CN102365308B - 聚异丁烯基聚氨酯 - Google Patents
聚异丁烯基聚氨酯 Download PDFInfo
- Publication number
- CN102365308B CN102365308B CN201080010942.8A CN201080010942A CN102365308B CN 102365308 B CN102365308 B CN 102365308B CN 201080010942 A CN201080010942 A CN 201080010942A CN 102365308 B CN102365308 B CN 102365308B
- Authority
- CN
- China
- Prior art keywords
- elastomeric polymer
- weight
- pib
- soft chain
- polyisobutene
- 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.)
- Active
Links
- 229920002367 Polyisobutene Polymers 0.000 title claims abstract description 150
- 239000004814 polyurethane Substances 0.000 title description 19
- 229920002635 polyurethane Polymers 0.000 title description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 103
- 229920000570 polyether Polymers 0.000 claims abstract description 65
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 150000004985 diamines Chemical class 0.000 claims abstract description 40
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004202 carbamide Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims description 149
- 150000002009 diols Chemical class 0.000 claims description 114
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 110
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 52
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 52
- 239000000126 substance Substances 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 46
- -1 polyoxypropylene Polymers 0.000 claims description 42
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical class C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 31
- 125000003118 aryl group Chemical group 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 229920001748 polybutylene Polymers 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000004593 Epoxy Substances 0.000 claims description 15
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 14
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 229920001451 polypropylene glycol Polymers 0.000 claims description 10
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- AAMHBRRZYSORSH-UHFFFAOYSA-N 2-octyloxirane Chemical compound CCCCCCCCC1CO1 AAMHBRRZYSORSH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000001188 haloalkyl group Chemical group 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical group [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 6
- IIGAAOXXRKTFAM-UHFFFAOYSA-N N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C Chemical compound N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C IIGAAOXXRKTFAM-UHFFFAOYSA-N 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 5
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000004954 trialkylamino group Chemical group 0.000 claims description 5
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 claims description 4
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 4
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 claims description 4
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 claims description 4
- 229960005082 etohexadiol Drugs 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007943 implant Substances 0.000 claims description 4
- 239000008280 blood Substances 0.000 claims description 3
- 210000004369 blood Anatomy 0.000 claims description 3
- 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 2
- 108091029845 Aminoallyl nucleotide Proteins 0.000 claims description 2
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 claims description 2
- 238000012377 drug delivery Methods 0.000 claims description 2
- 238000005538 encapsulation Methods 0.000 claims description 2
- 229920006351 engineering plastic Polymers 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 210000000056 organ Anatomy 0.000 claims description 2
- 210000004872 soft tissue Anatomy 0.000 claims description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims 4
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 claims 2
- MJAVQHPPPBDYAN-UHFFFAOYSA-N 2,6-dimethylbenzene-1,4-diamine Chemical compound CC1=CC(N)=CC(C)=C1N MJAVQHPPPBDYAN-UHFFFAOYSA-N 0.000 claims 2
- 239000005700 Putrescine Substances 0.000 claims 2
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims 2
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims 2
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims 2
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 21
- 239000004417 polycarbonate Substances 0.000 abstract description 20
- 229920000515 polycarbonate Polymers 0.000 abstract description 20
- 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 abstract description 4
- OYQYHJRSHHYEIG-UHFFFAOYSA-N ethyl carbamate;urea Chemical compound NC(N)=O.CCOC(N)=O OYQYHJRSHHYEIG-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 162
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 144
- 229920003224 poly(trimethylene oxide) Polymers 0.000 description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 36
- 239000000523 sample Substances 0.000 description 32
- 239000000243 solution Substances 0.000 description 32
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 28
- 239000011541 reaction mixture Substances 0.000 description 27
- 230000004580 weight loss Effects 0.000 description 27
- 230000015572 biosynthetic process Effects 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 238000004821 distillation Methods 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- 238000001704 evaporation Methods 0.000 description 18
- 230000008020 evaporation Effects 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 17
- 229920006395 saturated elastomer Polymers 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 150000002148 esters Chemical class 0.000 description 12
- 102220479831 Voltage-dependent L-type calcium channel subunit beta-2_P55K_mutation Human genes 0.000 description 10
- 125000001931 aliphatic group Chemical group 0.000 description 10
- 125000001072 heteroaryl group Chemical group 0.000 description 10
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 9
- RYECOJGRJDOGPP-UHFFFAOYSA-N Ethylurea Chemical compound CCNC(N)=O RYECOJGRJDOGPP-UHFFFAOYSA-N 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- 102220548960 Protein Bop_P80A_mutation Human genes 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 5
- 125000004641 (C1-C12) haloalkyl group Chemical group 0.000 description 5
- 229920002396 Polyurea Polymers 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 125000006711 (C2-C12) alkynyl group Chemical group 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 125000004104 aryloxy group Chemical group 0.000 description 4
- 238000000748 compression moulding Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000005956 isoquinolyl group Chemical group 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 229920003226 polyurethane urea Polymers 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 3
- 239000007857 degradation product Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000000569 multi-angle light scattering Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 125000005493 quinolyl group Chemical group 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229920002334 Spandex Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000002399 angioplasty Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000001769 aryl amino group Chemical group 0.000 description 2
- BFAKENXZKHGIGE-UHFFFAOYSA-N bis(2,3,5,6-tetrafluoro-4-iodophenyl)diazene Chemical compound FC1=C(C(=C(C(=C1F)I)F)F)N=NC1=C(C(=C(C(=C1F)F)I)F)F BFAKENXZKHGIGE-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- ZSCYJHGJGRSPAB-UHFFFAOYSA-N carbamic acid Chemical compound NC(O)=O.NC(O)=O ZSCYJHGJGRSPAB-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 150000002373 hemiacetals Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002356 laser light scattering Methods 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- FYRHIOVKTDQVFC-UHFFFAOYSA-M potassium phthalimide Chemical compound [K+].C1=CC=C2C(=O)[N-]C(=O)C2=C1 FYRHIOVKTDQVFC-UHFFFAOYSA-M 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000002098 pyridazinyl group Chemical group 0.000 description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012858 resilient material Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000007460 surgical drainage Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 230000009897 systematic effect Effects 0.000 description 2
- 229920006250 telechelic polymer Polymers 0.000 description 2
- 125000000335 thiazolyl group Chemical group 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- IOEPOEDBBPRAEI-UHFFFAOYSA-N 1,2-dihydroisoquinoline Chemical compound C1=CC=C2CNC=CC2=C1 IOEPOEDBBPRAEI-UHFFFAOYSA-N 0.000 description 1
- IRFSXVIRXMYULF-UHFFFAOYSA-N 1,2-dihydroquinoline Chemical compound C1=CC=C2C=CCNC2=C1 IRFSXVIRXMYULF-UHFFFAOYSA-N 0.000 description 1
- DPACDTRZNMMGJZ-UHFFFAOYSA-N 1,3-diisocyano-1,3,5,5-tetramethylcyclohexane Chemical compound CC1(C)CC(C)([N+]#[C-])CC(C)([N+]#[C-])C1 DPACDTRZNMMGJZ-UHFFFAOYSA-N 0.000 description 1
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 1
- XVOZHFAFSYOEEW-LIVOIKKVSA-N 1-o-[(2r,3s,5r)-2-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl] 4-o-(2,4-dinitrophenyl) butanedioate Chemical compound C1=CC(OC)=CC=C1C(C=1C=CC(OC)=CC=1)(C=1C=CC=CC=1)OC[C@@H]1[C@@H](OC(=O)CCC(=O)OC=2C(=CC(=CC=2)[N+]([O-])=O)[N+]([O-])=O)C[C@H](N2C(NC(=O)C(C)=C2)=O)O1 XVOZHFAFSYOEEW-LIVOIKKVSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- SQOAZCPAVPASRE-UHFFFAOYSA-N 2,4,4,6-tetramethylhept-1-ene Chemical compound CC(C)CC(C)(C)CC(C)=C SQOAZCPAVPASRE-UHFFFAOYSA-N 0.000 description 1
- ISZWTVCVSJVEOL-UHFFFAOYSA-N 2,5-dimethylhex-1-ene Chemical compound CC(C)CCC(C)=C ISZWTVCVSJVEOL-UHFFFAOYSA-N 0.000 description 1
- 101000734334 Arabidopsis thaliana Protein disulfide isomerase-like 1-1 Proteins 0.000 description 1
- 101000609815 Caenorhabditis elegans Protein disulfide-isomerase 1 Proteins 0.000 description 1
- 101000609840 Caenorhabditis elegans Protein disulfide-isomerase 2 Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KDCGOANMDULRCW-UHFFFAOYSA-N Purine Natural products N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 description 1
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 description 1
- JLHADLTXDDGZFX-UHFFFAOYSA-L [[acetyloxy(dibutyl)stannyl]oxy-dibutylstannyl] acetate Chemical compound CCCC[Sn](CCCC)(OC(C)=O)O[Sn](CCCC)(CCCC)OC(C)=O JLHADLTXDDGZFX-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000005018 aryl alkenyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000002527 bicyclic carbocyclic group Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- DFFDSQBEGQFJJU-UHFFFAOYSA-N butyl hydrogen carbonate Chemical compound CCCCOC(O)=O DFFDSQBEGQFJJU-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000000000 cycloalkoxy group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 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
- 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
- 230000006866 deterioration Effects 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- JKFAIQOWCVVSKC-UHFFFAOYSA-N furazan Chemical compound C=1C=NON=1 JKFAIQOWCVVSKC-UHFFFAOYSA-N 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- HOBCFUWDNJPFHB-UHFFFAOYSA-N indolizine Chemical compound C1=CC=CN2C=CC=C21 HOBCFUWDNJPFHB-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002513 isocyanates Chemical group 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229940059936 lithium bromide Drugs 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 238000011326 mechanical measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- LCLOXRAKDJBSMN-UHFFFAOYSA-N pentyl hydrogen carbonate Chemical compound CCCCCOC(O)=O LCLOXRAKDJBSMN-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl 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
- 150000003233 pyrroles Chemical class 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical class CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
Images
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
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6204—Polymers of olefins
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/26—Mixtures of macromolecular compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
-
- 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
- A61L29/049—Mixtures of macromolecular compounds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- 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
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/08—Materials for coatings
- A61L29/085—Macromolecular materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/06—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/10—Macromolecular materials
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transplantation (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Dermatology (AREA)
- Heart & Thoracic Surgery (AREA)
- Surgery (AREA)
- Vascular Medicine (AREA)
- Polyurethanes Or Polyureas (AREA)
- Materials For Medical Uses (AREA)
- Paints Or Removers (AREA)
Abstract
一种弹性聚合物,其包含:(1)占该弹性聚合物的10%-60%重量的硬链段,其中所述硬链段包括氨基甲酸乙酯、脲或氨基甲酸乙酯脲;和(2)占该弹性聚合物的40%-90%重量的软链段。所述软链段包含:(a)占软链段的至少2%重量的至少一种聚醚大分子二醇和/或至少一种聚碳酸酯大分子二醇;和(b)占软链段的至少2%重量的至少一种聚异丁烯大分子二醇和/或二胺。
Description
相关申请
本申请要求2009年1月12日提交的美国分案申请61/204,856、2009年3月26日提交的美国分案申请61/211,310和2009年10月23日提交的美国分案申请61/279,629的权益。上述申请的全部公开内容都通过引用结合入本文。
发明背景
热塑性聚氨酯、聚脲和聚氨酯脲代表多嵌段共聚物(segmentedblock copolymer)热塑性弹性体中的重要一族。它们能够被挤塑、注塑、压塑或溶纺。它们提供了大范围的物理性质和特性,包括高拉伸和撕裂强度、耐化学和磨损性、良好的加工性以及保护屏蔽性。根据组成,即柔软弹性链段的体积分数,这些聚合物可以是柔软的、橡胶状的或者硬的和刚性的材料。聚氨酯的硬链段由二异氰酸酯和小分子二醇增链剂构成,而软链段则主要是低分子量聚合二醇。同样地,聚脲或聚氨酯脲除二异氰酸酯外,还分别包含二胺和二醇与二胺的组合。聚合二醇包括聚酯二醇、聚醚二醇和聚二烯二醇。聚酯成分易于水解降解,聚醚成分没有足够的抗氧化降解性,特别是抗体内氧化降解性,聚二烯则受困于不充分的热和氧化稳定性。
在例如起搏器、去纤颤器、血管成形术气囊、外科引流管、透析装置等与血液接触的生化医药设备的生产中,聚氨酯是最常用的材料。然而,由于聚醚软链段的氧化,聚氨酯通常展现出不足的长期体内生物稳定性,尤其在与会催化氧化分解的金属接触的情况下。这一缺陷限制了聚氨酯在长期应用方面的使用。
聚异丁烯(PIB)基热塑性聚氨酯(TPU)提供高度的热稳定性、氧化稳定性和水解稳定性,但是聚异丁烯聚氨酯的机械特性不足。
发明简述
