foam |
| US5139832A (en) * | 1988-10-14 | 1992-08-18 | Mitsubishi Jukogyo Kabushiki Kaisha | Shape memory film |
| AU4192497A (en) * | 1996-09-23 | 1998-04-17 | Aortech International Plc | Polysiloxane-containing polyurethane elastomeric compositions |
-
2000
- 2000-07-18 AU AU57974/00A patent/AU776330B2/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5049591A (en) * | 1988-09-30 | 1991-09-17 | Mitsubishi Jukogyo Kabushiki Kaisha | Shape memory polymer foam |
| US5139832A (en) * | 1988-10-14 | 1992-08-18 | Mitsubishi Jukogyo Kabushiki Kaisha | Shape memory film |
| AU4192497A (en) * | 1996-09-23 | 1998-04-17 | Aortech International Plc | Polysiloxane-containing polyurethane elastomeric compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| AU5797400A (en) | 2001-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6858680B2 (en) | Shape memory polyurethane or polyurethane-urea polymers | |
| JP6875391B2 (en) | Polyurethane / urea substance | |
| US6437073B1 (en) | Non-elastomeric polyurethane compositions | |
| CA2267276C (en) | Polysiloxane-containing polyurethane elastomeric compositions | |
| US20070027285A1 (en) | Polyurethanes | |
| AU734927B2 (en) | Silicon-based polycarbonates | |
| US20090118455A1 (en) | Siloxane-containing polyurethane-urea compositions | |
| EP3302589A1 (en) | Process for the preparation of polyurethane solutions based on silicon-polycarbonate diols | |
| AU776330B2 (en) | Shape memory polyurethane or polyurethane-urea polymers | |
| AU740402B2 (en) | Non-elastomeric polyurethane compositions | |
| AU2004293126B2 (en) | Polyurethanes | |
| AU3947200A (en) | Siloxane-containing polyurethane-urea compositions | |
| AU710248B2 (en) | Polysiloxane-containing polyurethane elastomeric compositions | |
| AU710248C (en) | Polysiloxane-containing polyurethane elastomeric compositions |