现在发现,将聚醚二醇结合进PIB基软链段中(例如软链的10-30%重量),所生成的弹性聚合物具有显著改进的机械特性、加工性和抗氧化分解性。
在一个实施方案中,本发明是一种弹性聚合物,该聚合物包含:(1)占该弹性聚合物的10%-60%重量的硬链段,其中所述硬链段包括氨基甲酸乙酯、脲或氨基甲酸乙酯脲;和(2)占该弹性聚合物的40%-90%重量的软链段。优选所述软链段包含:(a)占软链段的至少2%重量的至少一种聚醚大分子二醇(macrodiol)和/或至少一种聚碳酸酯大分子二醇;和(b)占软链段的至少2%重量的至少一种聚异丁烯大分子二醇或二胺。优选所述弹性聚合物的数均分子量不低于约40千道尔顿。在另一实施方案中,所述弹性聚合物的数均分子量不低于约50千道尔顿。
在另一实施方案中,本发明是一种含有弹性聚合物的生产制品,所述弹性聚合物包含:(1)占该弹性聚合物的10%-60%重量的硬链段,其中所述硬链段包括氨基甲酸乙酯、脲或氨基甲酸乙酯脲;和(2)占该弹性聚合物的40%-90%重量的软链段。优选所述软链段包含:(a)占软链段的至少2%重量的至少一种聚醚大分子二醇和/或至少一种聚碳酸酯大分子二醇;和(b)占软链段的至少2%重量的至少一种聚异丁烯大分子二醇或二胺。优选所述弹性聚合物的数均分子量不低于约40千道尔顿。在另一实施方案中,所述弹性聚合物的数均分子量不低于约50千道尔顿。
在另一实施方案中,本发明是一种制备弹性聚合物的方法。该方法包括下述步骤:(a)形成一种混合物,该混合物包括至少一种聚异丁烯大分子二醇和/或二胺、至少一种聚醚大分子二醇和增链剂;和(b)使该混合物与二异氰酸酯反应,生成聚氨酯弹性聚合物。优选所述弹性聚合物包含:(i)占该弹性聚合物的10%-60%重量的硬链段,其中所述硬链段包括氨基甲酸乙酯、脲或氨基甲酸乙酯脲;和(ii)占该弹性聚合物的40%-90%重量的软链段。优选所述软链段包含:占该软链段的至少2%重量的至少一种聚醚大分子二醇和/或至少一种聚碳酸酯大分子二醇;和占该软链段的至少2%重量的至少一种聚异丁烯大分子二醇和/或二胺。优选所述弹性聚合物的数均分子量不低于约40千道尔顿。在另一实施方案中,所述弹性聚合物的数均分子量不低于约50千道尔顿。
在另一实施方案中,本发明是一种制备弹性聚合物的方法。该方法包括下述步骤:(a)使二异氰酸酯与包括至少一种聚异丁烯大分子二醇和/或二胺以及至少一种聚醚大分子二醇的混合物反应,形成具有末端反应性二异氰酸酯基的预聚物;和(b)使该预聚物与增链剂反应,得到弹性聚合物。优选所述弹性聚合物包含:(i)占该弹性聚合物的10%-60%重量的硬链段,其中所述硬链段包括氨基甲酸乙酯、脲或氨基甲酸乙酯脲;和(ii)占该弹性聚合物的40%-90%重量的软链段。优选所述软链段包含:占该软链段的至少2%重量的至少一种聚醚大分子二醇和/或至少一种聚碳酸酯大分子二醇;和占该软链段的至少2%重量的至少一种聚异丁烯大分子二醇和/或二胺。优选所述弹性聚合物的数均分子量不低于约40千道尔顿。在另一实施方案中,所述弹性聚合物的数均分子量不低于约50千道尔顿。
本发明的基于聚异丁烯的、含聚醚的热塑性聚氨酯可被用于制造弹性材料,这类弹性材料可用于生产生物医药设备例如起搏器、去纤颤器、血管成形术气囊、外科引流管、透析装置等。本发明弹性材料具有许多好处,优于此前公开的材料,包括其它聚异丁烯(PIB)基聚氨酯。特别是,如实施例部分公开的那样,将聚醚(例如聚环氧丁烷二醇,PTMO)加入到PIB基软链段中改进拉伸强度和伸长百分比。如实施例13所证实的那样,与市售对照如PellethaneTM2686-55D和2686-80A相比,含有PTMO的PIB基TPU显示出显著的氧化稳定性。体外12周(大体相当于体内10年)后,软链中具有10-20%PTMO的PIB-PTMOTPU显示6-15%重量损失,而PellethanesTM在约9周内完全分解。重量损失与PIB-PTMO TPU中的PTMO含量成直线比例。
附图说明
如附图所显示的,上述内容通过下面对本发明实施方案例的更详细描述将变得明显,附图中,类似的参考标记在所有图片中都指相同部分。这些附图不一定是依比例的,其重点是要证明本发明的实施方案。
图1是一个合成步骤实例的示意图,用于制备本发明可用的含聚异丁烯的热塑性聚氨酯。
图2是一个合成步骤实例的示意图,用于制备本发明的含聚异丁烯-聚醚的热聚氨酯。
图3是显示本发明热聚氨酯聚合物的八个样品的极限拉伸强度(UTS)的柱状图。
图4是显示本发明热聚氨酯聚合物的八个样品的断裂伸长值的柱状图。
图5是一个合成步骤实例的示意图,本发明用来制备基于PIB和PTMO链段的聚氨酯脲。
图6是本发明的60A 82PIB-PTMO聚氨酯的典型FTIR谱图。
图7是PellethaneTM P55D的FTIR谱图。
图8是本发明的各种PIB-PTMO聚氨酯的重量损失相对于时间的函数图。
图9是本发明的各种PIB-PTMO聚氨酯的12周重量损失相对于PTMO含量的函数图。
图10是本发明的各种PIB-PTMO聚氨酯的拉伸强度相对于时间的函数图,其中拉伸强度以原始未处理样品的百分数表示。
图11是本发明的PIB-PTMO聚氨酯样品“Sat 60A91”的气相渗透色谱(GPC)/折射率(RI)检测图。
图12是PellethaneTM P80A的GPC/RI图,用来与图11的“Sat60A91”的图作对照。
图13描述以300x倍放大率取得的PellethaneTM P55D的SEM图。
图14描述以300x倍放大率取得的本发明PIB-PTMO聚氨酯样品“80A73”的SEM图。
图15描述以300x倍放大率取得的本发明PIB-PTMO聚氨酯样品“80A82”的SEM图。
图16是描述以300x倍放大率取得的本发明PIB-PTMO聚氨酯样品“80A91”的SEM图。
发明详述
术语表
本文所用术语“多分散指数”(PDI)是给定聚合物样品中分子量分布的度量。计算的PDI是重均分子量除以数均分子量。
本文所用术语“大分子二醇”是指聚合二醇。例子包括下式的聚醚化合物:
HO-[CH(R)-(CH2)k-O]1-H,
(I)
和下式的聚异丁烯聚合物
式(I)和(II)中变量的值和优选值如下定义。
同样地,本文使用了短语“大分子二醇和/或二胺”,其中二胺是指结构与式(II)所示二醇相似但其中端羟基被氨基或烷基氨基替换的聚合二胺,如下定义。
本文所用术语“遥爪”,当用于聚合物时,是指带有官能化末端基的聚合物。遥爪聚合物的例子有上面给出的式(I)和(II)的二官能聚合物。遥爪聚合物可用于例如嵌段共聚物的合成。
本文所用术语“BDO”指1,4-丁二醇。
本文所用术语“MDI”指4,4’-亚甲基双(异氰酸苯酯)。
本文所用术语“PTMO”指聚环氧丁烷。
本文所用术语“PIB”指聚异丁烯,即由任选取代的丁二烯聚合形成的化合物。
本文所用术语“TPU”指热塑性聚氨酯。
本文所用术语“PIB-TPU”指通过任何已知方法得到的聚异丁烯基热塑性聚氨酯。该术语包括本文所述的弹性聚氨酯材料。
本文所用术语“PIB-PTMO-TPU”指通过任何已知方法得到的聚异丁烯基的、含聚环氧丁烷的热塑性聚氨酯,并且包括本文所述的弹性聚氨酯材料。
本文所用术语“引发剂残基”是指连接聚合物的两个线状链的二官能化合物部分。例如,在下式的聚异丁烯聚合物中,R1为引发剂残基,
其中变量的值和优选值如下定义。引发剂残基的例子分别包括用作引发剂的二枯基氯化物、甲基醚或酯的二枯基和5-叔丁基-1,3-二枯基。其它例子包括2,4,4,6-四甲基庚烯或2,5-二甲基己烯,它们在2,6-二氯-2,4,4,6-四甲基庚烷或2,5-二氯-2,5-二甲基己烷被用作引发剂时出现。在本发明领域中,许多其它阳离子型单官能和多官能引发剂都是已知的。
术语的定义
只要没有另外指出,本文所用术语“烷基”就是指式CnH2n+1的直链或支链饱和单价烃基。在一些实施方案中,n为1-18。在其它实施方案中,n为1-12。优选n为1-6。在一些实施方案中,n为1-1000,例如n为1-100。烷基可任选被-OH、-SH、卤素、氨基、氰基、硝基、C1-C12烷基、C1-C12卤代烷基、C1-C12烷氧基、C1-C12卤代烷氧基或C1-C12烷基硫基(sulfanyl)取代。在一些实施方案中,烷基可任选被一个或多个卤素、羟基、C1-C12烷基、C2-C12烯基或C2-C12炔基、C1-C12烷氧基或C1-C12卤代烷基取代。术语烷基也可指环烷基。
本文所用术语“环烷基”是指饱和环状烃,即所有环原子均为碳的化合物。在一些实施方案中,环烷基包含3-18个碳。优选环烷基包含3-6个碳。环烷基的例子包括但不局限于环丙基、环丁基、环戊基、环己基和环庚基。在一些实施方案中,环烷基可任选被一个或多个卤素、羟基、C1-C12烷基、C2-C12烯基、C2-C12炔基、C1-C12烷氧基或C1-C12卤代烷基取代。
本文所用术语“卤代烷基”包括被一个或多个F、Cl、Br或I取代的烷基,其中烷基如上定义。
本文所用术语“烷氧基”是指“烷基-O-”基,其中烷基如上定义。烷氧基的例子包括甲氧基或乙氧基。
本文所用术语“芳基”是指碳环芳基。优选芳基包含6-18个碳。芳基的例子包括但不限于苯基和萘基。芳基的例子包括被任选取代的基团,例如苯基、联苯基、萘基、菲基、蒽基、芘基、荧蒽基(fluoranthyl)或芴基。芳基可被任选取代。芳基上合适的取代基的例子包括卤素、羟基、C1-C12烷基、C2-C12烯基或C2-C12炔基、C3-C12环烷基、C1-C12卤代烷基、C1-C12烷氧基、芳氧基、芳基氨基或芳基。
本文所用术语“芳氧基”是指“芳基-O-”基,其中芳基如上定义。芳氧基的例子包括苯氧基或萘氧基。
本文所用术语“芳基胺”是指“芳基-NH-”、“芳基-N(烷基)-”或“(芳基)2-N-”基,其中芳基和烷基如上定义。
本文所用术语“杂芳基”是指含有一个或多个杂原子(O、S或N)的芳族基团。杂芳基可以是单环或多环,例如与一个或多个碳环芳基或其它单环杂芳基稠合的单环杂芳基环。本发明的杂芳基还包括被一个或多个氧代(oxo)部分取代的环系统。杂芳基的例子包括但不局限于吡啶基、哒嗪基、咪唑基、嘧啶基、吡唑基、三唑基、吡嗪基、喹啉基(quinolyl)、异喹啉基(isoquinolyl)、四唑基、呋喃基、噻吩基、异噁唑基、噻唑基、噁唑基、异噻唑基、吡咯基、喹啉基(quinolinyl)、异喹啉基(isoquinolinyl)、吲哚基、苯并咪唑基、苯并呋喃基(benzofuranyl)、邻二氮杂萘基、吲唑基、吲嗪基、酞嗪基、哒嗪基、三嗪基、异吲哚基、嘌呤基、噁二唑基、噻唑基、噻二唑基、呋咱基、苯并呋咱基、苯并噻吩基、苯并三唑基、苯并噻唑基、苯并噁唑基、喹唑啉基、喹喔啉基、1,5-二氮杂萘基、二氢喹啉基、四氢喹啉基、二氢异喹啉基、四氢异喹啉基、苯并呋喃基(benzofuryl)、呋吡啶基(fruopyridinyl)、吡咯并嘧啶基(pyrolopyrimidinyl)和吖吲哚基。
上述杂芳基可以是C-连接的或者N-连接的(当这是可能的时候)。例如,衍生自吡咯的基团可以是吡咯-1-基(N-连接的)或吡咯-3-基(C-连接的)。
杂芳基的合适的取代基如上对于芳基的定义。
烷基、环烷基的合适的取代基包括卤素、烷基、烯基、环烷基、环烯基、芳基、杂芳基、卤代烷基、氰基、硝基、卤代烷氧基。
芳基、杂芳基、烷基或环烷基中可取代碳原子上的合适取代基的进一步例子包括但不局限于-OH、卤素(-F、-Cl、-Br和-1)、-R、-OR、-CH2R、-CH2OR、-CH2CH2OR。各个R独立地为烷基。
在一些实施方案中,芳基、杂芳基或芳基烯基的芳基部分中可取代碳原子上的合适取代基包括但不局限于卤素、羟基、C1-C12烷基、C2-C12烯基或C2-C12炔基、C1-C12烷氧基、芳氧基、芳基氨基和C1-C12卤代烷基。
此外,上述基团还可以被=O、=S、=N-烷基取代。
在本发明的内容中,氨基可以是伯(-NH2)、仲(-NHRp)或叔(-NRpRq),其中Rp和Rq可以是烷基、烯基、炔基、烷氧基、环烷基、环烷氧基、芳基、杂芳基和双环碳环基团中的任何基团。二烷基氨基例如是被一个或两个烷基取代的氨基。
如上定义,三烷基氨基是基团-N+(Rt)3,其中Rt为烷基。
聚氨酯和聚脲
本文所使用的“聚氨酯”是指任何由通过氨基甲酸乙酯(氨基甲酸酯carbamate,-NH-COO-)键结合的有机单元链构成的聚合物。聚氨酯聚合物可通过使含有至少两个异氰酸酯官能团的分子与另一含有至少两个醇(羟基)基团的分子反应而形成。通过使异氰酸酯基-N=C=O与羟基-OH反应,可以制得氨基甲酸乙酯键。可以使用催化剂。同样,在聚脲中,连接键是通过使异氰酸酯基与氨基-NH2反应得到的脲基团(-NH-CO-NH-)。
例如,聚氨酯可以通过聚异氰酸酯与多元醇(其例子之一为大分子二元醇)的聚加成反应制备。该反应混合物可以包括其他添加剂。聚异氰酸酯是具有两个或多个异氰酸酯官能团的分子R1-(N=C=O)n≥2,多元醇是具有两个或多个羟基官能团的分子R2-(OH)n≥2。R1和R2分别独立为脂族或芳族部分。反应产物是含有氨基甲酸乙酯连接键的聚合物,-R1NHCOOR2-。
含有两个异氰酸酯基团的异氰酸酯被称为二异氰酸酯。异氰酸酯可以是芳族的,例如二苯甲烷二异氰酸酯(MDI)或甲苯二异氰酸酯(TDI);或者脂族的,例如己二异氰酸酯(HDI)或异佛尔酮二异氰酸酯(IPDI)。异氰酸酯的一个例子为聚二苯甲烷二异氰酸酯,其是具有2个、3个和4个或更多个异氰酸酯基的分子的掺合物,平均官能度为2.7。
含有两个羟基的多元醇被称为大分子二醇,具有三个羟基的多元醇则被称为大分子三醇。多元醇的例子包括聚碳酸酯多元醇、聚己内酯多元醇、聚丁二烯多元醇和聚硫多元醇。
使用添加剂例如催化剂、表面活性剂、发泡剂、交联剂、阻燃剂、抗光剂和填料来控制和改变反应过程以及聚合物的工作特性。
芳族异氰酸酯的例子有甲苯二异氰酸酯(TDI)和二苯甲烷二异氰酸酯(MDI)。TDI由2,4-和2,6-甲苯二异氰酸酯异构体的混合物构成。芳族二异氰酸酯的另一例子为TDI-80(TD-80),由80%2,4-异构体和20%2,6-异构体构成。
脂族(包括脂环族)异氰酸酯的例子有1,6-己二异氰酸酯(HDI)、1-异氰酸根-3-异氰酸根甲基-3,5,5-三甲基环己烷(异佛尔酮二异氰酸酯,IPDI)和4,4’-二异氰酸二环己基甲酯(H12MDI)。其它脂族异氰酸酯包括环己烷二异氰酸酯(CHDI)、四甲基二甲苯二异氰酸酯(TMXDI)和1,3-双(二异氰酸酯基甲基)环己烷(H6XDI)。
增链剂(f=2)和交联剂(f=3或3以上)是低分子量羟基和胺封端化合物,在聚氨酯纤维、弹性体、粘合剂以及某些结皮和微孔泡沫塑料的聚合物形态方面扮演着重要角色。增链剂和交联剂的例子有乙二醇(EG)、1,4-丁二醇(BDO)、二甘醇(DEG)、甘油和三羟甲基丙烷(TMP)。
聚氨酯、聚脲和聚氨酯脲的弹性体特性来自于聚合物链的“硬链段”和“软链段”区域结构的相分离。例如,包含氨基甲酸乙酯单元的硬链段可作为包含多元醇(例如大分子二醇)单元(例如聚异丁烯二醇、聚醚二醇和/或聚酯二醇)的软链段之间的交联键使用。不受限于任何具体理论,认为相分离的发生是因为占主要的非极性低熔点软链段与极性高熔点硬链段不相容。含多元醇的软链段是非固定的并且通常以蜷曲形式存在,而含异氰酸酯的硬链段(其还可包括增链剂)则是僵硬和固定的。因为硬链段与软链段共价偶联,它们抑制了聚合物链的塑性流动,由此产生了回弹性。当机械变形的时候,软链段的一部分解蜷受压,而硬链段变为在受压方向上排成一行。硬链段的该重取向以及随之发生的强烈氢键合有助于形成高的拉伸强度、伸长和抗撕裂值。
虽然聚氨酯的合成通常是经由异氰酸酯与醇反应形成的氨基甲酸乙酯(氨基甲酸酯carbamate)键而进行的,但这显得过度简化了。参见例如G.ODIAN;PRINCIPLES OF POLYMERIZATION,FOURTHED,Wiley Interscience,2004。因此,经由组分的重量百分比而非从结构方面来定义聚氨酯组成会更方便。
相应地,在一些实施方案中,本发明是一种弹性聚合物,该聚合物含有:(1)占该弹性聚合物的10%-60%重量的硬链段,其中所述硬链段包括氨基甲酸乙酯、脲或氨基甲酸乙酯脲;和(2)占该弹性聚合物的40%-90%重量的软链段。所述软链段包含占该软链段的至少2%重量的至少一种聚醚大分子二醇和/或至少一种聚碳酸酯大分子二醇,以及占该软链段的至少2%重量的至少一种聚异丁烯大分子二醇和/或二胺。
在某些实施方案中,所述弹性聚合物的数均分子量不低于约40千道尔顿(kDa)。在其它实施方案中,所述弹性聚合物的数均分子量不低于约50千道尔顿。在替代性实施方案中,所述弹性聚合物的数均分子量不低于约60kDa,不低于约70kDa,不低于约80kDa,不低于约90kDa,不低于约100kDa,不低于约110kDa,不低于约120kDa,不低于约130kDa,不低于约140kDa或不低于约150kDa。
在某些实施方案中,硬链段能以15%、20%、25%、30%、35%、40%、45%、50%或55%的量存在。
在某些实施方案中,软链段能以45%、50%、55%、60%、65%、70%、75%、80%或85%的量存在。聚醚和/或聚碳酸酯能以5%、10%、15%、20%、25%、30%、35%、40%、45%、50%、55%、60%、65%、70%、75%、80%或85%的量存在。聚异丁烯能以5%、10%、15%、20%、25%、30%、35%、40%、45%、50%、55%、60%、65%、70%、75%、80%或85%的量存在。
一种普通技术即可容易地确定合适的聚醚大分子二醇。优选至少一种聚醚大分子二醇为下式化合物
HO-[CH(R)-(CH2)k-O]l-H,
其中R在每次出现时独立为C1-C12烷基或-H;k为不小于1的整数;l为不小于1的整数。
一种普通技术即可容易地确定合适的聚异丁烯大分子二醇或二胺。优选至少一种聚异丁烯大分子二醇和/或二胺为下式化合物
其中各X独立为-OH、-NH2或-NHR4,并且其中R1为引发剂残基(如上定义)。R2、R3和R4各自独立为C1-C16烷基、C3-C16环烷基、C2-C16烯基、C3-C16环烯基、C2-C16炔基、C3-C16环炔基或C6-C18芳基,其中,R2或R3在每次出现时,独立地任选被一个或多个选自卤素(halo)、氰基、硝基、二烷基氨基、三烷基氨基、C1-C16烷氧基和C1-C16卤代烷基的基团取代。整数n和m各自独立为1-500。
优选聚异丁烯大分子二醇或二胺为羟基或氨基烯丙基遥爪聚异丁烯。在一个实施方案中,至少一种聚异丁烯大分子二醇或二胺的分子量为约400Da至约6000Da。例如,聚异丁烯大分子二醇或二胺为约500、1000、2000、3000、4000或5000Da。在某些实施方案中,至少一种聚异丁烯大分子二醇或二胺的分子量为约1000Da至约3000Da。例如,至少一种聚异丁烯大分子二醇或二胺的分子量为约1000、1500、2000或2500Da。
在优选的实施方案中,R2和R2各自独立为选自-CH2-CH=CH=CH2-、-CH2-CH2-CH2-CH2-、-CH2-CH2-CH2-和-CH2-CH(CH3)-CH2-的部分。
在一个实施方案中,本发明的弹性聚合物包含软链段,该软链段包括至少一种聚醚大分子二醇和至少一种聚碳酸酯大分子二醇,以及占该软链段的至少2%重量的至少一种聚异丁烯大分子二醇和/或二胺。
在另一实施方案中,本发明的弹性聚合物包含软链段,该软链段包括:(a)占软链段的约10%重量至约90%重量的至少一种聚异丁烯大分子二醇和/或二胺;和(b)占软链段的约10%重量至约90%重量的至少一种聚醚大分子二醇,或者占软链段的约10%重量至约90%重量的至少一种聚碳酸酯大分子二醇,或者占软链段的约10%重量至约90%重量的至少一种聚醚大分子二醇和至少一种聚碳酸酯大分子二醇。
例如,所述软链段可以包括占该软链段的约10%重量至约30%重量的至少一种聚碳酸酯大分子二醇。例如,所述软链段可以包括15%、20%或25%的量的至少一种聚碳酸酯大分子二醇。或者,所述软链段可以包括占该软链段的约10%重量至约30%重量的至少一种聚醚大分子二醇和至少一种聚碳酸酯大分子二醇。例如,所述软链段可以包括15%、20%或25%的量的至少一种聚醚大分子二醇和至少一种聚碳酸酯大分子二醇。
在一个实施方案中,所述软链段可以包括占该软链段的约10%重量至约30%重量的至少一种聚醚大分子二醇。例如,所述软链段可以包括15%、20%或25%的量的至少一种聚醚大分子二醇。
在另一个实施方案中,所述软链段可以包括占该软链段的约10%重量至约90%重量的至少一种聚异丁烯大分子二醇和/或二胺。例如,所述软链段可以包括20%、30%、40%、50%、60%、70%或80%的量的至少一种聚异丁烯大分子二醇和/或二胺。
在进一步的实施方案中,所述软链段可以包括占该软链段的约70%重量至约90%重量的至少一种聚异丁烯大分子二醇和/或二胺。例如,所述软链段可以包括70%、75%、80%或85%的量的至少一种聚异丁烯大分子二醇和/或二胺。
优选至少一种聚醚大分子二醇包括至少一种选自下列的成分:聚环氧乙烷二醇、聚氧丙烯二醇(poly(propylene oxide)diol)、聚环氧丙烷二醇(poly(trimethylene oxide)diol)、聚环氧丁烷二醇、聚环氧己烷二醇、聚环氧庚烷二醇、聚环氧辛烷二醇和聚环氧癸烷二醇。
本领域技术人员能够容易地确定合适的聚碳酸酯大分子二醇。优选所述至少一种聚碳酸酯大分子二醇包括至少一种选自下式聚碳酸亚烷基酯的化合物:
其中R7为氢、C1-C12直链或支链烷基或者C3-C12环烷基,q为大于1的整数,p为大于2的整数。优选R7为氢。聚碳酸亚烷基酯的例子包括聚碳酸亚丁酯二醇、聚碳酸亚戊酯二醇、聚碳酸亚己酯二醇或其共聚物。
在某些实施方案中,本发明的弹性聚合物包含占该弹性聚合物的约30%重量至约50%重量的硬链段。例如,所述硬链段的量可以为35%、40%或45%。
硬链段的例子包括通过使二异氰酸酯与增链剂反应形成的硬链段。本领域技术人员能够容易地确定合适的二异氰酸酯或增链剂。所述二异氰酸酯可以是至少一种选自下列的化合物:4,4’-亚甲基苯基二异氰酸酯、亚甲基二异氰酸酯、对苯二异氰酸酯、顺-环己烷-1,4-二异氰酸酯、反-环己烷-1,4-二异氰酸酯、顺-环己烷-1,4-二异氰酸酯和反-环己烷-1,4-二异氰酸酯的顺式混合物、1,6-己二异氰酸酯、2,4-甲苯二异氰酸酯、顺-2,4-甲苯二异氰酸酯、反-2,4-甲苯二异氰酸酯、顺-2,4-甲苯二异氰酸酯和反-2,4-甲苯二异氰酸酯的混合物、对四甲基二甲苯二异氰酸酯以及间四甲基二甲苯二异氰酸酯。增链剂可以是至少一种选自下列的化合物:1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,12-十二烷二醇、1,4-环己烷二甲醇、对苯二甲醇和1,4-双(2-羟基乙氧基)苯。优选二异氰酸酯为4,4’-亚甲基苯基二异氰酸酯,增链剂为1,4-丁二醇。
在优选的实施方案中,本发明的聚氨酯弹性体聚合物包含由羟基烯丙基遥爪聚异丁烯与聚环氧丁烷二醇形成的软链段和由4,4’-亚甲基二苯基二异氰酸酯与1,4-丁二醇形成的硬链段。
在另一优选方案中,本发明的聚氨酯弹性体聚合物包含衍生自羟基烯丙基遥爪聚异丁烯与聚环氧丁烷二醇的软链段和衍生自4,4’-亚甲基二苯基二异氰酸酯与1,4-丁二醇的硬链段。
在另一优选的实施方案中,本发明的聚氨酯弹性体聚合物包含由(a)羟基烯丙基二官能聚异丁烯和(b)聚环氧丁烷二醇或聚环氧己烷二醇形成的软链段,以及由(c)4,4’-亚甲基二苯基二异氰酸酯与(d)1,4-丁二醇形成的硬链段。
在某些实施方案中,本发明是一种含有任何上述聚氨酯弹性聚合物的制品。在优选的实施方案中,所述制品为医药设备或植入物。本发明所述制品的例子包括心脏起搏器、去纤颤器、导尿管、可植入假体、心脏辅助装置、人造器官、起搏器导线、去纤颤器导线、血液泵、气囊泵、V型分流器、生物传感器、用于细胞封装的膜、药物传递装置、伤口敷料、人造关节、骨科植入物或软组织替代物。在其他实施方案中,所述制品为纤维、薄膜、工程塑料、织物、涂膜和粘接性关节。
聚氨酯组合物的合成方法在聚合物化学领域通常是众所周知的。例如参见Gunter Oertel的《聚氨酯手册》第二版,Hanser出版社(1993)或者Malcolm P.Stevens的《聚合物化学》第三版,牛津大学出版社(1999)。这些出版物的相关章节通过引用被结合入本文。
本发明部分基于发现了新的改进的聚氨酯合成方法。因此,在一些实施方案中,本发明是一种制备聚氨酯弹性聚合物的方法(参见图2这种步骤的一个例子)。通常,所述方法包括下述步骤:(a)形成一种混合物,该混合物包括至少一种聚异丁烯大分子二醇和/或二胺、至少一种聚醚大分子二醇和增链剂;和(b)使该混合物与二异氰酸酯反应,生成聚氨酯弹性聚合物。优选所述弹性聚合物包含:(i)占该弹性聚合物的10%-60%重量的硬链段,其中所述硬链段包括氨基甲酸乙酯、脲或氨基甲酸乙酯脲;和(ii)占该弹性聚合物的40%-90%重量的软链段。优选所述软链段包含:占该软链段的至少2%重量的至少一种聚醚大分子二醇和/或至少一种聚碳酸酯大分子二醇;和占该软链段的至少2%重量的至少一种聚异丁烯大分子二醇和/或二胺。
任何一种或多种异氰酸酯、多元醇、增链剂或各种添加剂都可用于本发明的合成方法。例如,如上所述的聚醚大分子二醇和/或聚异丁烯大分子二醇及其混合物都可用于上述方法。可以使用任何量的上述成分及其组合。
在本发明的方法中,优选在约45℃至约120℃的温度形成所述混合物。例如,在约50、60、70、80、90、100或110℃的温度形成所述混合物。
在一些实施方案中,在催化剂例如辛酸亚锡的存在下形成所述混合物。其它催化剂在本发明领域是众所周知的,本领域技术人员都会使用。
在一个备选实施方案中,本发明是一种制备弹性聚合物的方法,包括下述步骤:(a)使二异氰酸酯与包括至少一种聚异丁烯大分子二醇和/或二胺以及至少一种聚醚大分子二醇的混合物反应,形成具有末端反应性二异氰酸酯基的预聚物;和(b)使该预聚物与增链剂反应,得到聚氨酯弹性聚合物。优选所述弹性聚合物包含:(i)占该弹性聚合物的10%-60%重量的硬链段,其中所述硬链段包括氨基甲酸乙酯、脲或氨基甲酸乙酯脲;和(ii)占该弹性聚合物的40%-90%重量的软链段。优选所述软链段包含:占该软链段的至少2%重量的至少一种聚醚大分子二醇和/或至少一种聚碳酸酯大分子二醇;和占该软链段的至少2%重量的至少一种聚异丁烯大分子二醇和/或二胺。
任何一种或多种异氰酸酯、多元醇、增链剂或各种添加剂都可用于本发明的合成方法。例如,如上所述的聚醚大分子二醇和/或聚异丁烯大分子二醇及其混合物都可用于上述方法。可以使用任何量的上述成分及其组合。
例如,上述方法所采用的至少一种聚醚大分子二醇为聚环氧乙烷二醇、聚氧丙烯二醇(poly(propylene oxide)diol)、聚环氧丙烷二醇(poly(trimethylene oxide)diol)、聚环氧丁烷二醇、聚环氧己烷二醇、聚环氧庚烷二醇、聚环氧辛烷二醇或聚环氧癸烷二醇。
优选上述方法所采用的至少一种聚碳酸酯大分子二醇为如上所述的聚碳酸亚烷基酯。
可用于上述方法的增链剂的例子为1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,12-十二烷二醇、1,4-环己烷二甲醇、对苯二甲醇和1,4-双(2-羟基乙氧基)苯。其他例子包括二胺增链剂。
实施例
材料
以收货状态使用Sn(Oct)2(辛酸亚锡,Polyscience)、4,4’-亚甲基双(异氰酸苯酯)(MDI,Aldrich,98%)、甲苯(Aldrich,99%)、氯仿(Aldrich,至少99.8%)、1,4-丁二醇(BDO,Aldrich,99%)、邻苯二甲酰亚胺,钾(Aldrich,98%)、LiBr(溴化锂试剂Aldrich,至少99%)、KOH(氢氧化钾,Aldrich)、Na2SO4(硫酸钠,Aldrich)、三氟乙酸(TFA,Aldrich),溴化四正丁基铵(TBAB,Alfa Aesar,至少98%)和聚环氧丁烷(PTMO,1000聚醚二醇,Aldrich)。在使用之前,将四氢呋喃(THF)或甲苯在金属钠和二苯酮上回流过夜,并在氮气氛下蒸馏。通过在硫酸上回流24小时纯化己烷。将它们用KOH水溶液洗涤三遍,然后用蒸馏水洗涤。然后,将它们在硫酸钠上于室温储存过夜。最后,在使用前,将它们在氮气氛下在CaH2上蒸馏。
测量
用Waters HPLC系统测量分子量,所述Waters HPLC系统装配有510型HPLC泵、410型差示折光剂、441型吸光度检测仪、在线多角激光光散射(MALLS)检测仪(MiniDawn,Wyatt Technology Inc.)、712型样品处理机和五个分别与以下系列相连的Ultrastyragel GPC柱:500、103、104、105和使用THF∶TBAB(98∶2,wt%)作为载体溶剂,流速为1mL/min。在室温(25℃)、大气条件下,用50N测力传感器,在Instron Model 4400R上以50mm/min伸长率,测量静态拉伸特性(杨氏模量、极限拉伸强度(本文缩写为“UTS”),伸长)。所有测试均按照ASTM D412进行。样品用ASTM模切成哑铃形。所有样品测试前均保持在室温和大气气氛下。用17000psi在160℃压塑聚合物。
实施例1:HO-烯丙基-聚异丁烯(PIB)-烯丙基-OH
通过将溴烯丙基遥爪PIB的THF溶液与KOH的水溶液一起在130℃加热3小时,实施HO-烯丙基-PIB-烯丙基-OH的合成。
例如,将Br-烯丙基-PIB-烯丙基-Br(Mn=2200,50g,0.023mol)溶解于无水THF(1升)中,向其中加入KOH(50g,0.9mol)的蒸馏水(500mL)溶液。将该混合物在反应器中于130℃加热3小时。将反应冷却至室温。使用旋转式汽化器蒸发THF。加入蒸馏甲醇(500mL),使沉淀物沉降。再将该沉淀物溶解于己烷(200mL),并慢慢加入到甲醇(600mL)中。使粘块沉淀。重复该过程两次,并将纯化聚合物最后在室温、真空下干燥24小时。收率:99%,GPC-MALLS∶Mn=2400,多分散指数(PDI)=1.16。
羟基遥爪PIB的代表性分子量数据列于下表1中。
表1:羟基烯丙基遥爪PIB的分子量数据
聚合物 | Mn(NMR) | Mn(GPC) | PDI |
1 | 4200 | 4300 | 1.10 |
2 | 2200 | 2400 | 1.16 |
3 | 1500 | 1600 | 1.17 |
实施例2:聚异丁烯基热塑性聚氨酯(PIB-TPU)的合成
实施例2中所用术语“一步法”和“两步法”指图1中示例的合成方案。
通过使用MDI和BDO作为增链剂,在1%mol辛酸亚锡(相对于MDI)存在下,在甲苯中于80℃实施聚氨酯(PU)的合成,该聚氨酯的软链段(SS)与硬链段(HS)之比为80∶20(wt∶wt),即PIB(4200)-TPU(样品编号PIB-TPU-4321)、PIB(2200)-TPU(样品编号PIB-TPU-2211)和PIB(1500)-TPU(样品编号PIB-TPU-1514)。
一步法
例如,如下合成材料PIB-TPU-2211。从无水甲苯(10mL)中共沸蒸馏HO-烯丙基-PIB-烯丙基-OH(Mn=2200,5.2g,2.36mmol)和BDO(212mg,2.36mmol)。将该混合物在45℃、真空下保持3小时。向该混合物中加入25mL无水甲苯,然后加入Sn(Oct)2(20mg,0.05mmol)的甲苯溶液。在干燥氮气的缓慢气流下,于80℃加热该混合物。将MDI(1.24g,4.96mmol)加入该混合物中,并将该混合物剧烈搅拌6小时。将该混合物冷却至室温,倒入模具中,在室温、空气中蒸发溶剂48小时。最后,在真空下、50℃将聚合物干燥12小时。反应物的代表性摩尔比和TPU的肖氏硬度列于下表2中。
表2:反应物的摩尔比和PIB TPU的肖氏硬度
1前体HO-烯丙基-PIB-烯丙基-OH的Mn
经过各种聚合时间后PIB-TPU-2211的Mn记载于表3中。直至6小时的时间观察到Mn的增加。聚氨酯在室温凝聚一周。对凝聚的样品观察到Mn=105000,PDI=2.4的进一步增加。
表3:聚合时间与相应的Mn数据
聚合时间(h) | Mn(GPC) | PDI(GPC) |
01 | 2200 | 1.16 |
0.5 | 23000 | 1.8 |
0.7 | 32000 | 1.8 |
3 | 66000 | 2.0 |
6 | 87000 | 2.2 |
168 | 105000 | 2.4 |
1前体HO-烯丙基-PIB-烯丙基-OH的Mn
表4中归纳了使用不同分子量的聚异丁烯制备而成的肖氏硬度为约60A硬度的PIB-TPU的Mn。由于PIB-TPU-1514不溶于THF∶TBAB(98∶2wt%)中,所以无法测定Mn。
表4:PIB-TPU(肖氏硬度60A)的GPC数据
编号 | Mn(GPC) | PDI(GPC) |
PIB-TPU-4321 | 110000 | 2.3 |
PIB-TPU-2211 | 92000 | 3.1 |
PIB-TPU-1321 | - | - |
通过一步合成法(参见图1),使用MDI和BDO作为增链剂,使用1%mol辛酸亚锡(相对于MDI)作为催化剂,在甲苯中于80℃实施聚氨酯的合成,该聚氨酯的软链段(SS)与硬链段(HS)之比为60∶40(wt%),例如PIB(4200)-TPU(样品编号PIB-TPU-4761)、PIB(2200)-TPU(样品编号PIB-TPU-2431)和PIB(1500)-TPU(样品编号PIB-TPU-1321)。
例如,如下合成材料PIB-TPU-2431。从无水甲苯(10mL)中共沸蒸馏HO-烯丙基-PIB-烯丙基-OH(Mn=2200,5.2g,2.36mmol)和BDO(637mg,7.08mmol)。将该混合物在45℃、真空下保持3小时。向该混合物中加入25mL无水甲苯,然后加入Sn(Oct)2(38mg,0.09mmol)的甲苯溶液。在干燥氮气的缓慢气流下,于80℃加热该混合物。将MDI(2.36g,9.44mmol)加入该混合物中,并将该混合物剧烈搅拌6小时。将该混合物冷却至室温,倒入模具中,在室温、空气中蒸发溶剂48小时。最后,在真空下、50℃将聚合物干燥12小时。
反应物的代表性摩尔比和TPU的肖氏硬度列于下表5中。
表5:反应物的摩尔比和PIB TPU的肖氏硬度
在THF∶TBAB(98∶2wt%)中实施TPU的GPC分析。所得分子量值(表6)在83000-91000范围内,PDI在1.8-2.2范围内。
表6:PIB-TPU(肖氏硬度80A)的GPC数据
编号 | Mn(GPC) | PDI(GPC) |
PIB-TPU-4761 | 87000 | 2.0 |
PIB-TPU-2431 | 91000 | 2.2 |
PIB-TPU-1321 | 83000 | 1.8 |
PIB-TPU的典型机械特性数据列于表7中。所得UTS在6-9MPa范围内,断裂伸长在40-400%范围内。随着硬链段与软链段之比的增加,杨氏模量增加,而断裂伸长降低。具有较高肖氏硬度的TPU的热加工比较软的TPU更难。由于PIB-TPU-2431和PIB-TPU-1321不能被模塑成平板,所以拉伸特性没有记录。
表7:PIB-TPU的机械特性数据
将聚合反应的催化剂由辛酸锡换成1,3-双乙酸基-1,1,3,3-四丁基二锡氧烷(DTDS),PIB-TPU-2211的UTS由9MPa增加至12MPa,断裂伸长从350%降至100%,如表8所示。
表8:PIB TPU 的机械特性数据
两步合成
在随后的实验中,聚氨酯合成技术被修改成加入1,4-丁二醇(BDO)作为最后的反应试剂。该过程由两步骤组成。(参见图1)第一步,将HO-烯丙基-PIB-烯丙基-OH与过量MDI混合,形成中间体PU。在随后的步骤中,使用1,4-丁二醇使这些中间体聚氨酯链增长,得到高分子量TPU。下面给出了具有代表性的工艺过程。
采用两步法,通过最后加入BDO,合成PIB-TPU-4321。从无水甲苯(10mL)中共沸蒸馏HO-烯丙基-PIB-烯丙基-OH(Mn=4200,5.2g,1.24mmol)。将该混合物在45℃、真空下保持3小时。向该混合物中加入25mL无水甲苯,然后加入Sn(Oct)2(15mg,0.037mmol)的甲苯溶液。在干燥氮气的缓慢气流下,于80℃加热该混合物。向其中加入MDI(930mg,3.72mmol),并将该混合物剧烈搅拌30分钟。将BDO(223mg,2,48mmol)加入该混合物中,并持续搅拌4小时。将该混合物冷却至室温,倒入模具中,在室温、空气中蒸发溶剂48小时。最后,在真空下、50℃将聚合物干燥12小时。
由表9可见,与通过一步法合成的聚合物相比,通过两步法合成得到的聚合物具有较高的分子量和窄的分子量分布。而两种情况的拉伸特性是相似的。加工则比通过一步法合成的相同TPU更容易。
表9:在不同条件下合成的PIB-TPU-4321的Mn和拉伸特性数据
步骤 | Mn(GPC) | PDI(GPC) | UTS(MPa) | 断裂伸长(%) |
一步 | 110000 | 2.3 | 7 | 200 |
两步 | 119000 | 1.6 | 7 | 150 |
实施例3:聚异丁烯/聚醚基热塑性氨基甲酸乙酯(PIB-PTMO-TPU)的
合成
按照图2例示的合成步骤,采用两步法合成TPU,该TPU具有不同比例的PIB和PTMO混合物作为软链段。BDO和MDI构成硬链段。在所有情况下,软链段与硬链段之比都保持在80∶20wt%。
例如,如下合成PIB-PTMO-82-6。从无水甲苯(10mL)中共沸蒸馏HO-烯丙基-PIB-烯丙基-OH(Mn=2200,5.2g,2.36mmol)和PTMO(Mn=1000,1.3g,1.3mmol)。将该混合物在45℃、真空下保持3小时。向该混合物中加入25mL无水甲苯,然后加入Sn(Oct)2(28.3mg,0.07mmol)的甲苯溶液。在干燥氮气的缓慢气流下,于80℃加热该混合物。将MDI(1.76g,7.02mmol)加入该混合物中,并将该混合物剧烈搅拌30分钟。向所得反应混合物中加入BDO(302mg,3.36mmol),并将该混合物在100℃搅拌4小时。将该混合物冷却至室温,倒入模具中,并在室温、空气中蒸发溶剂48小时。最后,在真空下、50℃将聚合物干燥12小时。
样品编号和PIB与PTMO的重量百分比数值列于表10中。
表10:PIB-PTMO TPU中的PIB与PTMO重量百分比数值
(肖氏硬度60A)
1HO-PIB-OH,Mn=2200,2HO-PTMO-OH,Mn=1000,3软∶硬=79∶21wt%TPU的GPC-RI示踪(traces)显示分子量的单模式(monomodal)分布,分子量值则在55000-140000范围内,PDI约为1.4-2.7。根据上述方法合成的TPU的分子量数据列于表11中。
表11:PIB-PTMO TPU(肖氏硬度≈60A)的分子量数据
编号 | Mn(GPC) | PDI(GPC) |
PIB-PTMO-91-6 | 94000 | 2.1 |
PIB-PTMO-82-6 | 129000 | 2.2 |
PIB-PTMO-73-6 | 137000 | 2.7 |
PIB-PTMO-64-6 | 95000 | 2.2 |
PIB-PTMO-55-6 | 85000 | 1.4 |
PIB-PTMO-28-6 | 55000 | 1.6 |
PTMO-60A | 33000 | 1.3 |
PIB-PTMO TPU的极限拉伸强度(UTS)约为4-20MPa,断裂伸长在400-740%范围内。聚合物的杨氏模量则在2-9MPa范围内。TPU的肖氏硬度和拉伸特性数据列于下表12中。
表12:PIB-PTMO TPU的肖氏硬度和拉伸特性数据
加入少量聚环氧丁烷二醇(PTMO),使聚合物的机械特性得到了显著提高。但是,即使进一步加入PTMO成分,该特性仍将保持大致近似。具有100%PTMO(PTMO-60A)的TPU也显示出相似的拉伸特性。
采用下述的两步法,合成具有更高硬链段与软链段之比的PIB-PTMO TPU。所有情况下都保持软链段与硬链段之比(SS∶HS)为65∶35%重量,同时改变PIB与PTMO之比(占软链段的重量百分比)。结果列于表13中。
表13:PIB与PTMO在PIB-PTMO TPU中的重量百分比
(肖氏硬度80A)
1HO-PIB-OH,Mn=2200,2HO-PTMO-OH,Mn=1000,3SS∶HS=65∶35wt%PIB-PTMO TPU的示例性合成
如下合成PIB-PTMO-82-8。从无水甲苯(10mL)中共沸蒸馏HO-烯丙基-PIB-烯丙基-OH(Mn=2200,5.2g,2.36mmol)和PTMO(Mn=1000,1.3g,1.3mmol)。将该混合物在45℃、真空下保持3小时。向该混合物中加入25mL无水甲苯,然后加入Sn(Oct)2(42mg,0.104mmol)的甲苯溶液。在干燥氮气的缓慢气流下,于80℃加热该混合物。将MDI(2.6g,10.38mmol)加入反应混合物中,并将该混合物剧烈搅拌30分钟。向反应混合物中加入BDO(605mg,6.72mmol),并将该混合物在100℃搅拌4小时。将该混合物冷却至室温,倒入模具中,并在室温、空气中蒸发溶剂48小时。最后,在真空下、50℃将聚合物干燥12小时。
肖氏硬度为80A的PIB-PTMO TPU的分子量数据列于表14中。聚合物的分子量在42000-138000范围内,PDI为1.9-3.8。
表14:PIB-PTMO TPU(肖氏硬度80A)的分子量数据
编号 | Mn(GPC) | PDI |
PIB-PTMO-91-8 | 84000 | 1.9 |
PIB-PTMO-82-8 | 119000 | 2.8 |
PIB-PTMO-73-8 | 138000 | 3.5 |
PIB-PTMO-64-8 | 130000 | 3.7 |
PIB-PTMO-28-8 | 40000 | 3.8 |
PTMO-80A | 42000 | 2.4 |
PIB-PTMO TPU(肖氏硬度80A)的极限拉伸强度(UTS)在18-25MPa范围内,断裂伸长在150-550%范围内。聚合物的杨氏模量则在11-32MPa范围内变化,高于具有较低肖氏硬度(60A)的PIB-PTMO TPU。随着PTMO浓度的增加,TPU的UTS和断裂伸长呈线性增加。含有PTMO-80A的PIB-PTMO TPU显示出最高的UTS和断裂伸长。TPU的肖氏硬度和拉伸特性数据列于下表15中。
表15:PIB-PTMO TPU的肖氏硬度和拉伸特性数据
(肖氏硬度80A)
在120℃实施的PIB-PTMO TPU的示例性合成
根据图2例示的合成方案,合成PTMO组分中的软链段不低于80%重量的PIB-PTMO TPU。改变软链段与硬链段之比(SS∶HS),以使肖氏硬度值达到60A-80A。
例如,如下合成PIB-PTMO-28-8。从无水甲苯(10mL)中共沸蒸馏HO-烯丙基-PIB-烯丙基-OH(Mn=2200,1.12g,0.51mmol)和PTMO(Mn=1000,4.48g,4.48mmol)。将该混合物在45℃、真空下保持3小时。向反应混合物中加入25mL无水甲苯,然后加入Sn(Oct)2(44.6mg,0.11mmol)的甲苯溶液。在干燥氮气的缓慢气流下,于80℃加热该混合物。将MDI(2.67g,10.7mmol)加入反应混合物中,并将该混合物剧烈搅拌30分钟。向反应混合物中加入BDO(520mg,5.7mmol),并将温度升至120℃。15分钟后,将温度降至100℃,并将该混合物在氮气下保持4小时。将该混合物冷却至室温,倒入模具中,并在室温、空气中蒸发溶剂48小时。最后,在真空下、50℃将聚合物干燥12小时。
下表16中给出了TPU的GPC数据,该TPU中的PTMO超过软链段的80%重量。与由相同起始原料但在100℃温度合成的聚合物(表11和14)相比,这些TPU的分子量值增加。
表16:PIB-PTMO TPU的分子量数据,
软链段包括不少于80%重量的PTMO(反应温度=120℃)
编号 | Mn(GPC) | PDI |
PIB-PTMO-28-6 | 105000 | 2.3 |
PTMO-60A | 113000 | 2.0 |
PIB-PTMO-28-8 | 87000 | 1.8 |
PTMO-80A | 102000 | 1.7 |
TPU的UTS、极限断裂伸长和杨氏模量数据列于下表17中。当将反应温度提高至120℃而改变合成过程后,PTMO-60A的UTS(与表12相比)由10MPa增加至20MPa。还观察到极限断裂伸长增加了200%。如表17所示,其它TPU也显示出得到提高的拉伸特性。先前已经描述了在100℃合成的PIB-PTMO-28-6(参见表12)和PIB-PTMO-28-8(参见表15)的拉伸数据。
表17:PIB-PTMO TPU的拉伸特性,软链段包括不少于80%重量的PTMO(反应温度=120℃)
PIB-PTMO-TPU的合成(肖氏硬度约95A)
采用上述两步法,合成肖氏硬度设计为约95A的PIB-PTMO TPU。所有情况下均保持软链段与硬链段之比(SS∶HS)为60∶40w∶w,同时如表18所示改变PIB与PTMO的重量比。
表18:PIB与PTMO在PIB-PTMO TPU中的重量百分比
(肖氏硬度95A)
1HO-PIB-OH,Mn=2200,2HO-PTMO-OH,Mn=1000,3SS∶HS=60∶40wt%
例如,如下合成PIB-PTMO-73-9。从无水甲苯(10mL)中共沸蒸馏HO-烯丙基-PIB-烯丙基-OH(Mn=2200,3.92g,1.78mmol)和PTMO(Mn=1000,1.68g,1.68mmol)。将该混合物在45℃、真空下保持3小时。向反应混合物中加入25mL无水甲苯,然后加入Sn(Oct)2(49mg,0.121mmol)的甲苯溶液。在干燥氮气的缓慢气流下,于80℃加热该混合物。将MDI(3.03g,12.12mmol)加入反应混合物中,并将该混合物剧烈搅拌30分钟。向反应混合物中加入BDO(780mg,8.66mmol),并将该混合物在100℃搅拌4小时。将该混合物冷却至室温,倒入模具中,并在室温、空气中蒸发溶剂48小时。最后,在真空下、50℃将聚合物干燥12小时。
肖氏硬度为95A的PIB-PTMO TPU的分子量数据列于表19中。聚合物的分子量在79000-111500范围内,PDI为1.6-3.4。
表19:PIB-PTMO TPU(肖氏硬度95A)的分子量数据
编号 | Mn(GPC) | PDI(GPC) |
PIB-PTMO-91-9* | - | - |
PIB-PTMO-82-9 | 87000 | 3.4 |
PIB-PTMO-73-9 | 79000 | 1.6 |
PIB-PTMO-64-9 | 105000 | 2.5 |
PIB-PTMO-55-9 | 111500 | 2.8 |
*TPU微溶于THF/TBAB混合物中
PIB-PTMO TPU(肖氏硬度95A)的UTS、肖氏硬度、撕裂强度和杨氏模量列于表20中。观测到聚合物的UTS和杨氏模量分别在14-42MPa和144-17MPa范围内。观测到断裂伸长在30-510%范围内。与PIB/PTMO之比同样为70/30重量的TPU,例如肖氏硬度为60A(PIB-PTMO-73-6)的PIB-PTMO-6和肖氏硬度为80A(PIB-PTMO-73-8)的PIB-PTMO-8TPU相比,PIB-PTMO-73-9具有更高的UTS和杨氏模量。
表20:PIB-PTMO-TPU的拉伸特性(肖氏硬度≈95A)
实施例4:聚异丁烯/聚碳酸亚烷基酯-基热塑性氨基甲酸乙酯
(PIB-PHMC-TPU)的合成
采用与图2例示的方案近似的方法,合成具有PIB与聚碳酸亚己基酯(PHMC)的混合物的TPU,其中PIB与聚碳酸亚己基酯之比按占软链段的重量百分比计为70∶30。硬链段包含BDO和MDI。硬链段与软链段之比HS∶SS按重量百分比计为21∶79。
下面给出PIB-PHMC-73-6的合成过程。如下合成PIB-PHMC-73-6。从无水甲苯(10mL)中共沸蒸馏HO-烯丙基-PIB-烯丙基-OH(Mn=2200,4.5g,2.04mmol)和PHMC(Mn=860,1.93g,2.27mmol)。将反应混合物在45℃、真空下保持3小时。向反应混合物中加入25mL无水甲苯,然后加入Sn(Oct)2(26.3mg,0.065mmol)的甲苯溶液。在干燥氮气的缓慢气流下,于80℃加热该反应混合物。将MDI(1.63g,6.51mmol)加入反应混合物中,并将该混合物剧烈搅拌30分钟。向反应混合物中加入BDO(200mg,2.2mmol),并将该混合物在100℃搅拌4小时。将反应混合物冷却至室温,倒入模具中,并在室温、空气中蒸发溶剂48小时。最后,在真空下、50℃将聚合物干燥12小时。
PIB-PHMC-73-6的极限拉伸强度(UTS)为10MPa,断裂伸长为约300%。聚合物的杨氏模量为10MPa,肖氏硬度(A)为约61A。
实施例5:含有聚异丁烯-二胺的弹性聚合物(H
2
N-烯丙基-PIB-烯丙基
-NH
2
)的制备
将氯烯丙基遥爪PIB与邻苯二甲酰亚胺钾的THF∶DMF(70∶30v∶v)溶液在回流条件下加热18小时,然后在NH2NH2·H2O存在下水解,由此实施H 2 N-烯丙基-PIB-烯丙基-NH 2 的合成。
例如,如下合成邻苯二甲酰亚胺-烯丙基-PIB-烯丙基-邻苯二甲酰亚胺。将C1-烯丙基-PIB-烯丙基-C1(Mn=2100,10g,0.0048mol)溶于无水THF(300mL)和无水DMF(100mL)中,然后加入邻苯二甲酰亚胺钾(50g,0.27mol),并将该混合物在干燥氮气氛回流18小时。将反应混合物冷却至室温,过滤并蒸发THF。向剩下的粘块加入甲醇,分离沉淀并将其溶于己烷中。使该溶液在甲醇中再沉淀。通过用己烷和甲醇进行溶解和再沉淀,将所得产物一步纯化。
H2N-烯丙基-PIB-烯丙基-NH2的典型合成过程如下所述。将邻苯二甲酰亚胺-烯丙基-PIB-烯丙基-邻苯二甲酰亚胺(9g,0.0042mol)溶于THF(200mL)中,并加入水合肼(15g)。将该混合物回流24小时。停止反应并冷却至室温。加入KOH溶液(10g,于25mL水中)并搅拌30分钟。在减压下蒸发THF,加入甲醇。将所得沉淀通过溶解于己烷,在甲醇中再沉淀进行纯化。收率:98%,NMR∶Mn=2100。
实施例6:聚异丁烯/聚环氧丁烷酯-基热塑性氨基甲酸乙酯
(PIB-PTMO-TPUU)的合成
如图3例示,通过具有BDO和MDI的H2N-烯丙基-PIB-烯丙基-NH2和HO-PTMO-OH的链延长,合成具有设定肖氏硬度80A的一系列PIB基聚氨酯。如表21所示,改变PIB∶PTMO的比例,但将SS∶HSw∶w之比保持在65∶35。合成路线如图5中所图示。
表21:PIB和PTMO在PIB-PTMO TPUU中的重量百分比
(肖氏硬度80A)
1H2N-PIB-NH2(Mn)=2100,2HO-PTMO-OH(Mn)=1000
PIB-PTMO-TPUU的示例性合成
如下合成PIB-TPUU-82-8。从无水甲苯(10mL)中共沸蒸馏H2N-烯丙基-PIB-烯丙基-NH2(Mn=2100,5.2g,2.36mmol)和PTMO(Mn=1000,1.3g,1.3mmol)。将该混合物在45℃、真空下保持3小时。向该混合物中加入25mL无水甲苯,然后加入Sn(Oct)2(42mg,0.104mmol)的甲苯溶液。在干燥氮气的缓慢气流下,于80℃加热该混合物。将MDI(2.6g,10.38mmol)加入反应混合物中,并将该混合物剧烈搅拌30分钟。向反应混合物中加入BDO(605mg,6.72mmol),并将该混合物在100℃搅拌4小时。将该混合物冷却至室温,倒入模具中,并在室温、空气中蒸发溶剂48小时。最后,在真空下、50℃将聚合物干燥12小时。
肖氏硬度为80A的PIB-PTMO TPUU的分子量数据列于表22中。聚合物的分子量在98700-119000范围内,PDI为1.6-2.8。
表22:PIB-PTMO TPUU(肖氏硬度80A)的分子量数据
编号 | Mn(GPC) | PDI(GPC) |
PIB-TPUU-82-8 | 104000 | 1.8 |
PIB-TPUU-73-8 | 98700 | 2.5 |
PIB-TPUU-64-8 | 106500 | 2.8 |
PIB-TPUU-19-8 | 119000 | 1.6 |
PIB-PTMO TPUU的UTS、肖氏硬度、撕裂强度和杨氏模量数据列于表23中。观测到聚合物的UTS在23-32MPa范围内,杨氏模量在5-50MPa范围内变化。观测到断裂伸长在250-675%范围内。
表23:PIB-PTMO-TPUU的拉伸特性(肖氏硬度≈80A)
实施例4:选定样品TPU的机械测量
如上测量八个样品的极限拉伸强度(UTS)和断裂伸长。
A,PIB-TPU-2221(不于表7),
B,PIB-PTMO-91-6(不于表12),
C,PIB-PTMO-82-6(不于表12),
D,PIB-PTMO-73-6(不于表12),
E,PIB-PTMO-64-6(不于表12),
F,PIB-PTMO-55-6(不于表12),
G,PIB-PTMO-28-6(示于表12),和
H,PTMO-60A(示于表17)。
按照上述实施例3描述的过程合成这些样品。这些样品的PTMO即聚醚二醇含量不同。
结果显示在图3和图4中。可以看出,与样品A相比,加入PTMO提高了PIB-基TPU的机械特性。而且,与不含任何PIB的样品H相比,基于PIB大分子二醇与聚醚大分子二醇的组合的TPU其机械特性优于单独基于PIB大分子二醇或者聚醚大分子二醇的TPU。
实施例7:聚异丁烯/聚醚基热塑性氨基甲酸乙酯(PIB-PTMO-TPU,50A
肖氏硬度)的合成
按照图2例示的合成步骤,采用两步法合成TPU,该TPU具有重量比为80∶20的PIB与PTMO的混合物作为软链段。BDO和MDI构成硬链段。软链段与硬链段之比保持在82∶18wt%。
例如,如下合成PIB-PTMO-82-5。通过从无水甲苯(10mL)溶液中共沸蒸馏,干燥HO-烯丙基-PIB-烯丙基-OH(Mn=2250,5.0g,2.2mmol)和PTMO(Mn=1000,1.25g,1.25mmol)。将该混合物在45℃、真空下保持3小时。向该混合物中加入25mL无水甲苯,然后加入Sn(Oct)2(20.3mg,0.05mmol)的甲苯溶液。在干燥氮气的缓慢气流下,于80℃加热该混合物。将MDI(1.32g,5.3mmol)加入该混合物中,并将该混合物剧烈搅拌30分钟。向反应混合物中加入BDO(170mg,1.87mmol),并将该混合物在100℃搅拌4小时。将该混合物冷却至室温,倒入模具中,并在室温、空气中蒸发溶剂48小时。最后,在真空下、50℃将聚合物干燥12小时。
该TPU显示出下列特性:Mn=75000,PDI=1.7,UTS=14MPa,断裂伸长=800%,杨氏模量=3MPa,弯曲模量=11MPa,撕裂强度=292pli。
实施例8:聚异丁烯/聚醚基热塑性氨基甲酸乙酯(PIB-PTMO-TPU,肖
氏硬度55A)的合成
按照图2例示的合成步骤,采用两步法合成TPU,该TPU具有重量比为80∶20的PIB与PTMO的混合物作为软链段。BDO和MDI构成硬链段。软链段与硬链段之比保持在81∶19wt%。
例如,如下合成PIB-PTMO-82-5.5。通过从无水甲苯(10mL)溶液中共沸蒸馏,干燥HO-烯丙基-PIB-烯丙基-OH(Mn=2250,5.4g,2.4mmol)和PTMO(Mn=1000,1.35g,1.35mmol)。将该混合物在45℃、真空下保持3小时。向该混合物中加入25mL无水甲苯,然后加入Sn(Oct)2(25.9mg,0.06mmol)的甲苯溶液。在干燥氮气的缓慢气流下,于80℃加热该混合物。将MDI(1.55g,6.21mmol)加入该混合物中,并将该混合物剧烈搅拌30分钟。向所得反应混合物中加入BDO(223mg,2.46mmol),并将该混合物在100℃搅拌4小时。将该混合物冷却至室温,倒入模具中,并在室温、空气中蒸发溶剂48小时。最后,在真空下、50℃将聚合物干燥12小时。
该TPU显示出下列特性:Mn=105000,PDI=2.0,UTS=13MPa,断裂伸长=900%,杨氏模量=3.6MPa,撕裂强度=295pli。
实施例9:(饱和)聚异丁烯/聚醚基热塑性氨基甲酸乙酯(PIB
饱和
-PTMO-TPU,肖氏硬度60A)的合成
按照图2例示的合成步骤,采用两步法合成TPU,该TPU具有不同重量比的羟基丙基遥爪PIB与PTMO的混合物作为软链段。BDO和MDI构成硬链段。软链段与硬链段之比保持在77∶23wt%。
例如,如下合成PIB饱和-PTMO-82-6。通过从无水甲苯(10mL)溶液中共沸蒸馏,干燥HO-丙基-PIB-丙基-OH(Mn=2000,5.3g,2.65mmol)和PTMO(Mn=1000,1.33g,1.33mmol),其中所述HO-丙基-PIB-丙基-OH(Mn=2000,5.3g,2.65mmol)是通过烯丙基遥爪PIB的硼氢化氧化得到的(Iván,B.;Kennedy,J.P.J.Polym.Sci.,Part A:Polym.Chem.1990,28,89)。将该混合物在45℃、真空下保持3小时。向该混合物中加入25mL无水甲苯,然后加入Sn(Oct)2(29.9mg,0.074mmol)的甲苯溶液。在干燥氮气的缓慢气流下,于80℃加热该混合物。将MDI(1.84g,7.36mmol)加入该混合物中,并将该混合物剧烈搅拌30分钟。向所得反应混合物中加入BDO(308mg,3.38mmol),并将该混合物在100℃搅拌4小时。将该混合物冷却至室温,倒入模具中,并在室温、空气中蒸发溶剂48小时。最后,在真空下、50℃将聚合物干燥12小时。
该TPU显示出下列特性:Mn=140000,PDI=2.2,UTS=20MPa,断裂伸长=550%,杨氏模量=6MPa。
实施例10:聚异丁烯(饱和)/聚醚基热塑性氨基甲酸乙酯(PIB
饱和
-PTMO-TPU,肖氏硬度80A)的合成
按照图2例示的合成步骤,用两步法合成TPU,该TPU具有不同重量比的羟基丙基遥爪PIB与PTMO的混合物作为软链段。BDO和MDI构成硬链段。所有情况都保持软链段与硬链段之比为66∶34wt%。
如下合成PIB饱和-PTMO-82-8。通过从无水甲苯(10mL)溶液中共沸蒸馏,干燥HO-丙基-PIB-丙基-OH(Mn=2000,5.2g,2.6mmol)和PTMO(Mn=1000,1.3g,1.3mmol)。将该混合物在45℃、真空下保持3小时。向该混合物中加入25mL无水甲苯,然后加入Sn(Oct)2(42.5mg,0.105mmol)的甲苯溶液。在干燥氮气的缓慢气流下,于80℃加热该混合物。将MDI(2.64g,10.54mmol)加入反应混合物中,并将该混合物剧烈搅拌30分钟。向反应混合物中加入BDO(604mg,6.64mmol),并将该混合物在100℃搅拌4小时。将该混合物冷却至室温,倒入模具中,并在室温、空气中蒸发溶剂48小时。最后,在真空下、50℃将聚合物干燥12小时。
该TPU显示出下列特性:Mn=85000,PDI=2.2,UTS=27MPa,断裂伸长=475%,杨氏模量=15MPa。
实施例11:聚异丁烯/聚醚基热塑性氨基甲酸乙酯(PIB-聚环氧丁烷
(PHMO)-TPU,肖氏硬度80A)的合成
按照图2例示的合成步骤,采用两步法合成TPU,该TPU具有不同重量比的PIB与PHMO的混合物作为软链段。BDO和MDI构成硬链段。保持软链段与硬链段之比为67∶33wt%。
例如,如下合成PIB-PHMO-82-8。通过从无水甲苯(10mL)溶液中共沸蒸馏,干燥HO-烯丙基-PIB-烯丙基-OH(Mn=2200,4.6g,2.1mmol)和PHMO(Mn=920,1.15g,1.25mmol)。将该混合物在45℃、真空下保持3小时。向该混合物中加入25mL无水甲苯,然后加入Sn(Oct)2(37.26mg,0.092mmol)的甲苯溶液。在干燥氮气的缓慢气流下,于80℃加热该混合物。将MDI(2.3g,9.22mmol)加入该混合物中,并将该混合物剧烈搅拌30分钟。向所得反应混合物中加入BDO(534mg,5.87mmol),并将该混合物在100℃搅拌4小时。将该混合物冷却至室温,倒入模具中,并在室温、空气中蒸发溶剂48小时。最后,在真空下、50℃将聚合物干燥12小时。
该TPU显示出下列特性:Mn=73000,PDI=3.4,UTS=18MPa,断裂伸长=280%,杨氏模量=27MPa。
实施例12:聚异丁烯(饱和)/聚醚基热塑性氨基甲酸乙酯(PIB
饱和
-PHMO-TPU,肖氏硬度60A)的合成
按照图2例示的合成步骤,用两步法合成TPU,该TPU具有不同重量比的羟基丙基遥爪PIB与PHMO的混合物作为软链段。BDO和MDI构成硬链段。所有情况都保持软链段与硬链段之比为76∶24wt%。
例如,如下合成PIB饱和-PHMO-82-6。通过从无水甲苯(10mL)溶液中共沸蒸馏,干燥HO-丙基-PIB-丙基-OH(Mn=2000,4.6g,2.3mmol)和PHMO(Mn=920,1.15g,1.25mmol)。将该混合物在45℃、真空下保持3小时。向该混合物中加入25mL无水甲苯,然后加入Sn(Oct)2(26.3mg,0.065mmol)的甲苯溶液。在干燥氮气的缓慢气流下,于80℃加热该混合物。将MDI(1.62g,6.48mmol)加入该混合物中,并将该混合物剧烈搅拌30分钟。向所得反应混合物中加入BDO(267mg,2.93mmol),并将该混合物在100℃搅拌4小时。将该混合物冷却至室温,倒入模具中,并在室温、空气中蒸发溶剂48小时。最后,在真空下、50℃将聚合物干燥12小时。
该TPU显示出下列特性:Mn=120000,PDI=3.4,UTS=16MPa,断裂伸长=550%,杨氏模量=6MPa。
实施例13:聚异丁烯(饱和)/聚醚基热塑性氨基甲酸乙酯(PIB
饱和
-PTMO-TPU,肖氏硬度95A)的无催化剂的合成
按照图2例示的合成步骤,用两步法合成TPU,该TPU具有不同重量比的羟丙基遥爪PIB与PTMO-二醇混合物作为软链段。BDO和MDI构成硬链段。所有情况都保持软链段与硬链段之比为60∶40wt%。
例如,如下合成PIB饱和-PTMO-82-9。通过从无水甲苯(10mL)溶液中共沸蒸馏,干燥HO-丙基-PIB-丙基-OH(Mn=2000,2.8g,1.4mmol)和PTMO(Mn=1000,0.8g,0.8mmol)。将该混合物在45℃、真空下保持3小时,向该混合物中加入25mL无水甲苯。在干燥氮气的缓慢气流下,将混合物的温度升至100℃。将MDI(1.92g,7.7mmol)加入该混合物中,并将该混合物剧烈搅拌1小时30分钟。向所得反应混合物中加入BDO(500mg,5.5mmol),并将该混合物在100℃搅拌4小时。将该混合物冷却至室温,倒入Teflon模具中,并在室温、空气中蒸发溶剂48小时。最后,在真空下、50℃将聚合物干燥12小时。
该TPU显示出下列特性:Mn=88000,PDI=3.7。
实施例14:嵌段聚异丁烯-基热塑性聚氨酯的长期体外生物稳定性
在50℃、加速条件下,在含有0.1M CoCl2的20%H2O2溶液中,研究含有混合聚异丁烯(PIB)/聚环氧丁烷(PTMO)软链段的热塑性聚氨酯(TPU)的长期体外生物稳定性,以预测对体内金属离子氧化降解的抗性。与商业对照品如PellethaneTM2686-55D和2686-80A相比,含有PTMO的PIB基TPU显示出显著的氧化稳定性。体外12周(大体相当于体内10年)后,软链中具有10-20%PTMO的PIB-PTMO TPU显示6-15%重量损失,而PellethanesTM在约9周内完全分解。重量损失与PIB-PTMO TPU中的PTMO含量成线性比例。ATR-FTIR光谱学通过因断链引起的大约1110cm-1脂族C-O-C拉伸峰高的一致性损失以及在大约1174cm-1因交联而出现的新峰,确认了PellethanesTM经由MIO的降解。在PIB-基TPU的光谱上,没有明显的这种吸收谱带。12周后,与PellethanesTM的100%相比,PIB-基TPU的拉伸强度显示出10-30%的下降。拉伸强度的下降与TPU中的PTMO含量大致相关。与拉伸强度有很好关联性的分子量结果在12周时显示出10-15%的轻微下降。PellethanesTM显示出Mn的戏剧性下降,而低分子量降解产品则有所增加。SEM显示PellethanesTM两周后出现严重破裂,而PIB-基TPU却呈现出连续的表面形态。重量损失、拉伸和SEM数据彼此良好相关,表明这些材料优异的生物稳定性。
材料和方法
聚氨酯
对比样品由PellethanesTM2363-55D和PellethanesTM2363-80A构成。如前所述合成具有各种硬度和PIB∶PTMO组成的聚氨酯,列于表24中。下面描述代表性TPU(60A,82)的两段法:通过使用无水甲苯(10mL)进行共沸蒸馏,干燥HO-烯丙基-PIB-烯丙基-OH(Mn=2200g/mol,5.2g,2.36mmol)和PTMO(Mn=1000g/mol,1.3g,1.3mmol)。将该混合物在45℃、真空下保持3小时。向其中加入25mL无水甲苯,然后加入Sn(Oct)2(28.3mg,0.07mmol)的甲苯溶液。在干燥氮气的缓慢气流下,于80℃加热该混合物。向其中加入MDI(1.76g,7.02mmol),并将该混合物剧烈搅拌30分钟。向其中加入BDO(302mg,3.36mmol),并将该混合物在100℃搅拌4小时。将该混合物冷却至室温,倒入模具中,并在室温、空气中蒸发溶剂48小时。最后,在真空下、50℃将聚合物干燥12小时。同样制备无PTMO的PIB TPU。使用由Kennedy(Iván,B.;Kennedy,J.P.J.Polym.Sci.,Part A:Polym.Chem.1990,28,89)开发的方法制备而成的HO-丙基-PIB-丙基-OH合成饱和PIB-PTMO。在加速降解之前,采用1H NMR和GPC表征聚氨酯。较硬的组合物(80A91,100A)不溶于GPC洗脱液。
表24.PIB和PTMO wt%
aHO-PIB-OH,Mn=2200g/mol
bHO-PTMO-OH,Mn=1000g/mol
将聚氨酯用C型Carver Laboratory Press在16,000lbs.载荷、160℃进行压塑。将其模塑成厚度为0.2mm-0.5mm的薄膜,并切成大致尺寸为3mm宽、30mm长的矩形条带。
体外加速降解
将样品放入管型瓶,浸泡在20%H2O2的0.1M CoCl2水溶液中,于50℃储存。每隔一天更换溶液,以确保游离基的稳定浓度。在1、2、4、6和12周的时间点,将专用样品从氧化环境中移出,用含水的1%Triton X-100表面活性剂溶液洗涤7次,用乙醇洗涤5次,用蒸馏水洗涤5次,并在真空下、80℃干燥至恒重。
表征法
干燥样品通过重量损失、ATR-FTIR、极限拉伸强度、断裂伸长、SEM和GPC表征鉴定。各数据点由三个相同的样品组成。定量数据中,报告值是三个样品的平均值。
ATR-FTIR
用金刚石晶体,在配备ATR用Thermo Electron Corporation SmartOrbit附件的Thermo Electron Corporation Nicolet 4700FR-IR上实施ATR-FTIR。对每个样品进行32次扫描,将其平均以获得具有代表性的谱图。将干燥干净的TPU条带分别放置在晶体上,用脚附件将其牢固缚住,并扫描用于分析。关注的范围大体在1700cm-1至1100cm-1之间,这包括HS降解产品(大约1650cm-1),SS降解部分(大约1110cm-1)和产品(大约1170cm-1)以及归一化(normalized)参考峰(大约1410cm-1)。
重量损失
在氧化处理之前和之后,在Sartorius MCI Analytic AC 210S天平上测量干燥聚氨酯膜的重量。
机械测试
在室温、大气条件下,以50lb进行拉伸测试。负荷加载于InstronModel Tensile Tester 4400R上以50mm/min伸长率直至失败。记录极限拉伸强度和断裂伸长。
GPC分析
用Waters HPLC系统测量分子量和分子量分布,该Waters HPLC系统装配有510型HPLC泵、410型差示折光剂、441型吸光度检测仪、线上多角激光光散射(MALLS)检测仪(MiniDawn,WyattTechnology Inc.)、712型样品处理机和五个分别与以下系列相连的Ultrastyragel GPC柱:500、103、104、105和使用THF∶TBAB(98∶2,wt∶wt)作为载体溶剂,流速为1mL/min。
扫描电子显微镜镜检
将干燥的经过处理的薄膜分离出一部分用于SEM分析。使用Denton Vacuum Desk IV Cold Cathode Sputter Coater,在金溅射涂膜的样品上观测表面形态。将这些样品以25%粉末溅射涂膜1.5分钟,相当于约金的厚度。使用JEOL型JSM 7401F场致发射扫描电子显微镜观测涂膜样品。取30x倍和300x倍放大率的数张代表性图片。
3.结果和讨论
ATR-FTIR
进行ATR-FTIR分析,确认MIO机理的存在和发展,正如Schubert及其同事们所提出的那样。根据他们提出的机理,羟基自由基可从聚醚链段夺取α-氢。所得自由基可与另一链自由基结合形成交联接头,或者与另一羟基自由基反应形成半缩醛。半缩醛氧化成酯,酯随后又酸解导致断链。因此,可以通过跟踪SS醚峰的消失和/或交联峰的出现来观测降解的发展。所有谱图均归一化至1410cm-1的峰,该峰对应于硬链段的芳族C-C延伸。
PIB-PTMO聚氨酯的FTIR谱图变化全都非常小。一个具有代表性的60A 82的谱图示于图6中。
正如可见的那样,1110cm-1处的脂族醚C-O-C吸光度没有可评估的变化,不存在大约1174cm-1处的C-O-C支化吸光度。但是,可观测到脂族吸光度随时间增加(在1470cm-1处的脂族CH2弯曲,1388cm-1处的PIB二甲基摆动,以及1410cm-1处的脂族α-CH2摆动)。这种表现可被合理地解释为是PIB链段在80℃真空干燥期间向表面迁移所致。这些PIB-PTMO TPU中可能没发生交联,因为没有显著的PTMO存在或运动使两个聚合物自由基在它们裂解之前结合。在PIB-PTMOTPU图谱中观察到了相似的结果。该分析包括饱和60A 91批次,以便测定PIB二醇中的饱和烯丙基部分是否容易被氧化。使用饱和二醇的TPU的FTIR谱图与包含不饱和二醇的TPU的谱图完全相同。而且,还包括PIB 60A TPU以确认在这些TPU中只有聚醚SS降解而没有HS降解。这一假设得到了确认,因为谱图完全没有显示出任何变化。由于没有聚醚降解,因此在1388cm-1处的PIB吸光度和1111cm-1处的醚吸光度都没有变化。也没有HS降解的任何证据。表25中列出了IR吸光度,可观察到变化趋势。
表25:指定的ATR-FTIR谱峰变化
波数(cm-1) | 暗示的峰分配 | P80A | P55D | PIB-PTMO |
1637 | NH2芳胺 | X | ||
1476 | 脂族CH2弯曲 | X | ||
1388 | PIB CH3摆动 | X | ||
1365 | 脂族α-CH2摆动 | X | X | X |
1173 | C-O-C支化 | X | X | |
1110 | 脂族C-O-C | X | X |
PellethaneTM样品显示出预期的表现,与先前的研究一致。P55D的谱图如图7所示。
谱图显示1109cm-1处的脂族C-O-C吸收在1周后明显减少,然后一直到6周变得更慢。同时,我们观察到1364cm-1处的脂族α-CH2吸收在仅仅1周后快速消失。1172cm-1处的C-O-C支化吸收也在1周时立即观察到了,之后就保持恒定量级。正如随后将要看到的,PellethanesTM在1周后持续恒定降解或加速降解,由此可良好地解释IR谱图。ATR-FTIR是表面表征技术,预料降解是从表面开始的。因此,我们得出结论:表面易被氧化的链段几乎是立即就被氧化了,并在接下来的几周内氧化加深,这从分析结果可以观察得到。
重量损失
图8是用重量损失相对于时间制作的图。PIB-PTMO TPU在12周后全部都显示出非常低的重量损失,根据组成在6-15%范围内变化。在60A批次中,与80/20组成的8%的重量损失相比,90/10组成显示出6%的更低重量损失。饱和60A 91的重量损失可参照不饱和60A 91的重量损失。同样地,在80A批次中,具有较低PTMO含量的TPU显示出较低的重量损失,30%、20%和10%PTMO分别为15%、10%和6%。更具体地说,重量损失可与聚氨酯中的PTMO含量相关。图9是12周时重量损失相对于PTMO含量制作的图。
可以看出,PIB-PTMO TPU的重量损失与PTMO含量大致呈线性关系。这一发现支持这些见解:即聚醚SS经由MIO降解,这些部分从聚氨酯分离出来。引人注意的是,60A 82的重量损失低于对其PTMO含量的预期重量损失。只含有PIB的TPU也显示出很小的重量损失,这与图相符。由于表面积与体积之比这样大,我们预期会见到表面的一些小磨耗。PellethaneTM对照样品在即使1周体外后也显示出可观的重量损失,而P80A和P55D则分别在大约7周和9周后完全降解。这些发现与先前关于这类聚醚基TPU的发现一致。
机械特性
图10是原始未处理样品的拉伸强度百分数相对于时间制成的图。
在P55D相对于PIB-PTMO TPU的图中可看出很大不同。在PIB-PTMO TPU中,尽管不同样品的拉伸损失比在变化,但能观测到所有样品的拉伸强度都显示最低限度的下降。PIB-PTMO TPU显示与PTMO含量粗略相关的不同损失。在60A批次中,不同组成的拉伸损失是可比较的。由于样品套不足,未能获得60A 91的12周数据点。不过,最长6周所观测到的趋势与饱和60A 91的非常近似。也观测到60A PIB样品的拉伸强度显示最低限度的下降,这表明没有降解,与重量损失和FTIR研究所证实的一样。这表明1-2MPa可能是在所用装样单元(load cell)和仪器所引起的实验误差范围内。在80A批次中,80/20组成的拉伸强度降低了~21%,而90/10组成则仅降低了~13%。80A 73样品(未显示)的拉伸强度初始有增加,随后出现较慢的下降。这是因为初始时发生交联,随后发生断链,这与该样品中PTMO量的增加是一致的。当PTMO为该量(总TPU的19.5%)时,链自由基浓度充足,从而能够发生交联和断链。虽然12周时的拉伸强度%大于其他PIB-PTMO TPU,将数据外推可以预测80A 73的拉伸强度在更长的时间间隔将发生更急剧的下降。
由于更大的结晶度,P55D显示出比P80A更强的抗降解性。由此,预期100A 82组成具有(即使不是更好也是)可与80A 82相比拟的强度,但我们还是看到更大的拉升下降。这可说明PIB比硬链段能更好地保护表面。一些样品实际上显示出抑制周期,其中拉伸强度直到2、4或甚至6周时才开始出现下降(特别是80A 82)。PIB-PTMO TPU的极限伸长在处理期间未出现显著的变化。PellethaneTM再次显示出预期的MIO行为。P55D在长至6周内随时间过去出现缓慢的拉升损失,在12周时无样品可测试。P80A(未显示)在一周后拉伸强度呈现初始增加,然后是缓慢减少。这是因为初始时发生链交联,以后出现断链,如在样品80A 73所观测到的。
GPC分析
将TPU样品溶解于THF∶TBAB(98∶2,wt∶wt)载体溶剂中。但部分较硬的组成不溶。具有代表性的饱和60A 91的GPC RI示踪显示于图11中。TBAB洗脱超过47分钟。
分子量的损失为最低限度,与重量损失和拉伸数据一致。6周后,分子量从130,000g/mol轻微减少至112,000g/mol,然后在12周时可忽略地降至110,000g/mol,同时PDI保持在1.6不变。这些数据与FTIR和拉伸数据一致。
图12给出了P80A的折光率示踪。数均分子量出现清楚的降低趋势,处理前为84,000g/mol,4周时降低为18,000g/mol,6周时降低至14,000g/mol。在4周内,一些低分子量降解产品出现清楚可见的上升。同时,分子量分布增加。这些发现与ATR-FTIR、重量损失和拉伸结果是一致的。P55D具有近似的表现,Mn下降,PDI增加。
SEM
图13-16给出了300x倍放大率的代表性SEM图。图13是P55D,显示随着处理时间出现“大龟裂”,这是常常观测到的现象。龟裂的表面密度随着时间增加,目测也确认了先前的数据。
在图14、图15和图16中,给出了80A系列的扫描电子显微镜照片,用以描述PTMO含量对表面形态的影响。这些TPU对降解的反应当然与PellethaneTM不同,但可看到表面瑕疵随PTMO含量增加而增加的趋势。80A73在12周后出现一些小孔和表面不光滑。80A82在12周后出现稍大的坑,80A91的表面形态在12周后未出现实质性的变化。在各种样品上经常看到一些小孔,但这预料不是因为降解形成的。在未降解的60A PIB样品上也看到同样的模式;因此这样的孔预料是压塑工艺的加工品。
60A系列呈现出类似的形态,90/10组成的表面瑕疵更少。100A82组成的形态可与80A91相比拟。
结论
体外12周后,这相当于大约体内10年,本发明的热塑性聚氨酯显示出最小量的降解和最小量的性能下降。使用不饱和PIB二醇代替饱和PIB二醇,对本发明聚氨酯的降解没有影响。未观测到PIB链段和硬链段发生降解。增加结合入本发明热塑性聚氨酯的聚醚二醇的量使降解速率增加,表明其降解与以前假设的PTMO-基热塑性聚氨酯降解机理一致。因此,低PTMO含量被认为在确保生物稳定性方面是令人满意的。
等同
虽然通过实施例对本发明进行了具体描述,但本领域技术人员都会理解,各种形式和细节上的变化都仍然是包含在本发明范围内的,其并未脱离所附权利要求所要求保护的发明范围。
Claims (39)
1.一种弹性聚合物,该聚合物包含:
(1)占该弹性聚合物的10%-60%重量的硬链段,其中所述硬链段包括氨基甲酸乙酯、脲或氨基甲酸乙酯脲;和
(2)占该弹性聚合物的40%-90%重量的软链段,其中所述软链段包含:
(a)占软链段的10%重量至30%重量的至少一种聚醚大分子二醇;和
(b)占软链段的70%重量至90%重量的至少一种聚异丁烯大分子二醇和/或二胺,
其中所述弹性聚合物的数均分子量不低于40千道尔顿,并且其中所述至少一种聚醚大分子二醇包括选自下列的至少一种:聚氧丙烯二醇、聚环氧丁烷二醇、聚环氧己烷二醇、聚环氧庚烷二醇、聚环氧辛烷二醇和聚环氧癸烷二醇。
2.权利要求1的弹性聚合物,其中该弹性聚合物的数均分子量不低于50千道尔顿。
4.权利要求1的弹性聚合物,其中所述硬链段以该占弹性聚合物的30%重量至50%重量的量存在。
5.权利要求1的弹性聚合物,其中所述聚异丁烯大分子二醇为羟基烯丙基遥爪聚异丁烯。
6.权利要求1的弹性聚合物,其中所述聚异丁烯大分子二醇为羟基烷基遥爪聚异丁烯。
7.权利要求6的弹性聚合物,其中所述聚异丁烯大分子二醇为羟基丙基遥爪聚异丁烯。
8.权利要求1的弹性聚合物,其中所述聚异丁烯二胺为氨基烯丙基遥爪聚异丁烯。
9.权利要求1的弹性聚合物,其中所述至少一种聚异丁烯大分子二醇的数均分子量为400Da至6000Da。
10.权利要求1的弹性聚合物,其中所述至少一种聚异丁烯大分子二醇的数均分子量为100Da至3000Da。
11.权利要求1的弹性聚合物,其中所述硬链段通过使二异氰酸酯与增链剂反应而形成。
12.权利要求11的弹性聚合物,其中所述二异氰酸酯包括选自下列的至少一种:4,4’-亚甲基苯基二异氰酸酯、亚甲基二异氰酸酯、对苯二异氰酸酯、环己烷-1,4-二异氰酸酯、1,6-己二异氰酸酯、2,4-甲苯二异氰酸酯、对四甲基二甲苯二异氰酸酯和间四甲基二甲苯二异氰酸酯。
13.权利要求11的弹性聚合物,其中所述增链剂包括选自下列的至少一种:1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,12-十二烷二醇、1,4-环己烷二甲醇、对苯二甲醇和1,4-双(2-羟基乙氧基)苯。
14.权利要求11的弹性聚合物,其中所述增链剂包括选自下列的至少一种:1,4-二氨基丁烷、1,5-二氨基戊烷、1,6-二氨基己烷、1,8-二氨基辛烷、1,9-二氨基壬烷、1,10-二氨基癸烷、1,12-二氨基十二烷、1,4-二氨基环己烷和2,5-二氨基二甲苯。
15.权利要求11的弹性聚合物,其中所述二异氰酸酯为4,4’-亚甲基苯基二异氰酸酯,其中所述增链剂为1,4-丁二醇。
16.权利要求1的弹性聚合物,其中所述软链段由羟基烯丙基遥爪聚异丁烯形成,所述硬链段由4,4’-亚甲基二苯基二异氰酸酯和1,4-丁二醇形成。
17.权利要求1的弹性聚合物,其中所述软链段由羟基烯丙基遥爪聚异丁烯和聚环氧丁烷二醇形成,所述硬链段由4,4’-亚甲基二苯基二异氰酸酯和1,4-丁二醇形成。
18.权利要求1的弹性聚合物,其中所述软链段衍生自羟基烯丙基遥爪聚异丁烯和聚环氧己烷二醇,所述硬链段衍生自4,4’-亚甲基二苯基二异氰酸酯和1,4-丁二醇。
19.权利要求1的弹性聚合物,其中所述软链段由(a)羟基烯丙基二官能聚异丁烯和(b)聚环氧丁烷二醇或聚环氧己烷二醇形成,所述硬链段由(c)4,4’-亚甲基二苯基二异氰酸酯和(d)1,4-丁二醇形成。
20.权利要求1的弹性聚合物,其中所述软链段包括占该软链段的10%重量至20%重量的至少一种聚醚大分子二醇。
21.一种含有弹性聚合物的生产制品,所述弹性聚合物包含:
(1)占该弹性聚合物的10%-60%重量的硬链段,该硬链段包括氨基甲酸乙酯、脲或氨基甲酸乙酯脲;和
(2)占该弹性聚合物的40%-90%重量的软链段,
其中所述软链段包含:
(a)占该软链段的10%重量至30%重量的至少一种聚醚大分子二醇;和
(b)占该软链段的70%重量至90%重量的至少一种聚异丁烯大分子二醇和/或二胺,
其中所述弹性聚合物的数均分子量不低于40千道尔顿,并且其中该制品为医学设备或植入物,并且其中所述至少一种聚醚大分子二醇包括选自下列的至少一种:聚氧丙烯二醇、聚环氧丁烷二醇、聚环氧己烷二醇、聚环氧庚烷二醇、聚环氧辛烷二醇和聚环氧癸烷二醇。
22.权利要求21的制品,其中所述弹性聚合物的数均分子量不低于50千道尔顿。
23.权利要求21的制品,该制品为纤维、工程塑料或涂膜。
24.权利要求21的制品,该制品为薄膜、织物或粘接性关节。
25.权利要求21的制品,该制品为导尿管、可植入假体、生物传感器、药物传递装置或伤口敷料。
26.权利要求21的制品,该制品为人造器官、血液泵、气囊泵、V型分流器或用于细胞封装的膜。
27.权利要求21的制品,该制品为心脏辅助装置或人造关节。
28.权利要求21的制品,该制品为心脏起搏器、去纤颤器、起搏器导线、去纤颤器导线、骨科植入物或软组织替代物。
29.一种制备弹性聚合物的方法,该方法包括下述步骤:
a)形成一种混合物,该混合物包括至少一种聚异丁烯大分子二醇和/或二胺、至少一种聚醚大分子二醇和增链剂;和
b)使该混合物与二异氰酸酯反应,生成弹性聚合物,其中,所述弹性聚合物包含:
(i)占该弹性聚合物的10%-60%重量的硬链段,该硬链段包括氨基甲酸乙酯、脲或氨基甲酸乙酯脲;和
(ii)占该弹性聚合物的40%-90%重量的软链段,所述软链段包含:
占该软链段的10%重量至30%重量的至少一种聚醚大分子二醇;和
占该软链段的70%重量至90%重量的至少一种聚异丁烯大分子二醇和/或二胺,
其中所述弹性聚合物的数均分子量不低于40千道尔顿,并且其中所述至少一种聚醚大分子二醇包括选自下列的至少一种:聚氧丙烯二醇、聚环氧丁烷二醇、聚环氧己烷二醇、聚环氧庚烷二醇、聚环氧辛烷二醇和聚环氧癸烷二醇。
30.权利要求29的方法,其中所述弹性聚合物的数均分子量不低于50千道尔顿。
32.权利要求29的方法,其中所述混合物在45℃至120℃的温度形成。
33.权利要求29的方法,其中所述混合物在催化剂存在下形成。
34.权利要求33的方法,其中所述催化剂为辛酸亚锡。
35.一种制备弹性聚合物的方法,该方法包括下述步骤:
a)使二异氰酸酯与包括至少一种聚异丁烯大分子二醇和/或二胺以及至少一种聚醚大分子二醇的混合物反应,形成具有末端反应性二异氰酸酯基的预聚物;和
b)使该预聚物与增链剂反应,得到弹性聚合物,其中所述弹性聚合物包含:
(i)占该弹性聚合物的10%-60%重量的硬链段,该硬链段包括氨基甲酸乙酯、脲或氨基甲酸乙酯脲;和
(ii)占该弹性聚合物的40%-90%重量的软链段,其中所述软链段包含:
占该软链段的10%重量至30%重量的至少一种聚醚大分子二醇;和
占该软链段的70%重量至90%重量的至少一种聚异丁烯大分子二醇和/或二胺,
其中所述弹性聚合物的数均分子量不低于40千道尔顿,并且其中所述至少一种聚醚大分子二醇包括选自下列的至少一种:聚氧丙烯二醇、聚环氧丁烷二醇、聚环氧己烷二醇、聚环氧庚烷二醇、聚环氧辛烷二醇和聚环氧癸烷二醇。
36.权利要求35的方法,其中所述弹性聚合物的数均分子量不低于50千道尔顿。
38.权利要求35的方法,其中所述增链剂包括选自下列的至少一种:1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,12-十二烷二醇、1,4-环己烷二甲醇、对苯二甲醇和1,4-双(2-羟基乙氧基)苯。
39.权利要求35的方法,其中所述增链剂包括选自下列的至少一种:1,4-二氨基丁烷、1,5-二氨基戊烷、1,6-二氨基己烷、1,8-二氨基辛烷、1,9-二氨基壬烷、1,10-二氨基癸烷、1,12-二氨基十二烷、1,4-二氨基环己烷和2,5-二氨基二甲苯。
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US20485609P | 2009-01-12 | 2009-01-12 | |
US61/204,856 | 2009-01-12 | ||
US21131009P | 2009-03-26 | 2009-03-26 | |
US61/211,310 | 2009-03-26 | ||
US27962909P | 2009-10-23 | 2009-10-23 | |
US61/279,629 | 2009-10-23 | ||
PCT/US2010/020733 WO2010081132A1 (en) | 2009-01-12 | 2010-01-12 | Polyisobutylene-based polyurethanes |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102365308A CN102365308A (zh) | 2012-02-29 |
CN102365308B true CN102365308B (zh) | 2014-03-12 |
Family
ID=42102758
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201080010942.8A Active CN102365308B (zh) | 2009-01-12 | 2010-01-12 | 聚异丁烯基聚氨酯 |
Country Status (6)
Country | Link |
---|---|
US (4) | US9574043B2 (zh) |
EP (3) | EP3670561B1 (zh) |
JP (1) | JP5638003B2 (zh) |
CN (1) | CN102365308B (zh) |
AU (1) | AU2010203373B2 (zh) |
WO (1) | WO2010081132A1 (zh) |
Families Citing this family (47)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060264577A1 (en) * | 2005-04-08 | 2006-11-23 | Rudolf Faust | Capping reactions in cationic polymerization; kinetic and synthetic utility |
US20100069578A1 (en) * | 2006-11-17 | 2010-03-18 | Rudolf Faust | Functional Hydrocarbon Polymers and Process for Producing Same |
CN102131530A (zh) | 2008-06-27 | 2011-07-20 | 心脏起搏器公司 | 聚异丁烯-氨基甲酸酯共聚物、聚异丁烯-脲共聚物和聚异丁烯-氨基甲酸酯/脲共聚物及含有这类共聚物的医疗器械 |
EP3670561B1 (en) | 2009-01-12 | 2023-12-06 | University Of Massachusetts Lowell | Polyisobutylene-based polyurethanes |
US8423140B2 (en) | 2009-06-01 | 2013-04-16 | Cardiac Pacemakers, Inc. | System and method for decompensation detection and treatment based on patient hemodynamics |
EP2467174B1 (en) | 2009-08-21 | 2018-09-26 | Cardiac Pacemakers, Inc. | Crosslinkable polyisobutylene-based polymers and medical devices containing the same |
US8374704B2 (en) * | 2009-09-02 | 2013-02-12 | Cardiac Pacemakers, Inc. | Polyisobutylene urethane, urea and urethane/urea copolymers and medical leads containing the same |
US8644952B2 (en) * | 2009-09-02 | 2014-02-04 | Cardiac Pacemakers, Inc. | Medical devices including polyisobutylene based polymers and derivatives thereof |
CA2780272A1 (en) * | 2009-11-11 | 2011-05-19 | The University Of Akron | Polyisobutylene-based polyurethanes, polyureas and/or polyurethane-polyureas and method for making same |
US8660663B2 (en) | 2010-12-20 | 2014-02-25 | Cardiac Pacemakers, Inc. | Lead having a conductive polymer conductor |
AU2012295332B2 (en) | 2011-08-12 | 2014-12-04 | Cardiac Pacemakers, Inc. | Method for coating devices using electrospinning and melt blowing |
US10285793B2 (en) | 2012-02-08 | 2019-05-14 | Boston Scientific Scimed, Inc. | Surgical scaffolds |
EP2866847B1 (en) | 2012-07-02 | 2018-08-22 | Boston Scientific Scimed, Inc. | Prosthetic heart valve formation |
EP2922888B1 (en) | 2012-11-21 | 2021-08-18 | The University of Massachusetts | High strength polyisobutylene polyurethanes |
US10343385B2 (en) | 2013-07-18 | 2019-07-09 | Boston Scientific Scimed, Inc. | Bodily implant |
US20150025608A1 (en) | 2013-07-22 | 2015-01-22 | Cardiac Pacemakers, Inc. | Lubricious, biocompatible hydrophilic thermoset coating using interpenetrating hydrogel networks |
WO2015053934A1 (en) | 2013-10-10 | 2015-04-16 | Medtronic, Inc. | Implantable medical devices including a polyether-polyurethane substrate with improved biostability, and methods |
DE102013016899A1 (de) | 2013-10-11 | 2015-05-21 | Josef Jansen | Gelenkspacer |
JP7109159B2 (ja) * | 2014-09-17 | 2022-07-29 | 日産化学株式会社 | 熱硬化性樹脂を含む膜形成組成物 |
US9980659B2 (en) * | 2014-09-26 | 2018-05-29 | NeuroRex Inc. | Bio-potential sensing materials as dry electrodes and devices |
US10426609B2 (en) | 2015-04-09 | 2019-10-01 | Boston Scientific Scimed, Inc. | Fiber reinforced prosthetic heart valve having undulating fibers |
US10299915B2 (en) | 2015-04-09 | 2019-05-28 | Boston Scientific Scimed, Inc. | Synthetic heart valves composed of zwitterionic polymers |
US10314696B2 (en) | 2015-04-09 | 2019-06-11 | Boston Scientific Scimed, Inc. | Prosthetic heart valves having fiber reinforced leaflets |
US10716671B2 (en) | 2015-07-02 | 2020-07-21 | Boston Scientific Scimed, Inc. | Prosthetic heart valve composed of composite fibers |
US10413403B2 (en) | 2015-07-14 | 2019-09-17 | Boston Scientific Scimed, Inc. | Prosthetic heart valve including self-reinforced composite leaflets |
US9855415B2 (en) | 2015-07-25 | 2018-01-02 | Cardiac Pacemakers, Inc. | Medical electrical lead with biostable PVDF-based materials |
US10195023B2 (en) | 2015-09-15 | 2019-02-05 | Boston Scientific Scimed, Inc. | Prosthetic heart valves including pre-stressed fibers |
JP6581303B2 (ja) * | 2015-12-17 | 2019-09-25 | カーディアック ペースメイカーズ, インコーポレイテッド | ポリイソブチレン−ポリウレタンを含むポリマー材料およびそれを含む医療デバイス並びに同ポリマー材料を製造する方法 |
US10618999B2 (en) * | 2016-01-26 | 2020-04-14 | The University Of Akron | Polyisobutylene-based poly(urethane-urea)s |
US10870952B2 (en) | 2016-03-18 | 2020-12-22 | Advanced Polymer Technologies Corp. | Using a polyol mixture comprising PBD for creating a PU-based artificial turf |
EP3455272B1 (en) * | 2016-05-10 | 2020-05-27 | Cardiac Pacemakers, Inc. | Thermoset polyisobutylene-polyurethanes and methods for making |
US10368982B2 (en) | 2016-05-19 | 2019-08-06 | Boston Scientific Scimed, Inc. | Prosthetic valves, valve leaflets and related methods |
WO2018020827A1 (ja) * | 2016-07-26 | 2018-02-01 | 富士フイルム株式会社 | 固体電解質組成物、固体電解質含有シートおよび全固体二次電池、固体電解質含有シートおよび全固体二次電池の製造方法、ならびに、セグメント化ポリマー、ポリマーおよびセグメント化ポリマーの非水溶媒分散物 |
EP3545040B1 (en) | 2016-09-23 | 2023-03-15 | The University of Massachusetts | Polyurethane, method of preparation, and article comprising the polyurethane |
US10465318B2 (en) | 2016-12-27 | 2019-11-05 | Boston Scientific Scimed Inc | Degradable scaffolding for electrospinning |
US11160907B2 (en) | 2017-03-02 | 2021-11-02 | Medtronic, Inc. | Medical device with a tubular portion comprising a thermoplastic elastomer with soft and hard segments, method for preparation thereof, and use thereof |
CN110536913B (zh) * | 2017-03-02 | 2022-03-04 | 中国科学院宁波材料技术与工程研究所 | 弹性体、其制备方法及其用途 |
US10526429B2 (en) | 2017-03-07 | 2020-01-07 | Cardiac Pacemakers, Inc. | Hydroboration/oxidation of allyl-terminated polyisobutylene |
CN110494170A (zh) | 2017-04-25 | 2019-11-22 | 波士顿科学国际有限公司 | 生物相容性聚异丁烯-纤维复合材料和方法 |
EP3668912B1 (en) | 2017-08-17 | 2021-06-30 | Cardiac Pacemakers, Inc. | Photocrosslinked polymers for enhanced durability |
US11472911B2 (en) | 2018-01-17 | 2022-10-18 | Cardiac Pacemakers, Inc. | End-capped polyisobutylene polyurethane |
US10882945B2 (en) * | 2018-03-26 | 2021-01-05 | Medtronic, Inc. | Modified polyisobutylene-based polymers, methods of making, and medical devices |
US20190292327A1 (en) * | 2018-03-26 | 2019-09-26 | Medtronic, Inc. | Poly(ether-carbonate)-based polymers and medical devices |
CN111375089B (zh) * | 2018-12-27 | 2022-06-21 | 南京理工大学 | 聚氨酯/纳米金刚石骨修复复合材料及其制备方法 |
CN111748086B (zh) * | 2020-07-20 | 2022-08-05 | 万华化学(四川)有限公司 | 聚异丁烯基聚碳酸酯共聚物及其制备方法 |
EP4192896A4 (en) * | 2020-08-06 | 2024-08-28 | Univ Akron | SYNTHESIS OF HIGH MOLECULAR AND HIGH STRENGTH POLYURETHANES BASED ON POLYISOBUTYLENE AND USE THEREOF |
WO2024168183A1 (en) * | 2023-02-09 | 2024-08-15 | Edwards Lifesciences Corporation | Long-term biostable thermoplastic compositions and medical devices containing the same |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5120813A (en) * | 1980-02-29 | 1992-06-09 | Th. Goldschmidt Ag | Moisture vapor permeable materials |
CA2114874A1 (en) * | 1993-02-08 | 1994-08-09 | Hanns-Peter Muller | Rigid hydrophobic polyurethanes |
Family Cites Families (377)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US655619A (en) * | 1899-09-13 | 1900-08-07 | William A Gay | Flue. |
US2240558A (en) | 1936-02-07 | 1941-05-06 | Standard Oil Dev Co | Nitrated diesel fuel and process of making same |
US2182513A (en) | 1936-05-14 | 1939-12-05 | Standard Oil Co | Method of sealing waxy surfaces |
US2202877A (en) | 1937-04-12 | 1940-06-04 | Gulf Oil Corp | Antioxidants and petroleum oils containing the same |
US2451420A (en) | 1943-07-28 | 1948-10-12 | Du Pont | Artificial yarns and process of producing the same |
US2463452A (en) | 1943-08-07 | 1949-03-01 | Du Pont | Adhesive compositions and adhesive sheets |
US3069236A (en) | 1955-03-10 | 1962-12-18 | Aerojet General Co | Method for the preparation of diborane |
US3148028A (en) | 1955-06-24 | 1964-09-08 | Aerojet General Co | Method for the preparation of diborane |
NL295726A (zh) | 1962-07-25 | |||
US3328372A (en) * | 1964-05-11 | 1967-06-27 | Exxon Research Engineering Co | Soluble high molecular weight polymers of cyclopentadiene |
NL6606553A (zh) * | 1965-06-18 | 1967-11-13 | ||
BE759829A (fr) * | 1969-12-03 | 1971-06-03 | Upjohn Co | Preparation de polyurethanes |
US3966624A (en) | 1971-07-15 | 1976-06-29 | Sun Oil Company Of Pennsylvania | Blended traction fluid containing hydrogenated polyolefin and an adamantane ether |
US3815611A (en) * | 1971-11-26 | 1974-06-11 | Medtronic Inc | Muscle stimulation and/or contraction detection device |
US3755265A (en) | 1972-04-04 | 1973-08-28 | Nasa | Highly fluorinated polyurethanes |
US4118427A (en) * | 1973-02-13 | 1978-10-03 | California Institute Of Technology | Curable liquid hydrocarbon prepolymers containing hydroxyl groups and process for producing same |
DE2418075A1 (de) | 1974-04-13 | 1975-10-30 | Bayer Ag | Thermoplastische polyurethan-elastomere mit verbesserter verarbeitbarkeit |
GB1527592A (en) * | 1974-08-05 | 1978-10-04 | Ici Ltd | Wound dressing |
US4157430A (en) | 1975-05-05 | 1979-06-05 | The Firestone Tire & Rubber Company | Amine terminated polymers and the formation of block copolymers |
US4154913A (en) | 1975-05-05 | 1979-05-15 | The Firestone Tire & Rubber Company | Amine terminated polymers and the formation of blocked copolymers |
US4157429A (en) | 1975-05-05 | 1979-06-05 | The Firestone Tire & Rubber Company | Amine terminated polymers and the formation of block copolymers |
GB1542319A (en) * | 1975-11-26 | 1979-03-14 | Exxon Research Engineering Co | Halogenated organoaluminium catalyst compositions and method of their preparation |
US4145515A (en) | 1976-12-01 | 1979-03-20 | Congoleum Corporation | Method of forming storage-stable polyurethane prepolymers |
US4352359A (en) * | 1977-08-19 | 1982-10-05 | Minnesota Mining And Manufacturing Company | Biomedical electrode |
US4230509A (en) | 1979-04-13 | 1980-10-28 | The United States Of America As Represented By The Secretary Of The Army | Pyrophoric flame composition |
US4304771A (en) | 1979-07-13 | 1981-12-08 | Usv Pharmaceutical Corporation | Antihypertensive amides |
US4316973A (en) * | 1979-09-10 | 1982-02-23 | The University Of Akron | Novel telechelic polymers and processes for the preparation thereof |
US4276394A (en) * | 1979-09-10 | 1981-06-30 | The University Of Akron | Novel telechelic polymers, block copolymers and processes for the preparation thereof |
US4342849A (en) * | 1979-09-10 | 1982-08-03 | The University Of Akron | Novel telechelic polymers and processes for the preparation thereof |
US4539996A (en) * | 1980-01-23 | 1985-09-10 | Minnesota Mining And Manufacturing Company | Conductive adhesive and biomedical electrode |
US4686137A (en) * | 1980-02-29 | 1987-08-11 | Thoratec Laboratories Corp. | Moisture vapor permeable materials |
US4861830A (en) * | 1980-02-29 | 1989-08-29 | Th. Goldschmidt Ag | Polymer systems suitable for blood-contacting surfaces of a biomedical device, and methods for forming |
US4675361A (en) * | 1980-02-29 | 1987-06-23 | Thoratec Laboratories Corp. | Polymer systems suitable for blood-contacting surfaces of a biomedical device, and methods for forming |
US4423185A (en) * | 1980-03-03 | 1983-12-27 | Asahi Kasei Kogyo Kabushiki Kaisha | Thermoplastic resinous composition |
US4430233A (en) | 1981-08-27 | 1984-02-07 | International Flavors & Fragrances Inc. | Branched chain ketones and uses thereof in augmenting or enhancing the aroma of perfumes, colognes and perfumed articles and the process for preparing same |
US4425264A (en) | 1981-08-27 | 1984-01-10 | International Flavors & Fragrances Inc. | Branched chain ketones used in augmenting or enhancing the aroma of perfumes, colognes and perfumed articles and the like process for preparing same |
US4374276A (en) | 1981-08-27 | 1983-02-15 | International Flavors & Fragrances Inc. | Novel branched chain ketones and the process for preparing same |
IL64952A (en) | 1982-02-08 | 1984-12-31 | Bromine Compounds Ltd | Intumescent fire retardant polymer compositions |
US4484586A (en) | 1982-05-27 | 1984-11-27 | Berkley & Company, Inc. | Hollow conductive medical tubing |
US4420411A (en) | 1982-06-04 | 1983-12-13 | International Flavors & Fragrances Inc. | Process for augmenting or enhancing the aroma of detergents using unsaturated branch chain ketones |
US4477604A (en) * | 1982-09-20 | 1984-10-16 | Oechsle Iii Sixtus J | Polyurethane compositions and their use as luting agents |
US4570270A (en) * | 1982-09-20 | 1986-02-18 | Oechsle Iii Sixtus J | Polyurethane compositions and their use as luting agents |
US4621172A (en) | 1982-12-22 | 1986-11-04 | Nec Corporation | Fast convergence method and system for echo canceller |
US4486572A (en) * | 1983-07-06 | 1984-12-04 | University Of Akron | Synthesis of amphiphilic block copolymers and networks |
US4518615A (en) | 1983-08-23 | 1985-05-21 | Warner-Lambert Company | Non-adhesive chewing gum base composition |
EP0153520A1 (en) | 1984-03-02 | 1985-09-04 | Morton Thiokol, Inc. | Radiation curable coating for photographic laminate |
US4508889A (en) | 1984-07-19 | 1985-04-02 | Desoto, Inc. | Preparation of isocyanate-terminated polyurethanes containing amino silanes |
US4767885A (en) * | 1984-08-06 | 1988-08-30 | University Of Akron | Sterically hindered binifers telechelic polymers made therefrom |
JPS6173666A (ja) | 1984-09-19 | 1986-04-15 | 日本ゼオン株式会社 | ポリウレタン又はポリウレタンウレアからなる抗血栓性材料及びその製造方法 |
GB2180123B (en) | 1984-12-21 | 1989-01-18 | Senezco Limited | Transponder systems |
US4888389A (en) * | 1985-02-05 | 1989-12-19 | University Of Akron | Amphiphilic polymers and method of making said polymers |
US4982038A (en) | 1985-03-19 | 1991-01-01 | Phillips Petroleum Company | Oxidative methylation of organic compounds |
US4600652A (en) | 1985-04-01 | 1986-07-15 | Warner-Lambert Company | Permanently bonded antithrombogenic polyurethane surface |
US4910321A (en) | 1985-06-20 | 1990-03-20 | University Of Akron | Living catalysts, complexes and polymers therefrom |
US4771082A (en) * | 1986-01-30 | 1988-09-13 | Solodovnik Valentin D | Polyurethane foam composition for immobilization in traumatology |
US5330520A (en) * | 1986-05-15 | 1994-07-19 | Telectronics Pacing Systems, Inc. | Implantable electrode and sensor lead apparatus |
JPS6345821A (ja) | 1986-08-13 | 1988-02-26 | Hitachi Tokyo Electron Co Ltd | 蒸気処理装置 |
EP0275907A3 (en) | 1987-01-23 | 1989-05-24 | Mobay Corporation | Rim polyurethane or polyurea compositions containing internal mold release agents |
US4880883A (en) * | 1987-06-03 | 1989-11-14 | Wisconsin Alumni Research Foundation | Biocompatible polyurethanes modified with lower alkyl sulfonate and lower alkyl carboxylate |
US5017664A (en) * | 1987-06-03 | 1991-05-21 | Wisconsin Alumni Research Foundation | Biocompatible polyurethane devices wherein polyurethane is modified with lower alkyl sulfonate and lower alkyl carboxylate |
EP0295640B1 (en) * | 1987-06-18 | 1993-02-03 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Polyurethane composition |
US4752626A (en) * | 1987-08-27 | 1988-06-21 | General Motors Corporation | Method of making low compression set urethane foams |
US5000875A (en) | 1987-10-16 | 1991-03-19 | E. I. Du Pont De Nemours And Company | Conductive filled fluoropolymers |
JPH054817Y2 (zh) | 1987-11-30 | 1993-02-08 | ||
US5149739A (en) * | 1988-08-01 | 1992-09-22 | The Bfgoodrich Company | Fiber-reinforced thermoplastic elastomer polyurethane compositions with either modified and/or unmodified polyolefins |
DE68912018T2 (de) | 1988-08-05 | 1994-04-28 | Edison Polymer Innovation | UV-härtbare Polymerzusammensetzung. |
US5171760A (en) | 1988-08-05 | 1992-12-15 | Edison Polymer Innovation Corp. | UV curable polymer formulation |
IT1227065B (it) | 1988-09-15 | 1991-03-14 | Ausimont Spa | Poliuretani fluorurati, contenenti blocchi gommosi a struttura polios siperfluoroalchilenica blocchi rigidi idrogenati, aventi migliorate proprieta' meccaniche. |
JPH02202908A (ja) | 1989-02-02 | 1990-08-13 | Nippon Zeon Co Ltd | ウレタン組成物 |
US4939184A (en) * | 1989-03-07 | 1990-07-03 | University Of Akron | Polyurethane foam |
EP0388480A1 (de) * | 1989-03-20 | 1990-09-26 | Siemens Aktiengesellschaft | Implantierbare Reizelektrode |
US5433730A (en) * | 1989-05-03 | 1995-07-18 | Intermedics, Inc. | Conductive pouch electrode for defibrillation |
US4928689A (en) * | 1989-05-15 | 1990-05-29 | Cardiac Pacemakers, Inc. | Rate adaptive cardiac pacer system having living cell tissue for sensing physiologic demand |
US5029585A (en) | 1989-07-14 | 1991-07-09 | Baxter International Inc. | Comformable intralumen electrodes |
US5194505A (en) * | 1989-09-29 | 1993-03-16 | E. I. Du Pont De Nemours And Company | Chlorosulfonated polyolefin-modified polyurethane and polyurea compositions and process for making same |
US5090422A (en) * | 1990-04-19 | 1992-02-25 | Cardiac Pacemakers, Inc. | Implantable electrode pouch |
US5282844A (en) * | 1990-06-15 | 1994-02-01 | Medtronic, Inc. | High impedance, low polarization, low threshold miniature steriod eluting pacing lead electrodes |
BR9003841A (pt) | 1990-08-06 | 1992-02-25 | Sika S A | Resina de poliuretana,adesivo,resina epoxi,processo para producao das ditas resinas,tinta e uso |
DE59108551D1 (de) * | 1990-08-16 | 1997-03-27 | Basf Ag | Verfahren zur Herstellung von Kohlenwasserstoffen und Polymeren mit allylischen Chloridendgruppen |
JP2969470B2 (ja) | 1990-10-18 | 1999-11-02 | 鐘淵化学工業株式会社 | 末端にアリル基を有するイソブチレン系重合体およびその製造方法 |
US5129404A (en) * | 1990-12-21 | 1992-07-14 | Intermedics, Inc. | Implantable endocardial lead with retractable fixation apparatus |
US5152299A (en) * | 1991-04-19 | 1992-10-06 | Intermedics, Inc. | Implantable endocardial lead with spring-loaded screw-in fixation apparatus |
IT1252660B (it) | 1991-12-23 | 1995-06-20 | Ausimont Spa | Poliuretani e poliuretani-uree fluorurati e processi per la loro preparazione |
DE4202033C2 (de) * | 1992-01-25 | 1995-06-22 | Escher Wyss Gmbh | Heiz- oder Kühlwalze |
DE69211360T2 (de) | 1992-02-10 | 1997-01-30 | Minnesota Mining & Mfg | Strahlungsvernetzte Elastomere |
US6010715A (en) * | 1992-04-01 | 2000-01-04 | Bertek, Inc. | Transdermal patch incorporating a polymer film incorporated with an active agent |
JP3857306B2 (ja) * | 1992-04-24 | 2006-12-13 | ザ ポリマー テクノロジー グループ,インコーポレイティド | 所定分子量レンジの分子を透過させるためのコポリマー及びそれらの非細孔性,半透過性膜並びにその使用 |
US5589563A (en) * | 1992-04-24 | 1996-12-31 | The Polymer Technology Group | Surface-modifying endgroups for biomedical polymers |
US5269810A (en) * | 1992-06-19 | 1993-12-14 | W. L. Gore & Associates, Inc. | Patch electrode |
US5324324A (en) * | 1992-10-13 | 1994-06-28 | Siemens Pacesetter, Inc. | Coated implantable stimulation electrode and lead |
US5322520A (en) * | 1992-11-12 | 1994-06-21 | Implemed, Inc. | Iontophoretic structure for medical devices |
US5340881A (en) * | 1992-11-16 | 1994-08-23 | The University Of Akron | Aldehyde-telechelic polyisobutylenes, catalytic method for preparing the same with high conversion and selectivity, and block copolymers made thereform |
JPH08505539A (ja) * | 1993-02-01 | 1996-06-18 | ダブリュ.エル.ゴア アンド アソシエーツ,インコーポレイティド | インプラント用電極 |
EP0612538A3 (en) * | 1993-02-22 | 1995-04-05 | Cardiac Pacemakers Inc | Metallized heart electrode. |
US5385579A (en) * | 1993-03-30 | 1995-01-31 | Siemens Pacesetter, Inc. | Myocardial body implantable lead |
GB9306887D0 (en) * | 1993-04-01 | 1993-05-26 | Graham Neil B | Random block copolymers |
JPH06345821A (ja) | 1993-04-12 | 1994-12-20 | Kanegafuchi Chem Ind Co Ltd | 不飽和基を有するイソブチレン系重合体の製造方法 |
US5476496A (en) * | 1993-06-01 | 1995-12-19 | Pacesetter Ab | Implantable medical electrode system having an indifferent electrode formed as a part of the electrode insulator sleeve |
JP3418434B2 (ja) | 1993-10-07 | 2003-06-23 | 鐘淵化学工業株式会社 | 末端に官能基を有する重合体及びその製造方法 |
US5637647A (en) * | 1993-10-15 | 1997-06-10 | University Of Massachusetts Lowell | Capping of living polymers |
CA2174246C (en) | 1993-10-29 | 2004-05-11 | Gary R. Schildgen | Method of manufacturing a medical electrical lead |
FR2713989B1 (fr) | 1993-12-21 | 1996-01-12 | Nipson | Imprimante à haute cadence d'impression et utilisations d'une telle imprimante. |
JPH07331223A (ja) | 1994-06-06 | 1995-12-19 | Kanegafuchi Chem Ind Co Ltd | 医療用粘着組成物 |
JPH07330591A (ja) | 1994-06-06 | 1995-12-19 | Kanegafuchi Chem Ind Co Ltd | 経皮吸収製剤 |
BE1008706A3 (fr) | 1994-09-28 | 1996-07-02 | Cockerill Rech & Dev | Produit pour la formation d'un revetement sur un support et procede de preparation de ce produit. |
US5442010A (en) * | 1994-10-04 | 1995-08-15 | Dow Corning Corporation | Epoxy-terminated polyisobutylene-polydimethylsiloxane compositions |
US5691062A (en) | 1995-02-16 | 1997-11-25 | Clemson University | Molecularly bonded inherently conductive polymers on substrates and shaped articles thereof |
CA2168938C (en) | 1995-03-13 | 2010-06-01 | Wolfgang Kaufhold | A thermoplastic polyurethane resin |
US5559067A (en) | 1995-03-31 | 1996-09-24 | Engelhard Corporation | Modified microsphere FCC catalysts and manufacture thereof |
GB9507393D0 (en) | 1995-04-10 | 1995-05-31 | Bp Chem Int Ltd | Polyolefin diols |
US5837313A (en) | 1995-04-19 | 1998-11-17 | Schneider (Usa) Inc | Drug release stent coating process |
US5639847A (en) | 1995-05-25 | 1997-06-17 | Mearthane Products Corp. | Preparation of conductive polyurethanes using a conductive quasi-solution |
US5630844A (en) | 1995-06-07 | 1997-05-20 | Novamed Medical Products Manufacturing, Inc. | Biocompatible hydrophobic laminate with thermoplastic elastomer layer |
US5681514A (en) | 1995-06-07 | 1997-10-28 | Sulzer Intermedics Inc. | Method for making an implantable conductive lead for use with a cardiac stimulator |
US5663234A (en) | 1995-06-15 | 1997-09-02 | The University Of Akron | Cationic multiblock thermoplastic elastomers |
GB9513713D0 (en) | 1995-07-05 | 1995-09-06 | Exxon Chemical Patents Inc | Curable elastomeric compositions and a process to produce curable elastomeric compositions |
US6369123B1 (en) | 1995-08-14 | 2002-04-09 | 3M Innovative Properties Company | Radiation-crosslinkable elastomers and photocrosslinkers therefor |
US5987746A (en) | 1996-02-21 | 1999-11-23 | Medtronic, Inc. | Method of making medical electrical lead |
DE19610350A1 (de) | 1996-03-15 | 1997-09-18 | Basf Ag | Initiatoren für die anionisch initiierte Polymerisation von wenigstens eine ethylenisch ungesättigte Gruppe aufweisenden Monomeren |
US5912302A (en) | 1996-06-11 | 1999-06-15 | Gadkari; Avinash Chandrakant | Elastomeric compositions and a process to produce elastomeric compositions |
US5755762A (en) | 1996-06-14 | 1998-05-26 | Pacesetter, Inc. | Medical lead and method of making and using |
US5741331A (en) * | 1996-07-29 | 1998-04-21 | Corvita Corporation | Biostable elastomeric polymers having quaternary carbons |
US5665823A (en) | 1996-08-30 | 1997-09-09 | Dow Corning Corporation | Polyisobutylene polymers having acrylic functionality |
US6200589B1 (en) * | 1996-09-13 | 2001-03-13 | The University Of Akron | Biological implants of semipermeable amphiphilic membranes |
AUPO251096A0 (en) * | 1996-09-23 | 1996-10-17 | Cardiac Crc Nominees Pty Limited | Polysiloxane-containing polyurethane elastomeric compositions |
ES2136927T3 (es) * | 1996-10-15 | 1999-12-01 | Advanced Elastomer Systems | Nuevos copolimeros de bloques de poliolefinas con poliuretanos, copoliesteres o copoliamidas y su uso. |
US5874484A (en) * | 1997-01-30 | 1999-02-23 | Shell Oil Company | Use of polyol mixtures in rigid and semi-rigid polyurethane foams |
WO1998033832A1 (en) | 1997-01-30 | 1998-08-06 | Shell Internationale Research Maatschappij B.V. | Use of polyol mixtures in rigid and semi-rigid polyurethane foams |
DE69805162T2 (de) | 1997-01-30 | 2002-10-31 | Kraton Polymers Research B.V., Amsterdam | Verwendung von polyolgemischen für polyurethan-(halb)hartschaumstoffe |
US5796044A (en) | 1997-02-10 | 1998-08-18 | Medtronic, Inc. | Coiled wire conductor insulation for biomedical lead |
US6117554A (en) | 1997-05-30 | 2000-09-12 | Poly-Med, Inc. | Modulated molecularly bonded inherently conductive polymers on substrates with conjugated multiple lamellae and shaped articles thereof |
US5886089A (en) | 1997-06-04 | 1999-03-23 | Gfx Technologies, Inc. | Grip and friction enhancement compositions |
US6005051A (en) * | 1997-08-06 | 1999-12-21 | The University Of Akron | Multi-component polymeric networks containing polyisobutylene |
US6072003A (en) * | 1997-08-25 | 2000-06-06 | Advanced Elastomer Systems, L.P. | Block copolymers of polyolefins with polyurethanes, copolyesters or copolyamides and their use |
US20020012694A1 (en) | 1997-09-17 | 2002-01-31 | Alfred J. Moo-Young | Transdermal administration of ment |
JP3671624B2 (ja) | 1997-10-27 | 2005-07-13 | 株式会社カネカ | ポリウレタン系弾性繊維 |
SE510868C2 (sv) | 1997-11-03 | 1999-07-05 | Artimplant Dev Artdev Ab | Formkroppar för användning som implantat i humanmedicin samt förfarande för framställning av sådana formkroppar |
US5991667A (en) | 1997-11-10 | 1999-11-23 | Vitatron Medical, B.V. | Pacing lead with porous electrode for stable low threshold high impedance pacing |
JP3539544B2 (ja) | 1998-01-06 | 2004-07-07 | シャープ株式会社 | 表面改質方法および表面改質粒子 |
US5902329A (en) | 1997-11-14 | 1999-05-11 | Pacesetter, Inc. | Explantable lead |
DE69822270T2 (de) | 1997-11-14 | 2005-01-13 | Sharp K.K. | Verfahren und Einrichtung zur Hertellung von modifizierten Partikeln |
US6093197A (en) * | 1997-12-08 | 2000-07-25 | Axon Engineering, Inc. | Spiral nerve cuff electrode implantation tool |
US5861023A (en) | 1997-12-16 | 1999-01-19 | Pacesetter, Inc. | Thrombus and tissue ingrowth inhibiting overlays for defibrillator shocking coil electrodes |
US5931862A (en) | 1997-12-22 | 1999-08-03 | Pacesetter, Inc. | Medical lead and method of making and using with sodium sulfosuccinic ester |
DE19800697B4 (de) | 1998-01-10 | 2009-04-02 | Biotronik Gmbh & Co. Kg | Einzel-Elektrodensonde, insbesondere für implantierbare Defibrillatoren |
WO1999051656A1 (en) | 1998-03-31 | 1999-10-14 | Sekisui Chemical Co., Ltd. | Polyesterurethane elastomers and process for their production |
US6256541B1 (en) | 1998-04-17 | 2001-07-03 | Cardiac Pacemakers, Inc. | Endocardial lead having defibrillation and sensing electrodes with septal anchoring |
US20020138123A1 (en) | 1998-04-21 | 2002-09-26 | Medtronic, Inc. | Medical electrical leads and indwelling catheters with enhanced biocompatibility and biostability |
EP1111442A4 (en) | 1998-08-26 | 2003-01-08 | Nissan Chemical Ind Ltd | AGENTS FOR TREATING LIQUID CRYSTAL ORIENTATION LAYERS AND A LIQUID CRYSTAL DEVICE USING THIS AND METHOD FOR ALIGNING LIQUID CRYSTALS |
CN1075103C (zh) | 1998-09-21 | 2001-11-21 | 深圳市奥博胶粘剂化工有限公司 | 一种聚氨酯粘接剂/密封胶组合物及其制备方法 |
JP2000119363A (ja) | 1998-10-13 | 2000-04-25 | Kanegafuchi Chem Ind Co Ltd | 末端にアルコール性水酸基を有する炭化水素系重合体及びその製造方法 |
US6361780B1 (en) | 1998-11-12 | 2002-03-26 | Cardiac Pacemakers, Inc. | Microporous drug delivery system |
JP4057174B2 (ja) | 1998-12-08 | 2008-03-05 | 株式会社カネカ | 粘着剤組成物および粘着製品の製造方法 |
JP2000264947A (ja) | 1999-03-18 | 2000-09-26 | Asahi Chem Ind Co Ltd | 硬化性組成物 |
JP5264030B2 (ja) | 1999-03-23 | 2013-08-14 | カーネギー−メロン ユニバーシティ | フリーラジカル的に(共)重合可能なモノマーの制御された重合のための触媒法、およびそれによって製造される官能性高分子系 |
JP3795697B2 (ja) | 1999-04-20 | 2006-07-12 | 株式会社カネカ | ポリウレタン系弾性繊維 |
US6253110B1 (en) | 1999-04-27 | 2001-06-26 | Medtronic Inc | Method for tissue stimulation and fabrication of low polarization implantable stimulation electrode |
US6869466B2 (en) | 1999-05-07 | 2005-03-22 | Unisearch Limited | Cucurbiturils and method for binding gases and volatiles using cucurbiturils |
EP1061092A1 (en) | 1999-06-17 | 2000-12-20 | Shell Internationale Researchmaatschappij B.V. | Process for the preparation of a rigid polyurethane foam. |
JP2001011319A (ja) | 1999-06-30 | 2001-01-16 | Kanegafuchi Chem Ind Co Ltd | 硬化性組成物 |
JP2001040064A (ja) | 1999-07-30 | 2001-02-13 | Kanegafuchi Chem Ind Co Ltd | 硬化性組成物 |
US6284682B1 (en) | 1999-08-26 | 2001-09-04 | The University Of British Columbia | Process for making chemically bonded sol-gel ceramics |
US6363286B1 (en) | 1999-09-24 | 2002-03-26 | Cardiac Pacemakers, Inc. | High impedance electrode assembly |
JP2001131879A (ja) | 1999-10-25 | 2001-05-15 | Kanegafuchi Chem Ind Co Ltd | 人工皮革 |
JP4154815B2 (ja) | 1999-10-28 | 2008-09-24 | ぺんてる株式会社 | バーコード読み取り装置 |
US6228945B1 (en) * | 1999-12-20 | 2001-05-08 | The University Of Akron | Three arm star compositions of matter having diblock arms based on polyisobutylene and methods of preparation |
US20010021743A1 (en) | 1999-12-28 | 2001-09-13 | Yuichiro Wakana | Method of producing a graft copolymer |
KR20020063300A (ko) | 2000-01-21 | 2002-08-01 | 미쓰이 가가쿠 가부시키가이샤 | 올레핀계 블록 공중합체, 그 제조방법 및 그 용도 |
US6426114B1 (en) | 2000-05-02 | 2002-07-30 | The University Of British Columbia | Sol-gel calcium phosphate ceramic coatings and method of making same |
US7013182B1 (en) | 2000-05-04 | 2006-03-14 | Cardiac Pacemakers, Inc. | Conductive polymer sheath on defibrillator shocking coils |
US6242058B1 (en) | 2000-05-12 | 2001-06-05 | Dow Corning Corporation | Method for forming coatings from radiation curable compositions containing alkenyl ether functional polyisobutylenes |
US6703433B1 (en) | 2000-05-12 | 2004-03-09 | Dow Corning Corporation | Radiation curable compositions containing alkenyl ether functional polyisobutylenes |
AU2001261960A1 (en) | 2000-05-19 | 2001-11-26 | The University Of British Columbia | Process for making chemically bonded composite hydroxide ceramics |
US6555619B1 (en) | 2000-06-29 | 2003-04-29 | The University Of Akron | Physically crosslinked amphiphilic networks, methods of preparation, and uses thereof |
US20020022826A1 (en) | 2000-08-14 | 2002-02-21 | Reynolds John R. | Burst electrode |
US6849667B2 (en) * | 2000-10-18 | 2005-02-01 | Mitsui Chemicals, Inc. | Foam of thermoplastic urethane elastomer composition and process for producing the foam |
TW541853B (en) * | 2000-11-10 | 2003-07-11 | Sumitomo Chemical Co | Polymeric fluorescent substance and polymer light-emitting device using the same |
US6533955B1 (en) | 2000-11-20 | 2003-03-18 | 3M Innovative Properties Company | Conductive fluoropolymers |
US6545097B2 (en) * | 2000-12-12 | 2003-04-08 | Scimed Life Systems, Inc. | Drug delivery compositions and medical devices containing block copolymer |
US6704604B2 (en) | 2000-12-28 | 2004-03-09 | Medtronic, Inc. | System and method for promoting selective tissue in-growth for an implantable medical device |
JP3785931B2 (ja) | 2000-12-28 | 2006-06-14 | 日本電気株式会社 | 入出力要求遮断方式、入出力要求遮断方法および入出力要求遮断用プログラムを記録した記録媒体 |
JP3808758B2 (ja) | 2001-03-22 | 2006-08-16 | 株式会社カネカ | イソブチレン系重合体の製造方法 |
US7396582B2 (en) | 2001-04-06 | 2008-07-08 | Advanced Cardiovascular Systems, Inc. | Medical device chemically modified by plasma polymerization |
US6730324B2 (en) | 2001-04-20 | 2004-05-04 | The University Of British Columbia | Biofunctional hydroxyapatite coatings and microspheres for in-situ drug encapsulation |
US6653365B2 (en) | 2001-05-01 | 2003-11-25 | Pentron Clinical Technologies, Llc | Dental composite materials and method of manufacture thereof |
US7589132B2 (en) | 2001-05-01 | 2009-09-15 | Pentron Clinical Technologies, Llc | Dental resins, dental composite materials, and method of manufacture thereof |
US7160941B2 (en) | 2001-05-01 | 2007-01-09 | Pentron Clinical Technologies, Llc | Dental composite materials and method of manufacture thereof |
US7470728B2 (en) | 2001-05-01 | 2008-12-30 | Pentron Clinical Technologies Llc | Dental glazes and method of manufacture and use thereof |
ITMI20011306A1 (it) | 2001-06-21 | 2002-12-21 | Ausimont Spa | Poliuretani vulcanizzabili |
US7363091B1 (en) | 2001-07-11 | 2008-04-22 | Pacesetter Inc. | Method of molding silicone elastomer drug carrier in an endocardial lead |
US6600956B2 (en) * | 2001-08-21 | 2003-07-29 | Cyberonics, Inc. | Circumneural electrode assembly |
US6852794B2 (en) | 2001-09-07 | 2005-02-08 | The Goodyear Tire & Rubber Company | Rubber compound containing a polyhedral oligomeric silsesquioxanes |
IN2014DN10834A (zh) | 2001-09-17 | 2015-09-04 | Psivida Inc | |
US20030073961A1 (en) | 2001-09-28 | 2003-04-17 | Happ Dorrie M. | Medical device containing light-protected therapeutic agent and a method for fabricating thereof |
EP1437055B1 (en) | 2001-10-16 | 2008-01-09 | Japan Tobacco Inc. | Feeding device of a splicing tape |
JP3969058B2 (ja) | 2001-10-31 | 2007-08-29 | 東ソー株式会社 | 軟質ポリウレタンフォームの製造方法 |
US7187980B2 (en) | 2001-11-09 | 2007-03-06 | Oscor Inc. | Cardiac lead with steroid eluting ring |
WO2003042273A1 (en) | 2001-11-14 | 2003-05-22 | Medtronic, Inc. | Compounds containing quaternary carbons, medical devices, and methods |
EP1446437B1 (en) * | 2001-11-14 | 2015-04-15 | Medtronic, Inc. | Compounds containing quaternary carbons, medical devices, and methods |
US6709514B1 (en) | 2001-12-28 | 2004-03-23 | Advanced Cardiovascular Systems, Inc. | Rotary coating apparatus for coating implantable medical devices |
DE10206123A1 (de) | 2002-02-14 | 2003-09-04 | Wacker Chemie Gmbh | Organopolysiloxan/Polyharnstoff/Polyurethan-Blockcopolymer aufweisende textile Gebilde |
US6777026B2 (en) | 2002-10-07 | 2004-08-17 | Lord Corporation | Flexible emissive coatings for elastomer substrates |
US7196142B2 (en) * | 2002-04-04 | 2007-03-27 | The University Of Akron | Polyisobutylene-based block anionomers and cationomers and synthesis thereof |
US20030236513A1 (en) | 2002-06-19 | 2003-12-25 | Scimed Life Systems, Inc. | Implantable or insertable medical devices for controlled delivery of a therapeutic agent |
US7292890B2 (en) * | 2002-06-20 | 2007-11-06 | Advanced Bionics Corporation | Vagus nerve stimulation via unidirectional propagation of action potentials |
AUPS318202A0 (en) | 2002-06-26 | 2002-07-18 | Cochlear Limited | Parametric fitting of a cochlear implant |
JP2006500088A (ja) | 2002-08-13 | 2006-01-05 | メドトロニック・インコーポレーテッド | ポリマーの被覆及び支持体間の改良された付着を示す医用デバイス |
US7438925B2 (en) | 2002-08-26 | 2008-10-21 | Biovention Holdings Ltd. | Drug eluting coatings for medical implants |
DE10241853B3 (de) * | 2002-09-09 | 2004-01-22 | Byk-Chemie Gmbh | Polymeres Harnstoffurethan als Rheologiesteuerungsmittel und Verfahren zur Herstellung |
CA2499347A1 (en) * | 2002-09-17 | 2004-04-01 | Medtronic, Inc. | Compounds containing quaternary carbons and silicon-containing groups, medical devices, and methods |
US20040063805A1 (en) | 2002-09-19 | 2004-04-01 | Pacetti Stephen D. | Coatings for implantable medical devices and methods for fabrication thereof |
US6770729B2 (en) | 2002-09-30 | 2004-08-03 | Medtronic Minimed, Inc. | Polymer compositions containing bioactive agents and methods for their use |
US7231259B2 (en) | 2002-10-04 | 2007-06-12 | Pacesetter, Inc. | Body implantable lead comprising electrically conductive polymer conductors |
HUP0203632A3 (en) | 2002-10-25 | 2005-08-29 | Furukawa Electric Technologiai | Recyclable crosslinked polymers with saturated main chain and thermally reversible urethane crosslink points |
US6896965B1 (en) | 2002-11-12 | 2005-05-24 | Advanced Cardiovascular Systems, Inc. | Rate limiting barriers for implantable devices |
EP1567559A4 (en) | 2002-11-12 | 2008-04-16 | Polymer Technology Group Inc | REGULATION OF MOLECULAR POLYMER SURFACE ARCHITECTURE USING AMPHIPATHIC TERMINAL GROUPS |
JP4160379B2 (ja) | 2002-12-26 | 2008-10-01 | 株式会社カネカ | 熱可塑性エラストマー組成物 |
US20050043585A1 (en) * | 2003-01-03 | 2005-02-24 | Arindam Datta | Reticulated elastomeric matrices, their manufacture and use in implantable devices |
US8016752B2 (en) | 2003-01-17 | 2011-09-13 | Gore Enterprise Holdings, Inc. | Puncturable catheter |
US6960207B2 (en) | 2003-01-21 | 2005-11-01 | St Jude Medical, Daig Division, Inc. | Ablation catheter having a virtual electrode comprising portholes and a porous conductor |
DE10303275A1 (de) | 2003-01-28 | 2004-07-29 | Basf Ag | Funktionalisierung von ungesättigten Isobutenpolymeren durch Hydroborierung |
US20040147994A1 (en) | 2003-01-28 | 2004-07-29 | Cardiac Pacemakers, Inc. | Tachy lead system optimized for septal placement |
US20050079199A1 (en) | 2003-02-18 | 2005-04-14 | Medtronic, Inc. | Porous coatings for drug release from medical devices |
US20080051866A1 (en) | 2003-02-26 | 2008-02-28 | Chao Chin Chen | Drug delivery devices and methods |
US6926919B1 (en) | 2003-02-26 | 2005-08-09 | Advanced Cardiovascular Systems, Inc. | Method for fabricating a coating for a medical device |
US7172575B2 (en) | 2003-03-05 | 2007-02-06 | Advanced Cardiovascular Systems, Inc. | Catheter balloon having a lubricious coating |
US20040186545A1 (en) | 2003-03-20 | 2004-09-23 | Rosero Spencer Z. | Temporary percutaneous cardioverter-defibrillator |
US7065411B2 (en) | 2003-04-23 | 2006-06-20 | Medtronic, Inc. | Electrical medical leads employing conductive aerogel |
GB0311121D0 (en) * | 2003-05-15 | 2003-06-18 | Avecia Ltd | Polyurethane dispersants |
US20050060022A1 (en) * | 2003-05-21 | 2005-03-17 | Felt Jeffrey C. | Polymer stent |
WO2004114732A1 (en) | 2003-06-19 | 2004-12-29 | World Properties, Inc. | Material including a liquid crystalline polymer and a polyhedral oligomeric silsesquioxane (poss) filler |
US6969744B2 (en) | 2003-06-19 | 2005-11-29 | University Of Southern Mississippi | Living and quasiliving cationic telechelic polymers quenched by N-substituted pyrrole and methods for their preparation |
WO2004113400A2 (en) | 2003-06-20 | 2004-12-29 | Scimed Life Systems, Inc. | End-cappped polymer chains and products thereof |
DE10328854A1 (de) | 2003-06-26 | 2005-01-13 | Basf Ag | Verfahren zur Herstellung von Polyisobutenen |
EP1639024A4 (en) * | 2003-07-01 | 2008-03-12 | Univ Akron Akron Ohio | THERMOPLASTIC ELASTOMERS MULTIPLOCK COPOLYMERS OF ISOBUTYLENE AND NORBORNE |
US7364585B2 (en) | 2003-08-11 | 2008-04-29 | Boston Scientific Scimed, Inc. | Medical devices comprising drug-loaded capsules for localized drug delivery |
KR100579007B1 (ko) | 2003-08-13 | 2006-05-12 | 주식회사 루밴틱스 | 대전 방지 특성을 가진 광섬유 코팅용 광경화형 고분자수지 조성물 |
US7953499B2 (en) | 2003-09-30 | 2011-05-31 | Cardiac Pacemakers, Inc. | Drug-eluting electrode |
US20050080470A1 (en) | 2003-10-09 | 2005-04-14 | Randy Westlund | Intramyocardial lead implantation system and method |
GB0323733D0 (en) | 2003-10-10 | 2003-11-12 | Univ Heriot Watt | Conductive polymer |
GB0326286D0 (en) | 2003-11-11 | 2003-12-17 | Vantico Gmbh | Initiator systems for polymerisable compositions |
US7807722B2 (en) | 2003-11-26 | 2010-10-05 | Advanced Cardiovascular Systems, Inc. | Biobeneficial coating compositions and methods of making and using thereof |
US7119138B1 (en) | 2003-12-19 | 2006-10-10 | Inmat Inc. | Barrier coating of a mixture of cured and uncured elastomeric polymers and a dispersed layered filler in a liquid carrier and coated articles |
GB0401202D0 (en) | 2004-01-20 | 2004-02-25 | Ucl Biomedica Plc | Polymer for use in conduits and medical devices |
US7572515B2 (en) | 2004-01-20 | 2009-08-11 | World Properties, Inc. | Circuit materials, circuits, multi-layer circuits, and methods of manufacture thereof |
US7280875B1 (en) | 2004-02-04 | 2007-10-09 | Pacesetter, Inc. | High strength, low resistivity electrode |
US7056985B2 (en) * | 2004-02-11 | 2006-06-06 | University Of Massachusetts Lowell | End-capped polymer chains and products thereof |
US20050180919A1 (en) | 2004-02-12 | 2005-08-18 | Eugene Tedeschi | Stent with radiopaque and encapsulant coatings |
US20070190108A1 (en) * | 2004-05-17 | 2007-08-16 | Arindam Datta | High performance reticulated elastomeric matrix preparation, properties, reinforcement, and use in surgical devices, tissue augmentation and/or tissue repair |
US7105622B2 (en) * | 2004-06-02 | 2006-09-12 | The University Of Akron | Hybrid polyurethanes |
US20050288476A1 (en) * | 2004-06-17 | 2005-12-29 | Iskender Yilgor | Thermoplastic copolymers through stoichiometric reactions between diisocyanates and oligomeric diols and diamines |
CA2471006A1 (en) | 2004-06-23 | 2005-12-23 | Bayer Inc. | Silica reinforced elastomer compounds prepared with dry liquid modifiers |
JP2006274235A (ja) | 2004-07-30 | 2006-10-12 | Fuji Photo Film Co Ltd | 重合性組成物、光学異方性層及びその製造方法、光学補償素子、液晶表示装置及び液晶プロジェクタ |
JP4155243B2 (ja) | 2004-08-04 | 2008-09-24 | トヨタ自動車株式会社 | 電磁駆動弁 |
US20060047083A1 (en) * | 2004-08-30 | 2006-03-02 | Iskender Yilgor | Triblock copolymers and their production methods |
US7289856B1 (en) | 2004-09-29 | 2007-10-30 | Pacesetter, Inc. | Medical electrical lead containing a pyroelectric material |
US7347751B2 (en) * | 2004-09-30 | 2008-03-25 | Cardiac Pacemakers, Inc. | Cardiac lead implantation system |
DE102004048991B4 (de) | 2004-10-04 | 2010-01-28 | Biotronik Crm Patent Ag | Elektrodenleitung |
GB0428444D0 (en) | 2004-12-29 | 2005-02-02 | Cambridge Display Tech Ltd | Conductive polymer compositions in opto-electrical devices |
US8075906B2 (en) | 2005-02-01 | 2011-12-13 | Boston Scientific Scimed, Inc. | Medical devices having polymeric regions with copolymers containing hydrocarbon and heteroatom-containing monomeric species |
US20060264577A1 (en) * | 2005-04-08 | 2006-11-23 | Rudolf Faust | Capping reactions in cationic polymerization; kinetic and synthetic utility |
US20060235499A1 (en) | 2005-04-14 | 2006-10-19 | Cardiac Pacemakers, Inc. | Coated lead fixation electrode |
US20060249446A1 (en) | 2005-05-04 | 2006-11-09 | Gary Yeager | Solvent-resistant composite membrane composition |
US20070051531A1 (en) | 2005-09-08 | 2007-03-08 | Harshad Borgaonkar | Drug eluting coatings for a medical lead and method therefor |
US7630749B2 (en) | 2005-11-07 | 2009-12-08 | Gore Enterprise Holdings, Inc. | Implantable electrophysiology lead body |
US7553546B1 (en) | 2005-11-16 | 2009-06-30 | Pacesetter, Inc. | Polyethylene oxide and silicone copolymers and their usage on medical devices |
US7715922B1 (en) * | 2005-11-16 | 2010-05-11 | Pacesetter, Inc. | Polyethylene oxide and polyisobutylene copolymers and their usage on medical devices |
US8034874B2 (en) | 2005-11-23 | 2011-10-11 | Boston Scientific Scimed, Inc. | Medical devices having polymeric regions that contain fluorocarbon-containing block copolymers |
US20070122361A1 (en) | 2005-11-29 | 2007-05-31 | Weitao Jia | Tooth colorant and whitener, method of manufacture, and method of use thereof |
US20070128246A1 (en) | 2005-12-06 | 2007-06-07 | Hossainy Syed F A | Solventless method for forming a coating |
US7501179B2 (en) | 2005-12-21 | 2009-03-10 | Boston Scientific Scimed, Inc. | Block copolymer particles |
US20070142560A1 (en) | 2005-12-21 | 2007-06-21 | Young-Ho Song | Block copolymer particles |
US20070190104A1 (en) | 2006-02-13 | 2007-08-16 | Kamath Kalpana R | Coating comprising an adhesive polymeric material for a medical device and method of preparing the same |
US7981509B2 (en) * | 2006-02-13 | 2011-07-19 | Donaldson Company, Inc. | Polymer blend, polymer solution composition and fibers spun from the polymer blend and filtration applications thereof |
US7465777B2 (en) | 2006-03-02 | 2008-12-16 | Boston Scientific Scimed, Inc. | Hybrid polymer materials from reactive extrusion for medical devices |
USD579758S1 (en) | 2006-03-23 | 2008-11-04 | Ykk Ap Inc. | Sash lock |
US7881808B2 (en) | 2006-03-29 | 2011-02-01 | Cardiac Pacemakers, Inc. | Conductive polymeric coating with optional biobeneficial topcoat for a medical lead |
US20070282411A1 (en) | 2006-03-31 | 2007-12-06 | Brian Franz | Compliant electrical stimulation leads and methods of fabrication |
US7737060B2 (en) | 2006-03-31 | 2010-06-15 | Boston Scientific Scimed, Inc. | Medical devices containing multi-component fibers |
EP2004715A2 (en) | 2006-04-07 | 2008-12-24 | University Of Massachusetts Lowell | Method to prepare block copolymers by the combination of cationic and anionic polymerization |
US20100249296A1 (en) | 2006-04-13 | 2010-09-30 | Kaneka Corporation | Rubber stopper composition and medical rubber stopper |
US7689291B2 (en) | 2006-05-01 | 2010-03-30 | Cardiac Pacemakers, Inc. | Lead with fibrous matrix coating and methods related thereto |
US7727541B2 (en) | 2006-05-18 | 2010-06-01 | Boston Scientific Scimed, Inc. | Medical devices having polymeric regions based on vinyl ether block copolymers |
US7951194B2 (en) | 2006-05-26 | 2011-05-31 | Abbott Cardiovascular Sysetms Inc. | Bioabsorbable stent with radiopaque coating |
US7998124B2 (en) | 2006-05-31 | 2011-08-16 | Kaneka Corporation | Catheter tube and catheter comprising the tube |
US20080095918A1 (en) | 2006-06-14 | 2008-04-24 | Kleiner Lothar W | Coating construct with enhanced interfacial compatibility |
ATE542492T1 (de) | 2006-06-20 | 2012-02-15 | Boston Scient Ltd | Medizinische vorrichtungen mit verbundstoffen |
US9028859B2 (en) | 2006-07-07 | 2015-05-12 | Advanced Cardiovascular Systems, Inc. | Phase-separated block copolymer coatings for implantable medical devices |
DE102006037582A1 (de) | 2006-08-11 | 2008-02-14 | Bayer Materialscience Ag | Antistatische und elektrisch leitfähige Polyurethane |
US20080108773A1 (en) | 2006-11-06 | 2008-05-08 | Wicks Douglas A | Polyurethane dispersions containing POSS nanoparticles |
US20100069578A1 (en) * | 2006-11-17 | 2010-03-18 | Rudolf Faust | Functional Hydrocarbon Polymers and Process for Producing Same |
US8163826B2 (en) | 2006-11-21 | 2012-04-24 | Schlumberger Technology Corporation | Polymeric acid precursor compositions and methods |
US20080124555A1 (en) | 2006-11-29 | 2008-05-29 | 3M Innovative Properties Company | Polymerizable composition comprising perfluoropolyether urethane having ethylene oxide repeat units |
CA2670786C (en) * | 2006-11-30 | 2015-06-23 | The University Of Akron | Polyisobutylenes, and process for making same |
US20160024340A1 (en) | 2006-12-14 | 2016-01-28 | Ppg Industries Ohio, Inc. | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
US20080167710A1 (en) | 2007-01-05 | 2008-07-10 | Vipul Bhupendra Dave | Medical Device Having Regions With Various Agents Dispersed Therein and a Method for Making the Same |
US20080175881A1 (en) | 2007-01-18 | 2008-07-24 | Boston Scientific Scimed, Inc. | Blood-contacting medical devices for the release of nitric oxide and anti-restenotic agents |
US20080194736A1 (en) | 2007-02-13 | 2008-08-14 | Minqiu Lu | PVC nanocomposite manufacturing technology and applications |
US20080208325A1 (en) | 2007-02-27 | 2008-08-28 | Boston Scientific Scimed, Inc. | Medical articles for long term implantation |
CN101686854B (zh) | 2007-03-09 | 2012-11-28 | 阿克伦大学 | 生物人工胰及其制备方法 |
JP5067419B2 (ja) * | 2007-03-16 | 2012-11-07 | 宇部興産株式会社 | 酸化亜鉛単結晶の製造方法 |
JP2008238761A (ja) | 2007-03-29 | 2008-10-09 | Toyoda Gosei Co Ltd | ポリウレタン材料及びその製造方法 |
CA2683844C (en) | 2007-04-12 | 2015-06-02 | Joseph P. Kennedy | Injectible cyanoacrylate-functionalized polyisobutylenes |
CN101809062B (zh) | 2007-06-19 | 2014-05-28 | 阿克伦大学 | 单封端的聚异丁烯及其制造方法 |
US7899552B2 (en) | 2007-10-15 | 2011-03-01 | Cardiac Pacemakers, Inc. | Conductive composite electrode material |
US8580900B2 (en) | 2007-11-01 | 2013-11-12 | The University Of Akron | Thermoplastic amphiphilic co-networks |
JP2009132832A (ja) | 2007-11-30 | 2009-06-18 | Asahi Glass Co Ltd | 一液型ポリウレタン系硬化性組成物およびこれを用いた接着剤 |
US20090156772A1 (en) | 2007-12-12 | 2009-06-18 | Boston Scientific Scimed, Inc. | Melt processed materials for medical articles |
FR2925062B1 (fr) | 2007-12-18 | 2011-03-04 | Michelin Soc Tech | Composition de caoutchouc notamment pour la fabrication de pneumatique |
FR2925061B1 (fr) | 2007-12-18 | 2010-01-15 | Michelin Soc Tech | Composition de caoutchouc notamment pour la fabrication de pneumatique |
US8349123B2 (en) | 2008-04-01 | 2013-01-08 | Henkel Corporation | High heat resistant adhesive and sealant compositions |
US20090292094A1 (en) | 2008-05-21 | 2009-11-26 | E. I. Dupont De Nemours And Company | Fluoropolymer Composition |
US8452258B2 (en) | 2008-06-20 | 2013-05-28 | Movirtu Limited | Method and system to implement telephone billing to incentivize shared mobile phone usage |
CN102131530A (zh) | 2008-06-27 | 2011-07-20 | 心脏起搏器公司 | 聚异丁烯-氨基甲酸酯共聚物、聚异丁烯-脲共聚物和聚异丁烯-氨基甲酸酯/脲共聚物及含有这类共聚物的医疗器械 |
US8372468B2 (en) * | 2008-09-19 | 2013-02-12 | Cardiac Pacemakers, Inc. | Surface modification to improve lubricity, abrasion resistance and temperature resilience of leads |
WO2010039986A1 (en) | 2008-10-01 | 2010-04-08 | The University Of Akron | Polymers having both hard and soft segments, and process for making same |
US8285396B2 (en) | 2009-01-05 | 2012-10-09 | Kenergy, Inc. | MRI compatible electrical lead for an implanted electronic medical device |
EP3670561B1 (en) | 2009-01-12 | 2023-12-06 | University Of Massachusetts Lowell | Polyisobutylene-based polyurethanes |
WO2010107530A2 (en) | 2009-03-17 | 2010-09-23 | Cardiac Pacemakers, Inc. | Porous fiber electrode coating and related methods |
US8765238B2 (en) | 2009-03-18 | 2014-07-01 | Boston Scientific Scimed, Inc. | Polymeric/inorganic composite materials for use in medical devices |
US8155759B2 (en) * | 2009-03-20 | 2012-04-10 | Innovia, Llc | Pacemaker lead and method of making same |
US20120077934A1 (en) | 2009-03-23 | 2012-03-29 | University Of Massachusetts | Functional Polyisobutylene Based Macromonomers And Methods For Making And Using The Same |
US20100298769A1 (en) | 2009-05-21 | 2010-11-25 | Boston Scientific Scimed, Inc. | Implantable medical devices for therapeutic agent delivery |
EP2467174B1 (en) | 2009-08-21 | 2018-09-26 | Cardiac Pacemakers, Inc. | Crosslinkable polyisobutylene-based polymers and medical devices containing the same |
US20110051581A1 (en) | 2009-08-25 | 2011-03-03 | Seagate Technology Llc | Vibration analysis methodology using data storage devices |
US8374704B2 (en) * | 2009-09-02 | 2013-02-12 | Cardiac Pacemakers, Inc. | Polyisobutylene urethane, urea and urethane/urea copolymers and medical leads containing the same |
US8644952B2 (en) * | 2009-09-02 | 2014-02-04 | Cardiac Pacemakers, Inc. | Medical devices including polyisobutylene based polymers and derivatives thereof |
CA2780272A1 (en) | 2009-11-11 | 2011-05-19 | The University Of Akron | Polyisobutylene-based polyurethanes, polyureas and/or polyurethane-polyureas and method for making same |
US20110152989A1 (en) | 2009-12-23 | 2011-06-23 | Pacesetter, Inc. | Soft abrasion-resistant polyisobutylene urethane copolymers |
EP2526156A1 (en) | 2010-01-21 | 2012-11-28 | Sun Chemical Corporation | Low-voc solvent systems |
EP2555762B1 (en) | 2010-04-06 | 2018-01-31 | Syracuse University | System and method for the release of nitric oxide using nanoscale media |
US9249254B2 (en) | 2010-04-22 | 2016-02-02 | Syracuse University | Polyhedral oligomeric silsesquioxane polyurethanes |
FR2962368B1 (fr) | 2010-07-09 | 2012-08-31 | Michelin Soc Tech | Objet pneumatique pourvu d'une couche etanche aux gaz a base d'un melange d'un caoutchouc butyl et d'un elastomere thermoplastique |
US8969424B2 (en) | 2010-10-15 | 2015-03-03 | Evoqua Water Technologies Llc | Anion exchange membranes and process for making |
JP5889907B2 (ja) | 2010-10-15 | 2016-03-22 | エヴォクア ウォーター テクノロジーズ エルエルシーEvoqua Water Technologiesllc | カチオン交換膜を製造するためのモノマー溶液の製造方法 |
CN103314029B (zh) | 2010-11-11 | 2015-05-13 | 陶氏环球技术有限责任公司 | 聚氨酯基绝缘玻璃密封剂 |
US8660663B2 (en) | 2010-12-20 | 2014-02-25 | Cardiac Pacemakers, Inc. | Lead having a conductive polymer conductor |
JP5742226B2 (ja) | 2011-01-04 | 2015-07-01 | 凸版印刷株式会社 | ガスバリア性積層体及びその製造方法並びにガスバリア性積層フィルム |
US9957346B2 (en) | 2011-02-23 | 2018-05-01 | The University Of Akron | Melt processible polyureas and polyurea-urethanes, method for the production thereof and products made therefrom |
US20130041108A1 (en) | 2011-05-19 | 2013-02-14 | Joseph P. Kennedy | Polymers having both hard and soft segments, and process for making same |
CA2840220A1 (en) | 2011-06-30 | 2013-01-03 | The University Of Akron | Method for the synthesis of low cost initiators for telechelic polyisobutylenes |
WO2013005004A1 (en) | 2011-07-02 | 2013-01-10 | Ucl Business Plc | Implantable small diameter drainage conduit |
AU2012295332B2 (en) | 2011-08-12 | 2014-12-04 | Cardiac Pacemakers, Inc. | Method for coating devices using electrospinning and melt blowing |
JP5974013B2 (ja) | 2011-09-22 | 2016-08-23 | 株式会社カネカ | 硬化性組成物およびその硬化物 |
CN102304679B (zh) | 2011-09-28 | 2013-01-30 | 宋玉军 | 一种非晶纳米晶梯度功能材料及其制备方法 |
US9655720B2 (en) | 2011-10-13 | 2017-05-23 | The Research Foundation For The State University Of New York | Polymeric heart valve |
FR2981937B1 (fr) | 2011-10-28 | 2013-11-08 | Michelin Soc Tech | Composition elastomerique presentant une tres bonne dispersion de la charge dans la matrice elastomerique |
WO2013078139A1 (en) | 2011-11-23 | 2013-05-30 | Cardiac Pacemakers, Inc. | Fibrous matrix coating materials |
WO2013087657A1 (fr) | 2011-12-12 | 2013-06-20 | Compagnie Generale Des Etablissements Michelin | Composition elastomerique presentant une tres bonne dispersion de la charge dans la matrice elastomerique |
FR2984340B1 (fr) | 2011-12-16 | 2018-01-12 | Soc Tech Michelin | Pneumatique pourvu d'un flanc externe a base d'un melange d'un elastomere dienique et d'un elastomere thermoplastique |
FR2984339B1 (fr) | 2011-12-16 | 2018-01-12 | Soc Tech Michelin | Pneumatique pourvu d'une bande de roulement a base d'un melange d'un elastomere dienique et d'un elastomere thermoplastique |
FR2984335B1 (fr) | 2011-12-16 | 2018-01-12 | Societe De Technologie Michelin | Pneumatique pourvu d'une couche interne a base d'un melange d'un elastomere dienique et d'un elastomere thermoplastique |
JP5879146B2 (ja) | 2012-02-16 | 2016-03-08 | 積水化成品工業株式会社 | 電極用パッド |
NZ717683A (en) | 2012-06-07 | 2018-04-27 | Aragon Pharmaceuticals Inc | Crystalline forms of an androgen receptor modulator |
JP2015514850A (ja) | 2012-06-18 | 2015-05-21 | ペトロケミカル サプライ インコーポレーテッド | 内部ビニリデンを有するポリイソブチレン組成物及びポリイソブチレン重合体組成物の製造方法 |
JP2015533859A (ja) | 2012-07-23 | 2015-11-26 | アクロン大学 | 有機修飾モンモリロナイトを含有するポリイソブチレン系ポリウレタン |
US20140074201A1 (en) | 2012-09-11 | 2014-03-13 | Cardiac Pacemakers, Inc. | Conformal porous thin layer coating and method of making |
US20140096964A1 (en) | 2012-10-10 | 2014-04-10 | Baker Hughes Incorporated | Nanoparticle modified fluids and methods of manufacture thereof |
EP2922888B1 (en) | 2012-11-21 | 2021-08-18 | The University of Massachusetts | High strength polyisobutylene polyurethanes |
USD689734S1 (en) | 2013-02-22 | 2013-09-17 | Hamilton Beach Brands, Inc. | Food processor |
US9604281B2 (en) | 2013-03-13 | 2017-03-28 | Syracuse University | Method to control void formation in nanomaterials using core/alloy nanoparticles with stainless interfaces |
JP6283092B2 (ja) | 2013-03-14 | 2018-02-21 | ナノシス・インク. | 多面体オリゴマー状シルセスキオキサンナノ結晶安定化リガンド |
MY185746A (en) | 2013-07-17 | 2021-06-03 | Basf Se | High-reactivity polyisobutylene having a high content of vinylidene double bonds in the side chains |
US9341948B2 (en) | 2013-08-24 | 2016-05-17 | Polyera Corporation | Photopatternable materials and related electronic devices and methods |
CN106659895B (zh) | 2014-07-11 | 2019-06-25 | 心脏起搏器股份公司 | 用于慢性可植入装置的聚合物馈通件 |
CN104231207A (zh) | 2014-09-18 | 2014-12-24 | 苏州市雄林新材料科技有限公司 | 一种回收碳纤维增强tpu复合材料及其制备方法 |
CN104592850B (zh) | 2014-12-31 | 2017-06-23 | 三棵树涂料股份有限公司 | 超亲水透明防雾涂层的制备方法 |
CN104610902B (zh) | 2015-02-12 | 2018-01-30 | 厦门誉匠复合材料有限公司 | 快速后固化聚氨酯热熔胶及其制备方法 |
WO2016171975A1 (en) | 2015-04-23 | 2016-10-27 | Cardiac Pacemakers, Inc. | Compositions and methods for copolymer solutions with high weight percent copolymers |
US10405975B2 (en) | 2015-10-07 | 2019-09-10 | Boston Scientific Scimed, Inc. | Cultured cell leaflet material |
JP6581303B2 (ja) | 2015-12-17 | 2019-09-25 | カーディアック ペースメイカーズ, インコーポレイテッド | ポリイソブチレン−ポリウレタンを含むポリマー材料およびそれを含む医療デバイス並びに同ポリマー材料を製造する方法 |
US10472457B2 (en) | 2016-01-21 | 2019-11-12 | The University Of Akron | Initiators for living carbocationic polymerization |
EP3455272B1 (en) | 2016-05-10 | 2020-05-27 | Cardiac Pacemakers, Inc. | Thermoset polyisobutylene-polyurethanes and methods for making |
CN106129383B (zh) | 2016-09-05 | 2018-09-07 | 哈尔滨工业大学 | 一种具有纳米级两相梯度分布结构的球形锂离子电池正极材料及其合成方法 |
US10526429B2 (en) | 2017-03-07 | 2020-01-07 | Cardiac Pacemakers, Inc. | Hydroboration/oxidation of allyl-terminated polyisobutylene |
EP3668912B1 (en) | 2017-08-17 | 2021-06-30 | Cardiac Pacemakers, Inc. | Photocrosslinked polymers for enhanced durability |
US11472911B2 (en) | 2018-01-17 | 2022-10-18 | Cardiac Pacemakers, Inc. | End-capped polyisobutylene polyurethane |
-
2010
- 2010-01-12 EP EP20151066.6A patent/EP3670561B1/en active Active
- 2010-01-12 AU AU2010203373A patent/AU2010203373B2/en active Active
- 2010-01-12 CN CN201080010942.8A patent/CN102365308B/zh active Active
- 2010-01-12 EP EP10700645.4A patent/EP2385960B1/en active Active
- 2010-01-12 WO PCT/US2010/020733 patent/WO2010081132A1/en active Application Filing
- 2010-01-12 EP EP23203668.1A patent/EP4282449A3/en active Pending
- 2010-01-12 JP JP2011545506A patent/JP5638003B2/ja active Active
- 2010-01-12 US US12/685,858 patent/US9574043B2/en active Active
-
2012
- 2012-11-20 US US13/681,811 patent/US8962785B2/en active Active
-
2017
- 2017-01-27 US US15/417,262 patent/US10513576B2/en active Active
-
2019
- 2019-12-06 US US16/706,363 patent/US11174336B2/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5120813A (en) * | 1980-02-29 | 1992-06-09 | Th. Goldschmidt Ag | Moisture vapor permeable materials |
CA2114874A1 (en) * | 1993-02-08 | 1994-08-09 | Hanns-Peter Muller | Rigid hydrophobic polyurethanes |
Non-Patent Citations (1)
Title |
---|
Sung Chul Yoon, et al..Surface and Bulk Structure of Segmented Poly(ether urethanes) with Perfluoro Chain Extenders. 5. Incorporation of Poly(dimethylsi1oxane) and Polyisobutylene Macroglycols.《Macromolecules》.1994,第27卷(第6期),第1548-1554页. * |
Also Published As
Publication number | Publication date |
---|---|
US9574043B2 (en) | 2017-02-21 |
CN102365308A (zh) | 2012-02-29 |
EP4282449A3 (en) | 2024-02-28 |
US11174336B2 (en) | 2021-11-16 |
AU2010203373B2 (en) | 2013-08-01 |
EP3670561A2 (en) | 2020-06-24 |
US20100179298A1 (en) | 2010-07-15 |
US8962785B2 (en) | 2015-02-24 |
JP2012515231A (ja) | 2012-07-05 |
US20130079487A1 (en) | 2013-03-28 |
US20170137558A1 (en) | 2017-05-18 |
JP5638003B2 (ja) | 2014-12-10 |
EP3670561A3 (en) | 2020-08-19 |
US20200109232A1 (en) | 2020-04-09 |
US10513576B2 (en) | 2019-12-24 |
AU2010203373A1 (en) | 2011-08-11 |
EP2385960A1 (en) | 2011-11-16 |
EP3670561B1 (en) | 2023-12-06 |
EP4282449A2 (en) | 2023-11-29 |
WO2010081132A1 (en) | 2010-07-15 |
EP2385960B1 (en) | 2020-03-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102365308B (zh) | 聚异丁烯基聚氨酯 | |
US4739013A (en) | Polyurethanes | |
US4810749A (en) | Polyurethanes | |
US5229431A (en) | Crack-resistant polycarbonate urethane polymer prostheses and the like | |
US5133742A (en) | Crack-resistant polycarbonate urethane polymer prostheses | |
US4447590A (en) | Extrudable polyurethane for prosthetic devices prepared from a diisocyanate, a polytetramethylene ether polyol and 1,4 butane diol | |
US4523005A (en) | Extrudable polyurethane for prosthetic devices prepared from a diisocyanate, a polytetramethylene ether polyol, and 1,4-butane diol | |
JP4335448B2 (ja) | 生体医用ポリウレタン、その調製方法及び使用方法 | |
US5430121A (en) | Thermoplastic polyurethanes modified by siloxane block copolymers | |
EP3436498B1 (en) | Biodegradable and/or bioabsorbable thermoplastic polyurethanes | |
Dandeniyage et al. | Development of high strength siloxane poly (urethane‐urea) elastomers based on linked macrodiols for heart valve application | |
AU2016274604A1 (en) | Process for the preparation of polyurethane solutions based on silicon-polycarbonate diols | |
CN112672772A (zh) | 用于生物医疗应用的两性离子聚合物 | |
WO2024104273A1 (zh) | 聚碳酸酯聚二甲基硅氧烷型聚氨酯脲及制备方法 | |
EP1860132A2 (en) | Thermoplastic polyurethane and use thereof | |
CN114524913B (zh) | 一种高柔性、高弹性、降解可调控的可吸收聚氨酯弹性体、制备方法及应用 | |
EP0548256A1 (en) | Biostable polyurethane products | |
EP0332719B1 (en) | Polyurethanes | |
JP3047102B2 (ja) | ポリウレタン | |
AU657267B2 (en) | Polyurethane or polyurethane-urea elastomeric compositions | |
Lipik et al. | Synthesis of biodegradable thermoplastic elastomers (BTPE) based on epsilon-caprolactone | |
EP3303447B1 (en) | Synthesis of polycarbonate siloxane diols | |
TW202421779A (zh) | 生物降解性聚胺酯樹脂 | |
JP2952476B2 (ja) | 繊維形成性ポリウレタン溶液 | |
Adhikari et al. | Advantages of reactive extrusion for the synthesis of polyurethanes for biomedical applications |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |