CN115124659A - Organosilicone polyurethane material with high blood compatibility and preparation method thereof - Google Patents
Organosilicone polyurethane material with high blood compatibility and preparation method thereof Download PDFInfo
- Publication number
- CN115124659A CN115124659A CN202210931449.4A CN202210931449A CN115124659A CN 115124659 A CN115124659 A CN 115124659A CN 202210931449 A CN202210931449 A CN 202210931449A CN 115124659 A CN115124659 A CN 115124659A
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- CN
- China
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- parts
- organic silicon
- solvent
- polyurethane material
- silicon polyurethane
- Prior art date
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 156
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 156
- 239000000463 material Substances 0.000 title claims abstract description 80
- 210000004369 blood Anatomy 0.000 title claims abstract description 21
- 239000008280 blood Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 98
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 98
- 239000010703 silicon Substances 0.000 claims abstract description 98
- 238000006243 chemical reaction Methods 0.000 claims abstract description 93
- -1 polydimethylsiloxane Polymers 0.000 claims description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 238000010438 heat treatment Methods 0.000 claims description 46
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 26
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 26
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 22
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 22
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical group C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 239000003999 initiator Substances 0.000 claims description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 19
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 18
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 17
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 229920001296 polysiloxane Polymers 0.000 claims description 14
- 238000011049 filling Methods 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 244000028419 Styrax benzoin Species 0.000 claims description 11
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 11
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 11
- 229960002130 benzoin Drugs 0.000 claims description 11
- 235000019382 gum benzoic Nutrition 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004970 Chain extender Substances 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 5
- UACSZOWTRIJIFU-UHFFFAOYSA-N hydroxymethyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCO UACSZOWTRIJIFU-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- 150000001451 organic peroxides Chemical class 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 3
- BCAIDFOKQCVACE-UHFFFAOYSA-N 3-[dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azaniumyl]propane-1-sulfonate Chemical compound CC(=C)C(=O)OCC[N+](C)(C)CCCS([O-])(=O)=O BCAIDFOKQCVACE-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims 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 claims description 3
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 3
- YVQBOKCDPCUWSP-UHFFFAOYSA-N oxonane Chemical compound C1CCCCOCCC1 YVQBOKCDPCUWSP-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 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 3
- UYPYRKYUKCHHIB-UHFFFAOYSA-N trimethylamine N-oxide Chemical compound C[N+](C)(C)[O-] UYPYRKYUKCHHIB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- BEWCNXNIQCLWHP-UHFFFAOYSA-N 2-(tert-butylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(C)(C)C BEWCNXNIQCLWHP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 claims description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000005215 alkyl ethers Chemical class 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- WTQUVYBGJUBJSW-UHFFFAOYSA-N oxacycloundecane Chemical compound C1CCCCCOCCCC1 WTQUVYBGJUBJSW-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- WHALSQRTWNBBCV-UHFFFAOYSA-N s-aminosulfanylthiohydroxylamine Chemical compound NSSN WHALSQRTWNBBCV-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- KDAKDBASXBEFFK-UHFFFAOYSA-N 2-(tert-butylamino)ethyl prop-2-enoate Chemical compound CC(C)(C)NCCOC(=O)C=C KDAKDBASXBEFFK-UHFFFAOYSA-N 0.000 claims 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- 230000002308 calcification Effects 0.000 abstract description 29
- 210000003709 heart valve Anatomy 0.000 abstract description 11
- 239000007943 implant Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 56
- 239000000047 product Substances 0.000 description 43
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 42
- 239000004810 polytetrafluoroethylene Substances 0.000 description 42
- 210000001772 blood platelet Anatomy 0.000 description 31
- 239000000126 substance Substances 0.000 description 25
- 238000009661 fatigue test Methods 0.000 description 22
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 15
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 15
- 238000001816 cooling Methods 0.000 description 15
- 230000001678 irradiating effect Effects 0.000 description 12
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 11
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 150000003254 radicals Chemical group 0.000 description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003146 anticoagulant agent Substances 0.000 description 2
- 229940127219 anticoagulant drug Drugs 0.000 description 2
- 230000010100 anticoagulation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
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- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
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- XBNOMKROXZGMFW-UHFFFAOYSA-N 3-[(3-hydroxyphenyl)disulfanyl]phenol Chemical compound OC1=CC=CC(SSC=2C=C(O)C=CC=2)=C1 XBNOMKROXZGMFW-UHFFFAOYSA-N 0.000 description 1
- OTKLRHWBZHQJOP-UHFFFAOYSA-N 3-aminopropyl prop-2-enoate Chemical compound NCCCOC(=O)C=C OTKLRHWBZHQJOP-UHFFFAOYSA-N 0.000 description 1
- MERLDGDYUMSLAY-UHFFFAOYSA-N 4-[(4-aminophenyl)disulfanyl]aniline Chemical compound C1=CC(N)=CC=C1SSC1=CC=C(N)C=C1 MERLDGDYUMSLAY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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- 229910019142 PO4 Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
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- 210000000481 breast Anatomy 0.000 description 1
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- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
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Abstract
The invention discloses an organic silicon polyurethane material with high blood compatibility and a preparation method thereof, belonging to the technical field of heart valves. The invention establishes a novel and simple preparation method of the organic silicon polyurethane material based on the functional reaction of polyaddition and unsaturated double bonds, and the prepared organic silicon polyurethane material shows good thermodynamic compatibility, excellent calcification resistance, mechanical property and blood compatibility, and has extremely high value in the development and application of a plurality of medical implant materials such as heart valves and the like.
Description
Technical Field
The invention belongs to the technical field of heart valves, and particularly relates to an organic silicon polyurethane material with high blood compatibility and a preparation method thereof.
Background
With the increasing pace of life, the decreasing environmental quality, the aging population and other problems, the number of patients with valvular heart diseases is increasing year by year. According to the survey results of cardiovascular health and disease reports in China, more than 2500 million heart valve disease patients in China in 2010 are shown, and the number of people is predicted to increase to 4000 million people by 2025. At present, the artificial heart valve replacement is the best means for treating heart valve diseases, however, only 1-2% of patients in our country receive surgical intervention due to low cognition rate and high treatment price.
To date, the heart valve prostheses widely used in clinical applications mainly include both mechanical valves and biological valves. The mechanical valve is made of pyrolytic carbon material, the service life of the mechanical valve can be more than 30 years, but a patient implanted with the mechanical valve must receive long-term anticoagulation treatment, and the risk of infection of the patient with the artificial valve endocarditis is high. The biological valve is prepared by fixing porcine or bovine pericardium through glutaraldehyde, has good hemodynamic performance, low thrombosis incidence and no need of lifelong anticoagulation; however, biological valves have a limited life span, and tissue is subject to degradation and calcification after prolonged use, which may risk the patient to re-surgically replace the valve. Therefore, the development of a prosthetic heart valve having both excellent mechanical properties and blood compatibility is a trend in the future.
As is well known, polyurethane is a highly elastic polymer composed of soft segments and hard segments, and is widely used in cardiac pacemakers, catheters, breast prostheses, artificial hearts, and the like. In long-term medical implant materials, compared with polyether polyurethane and polyester polyurethane, silicone polyurethane is attracting much attention because of its high thermal stability and biological stability. In addition, the organosilicon has low surface energy, small modulus and smooth surface, and can effectively desorb pollutants such as platelets in high-speed flowing blood, thereby achieving the aim of resisting pollution. Thermoplastic silicone polyurethane is used for polymer valves deployed by the south African Strong Access Technologies and by the U.S. Foldax corporation. However, the higher hydrophobicity of the silicone polyurethane surface makes it susceptible to protein adsorption deposition upon contact with blood, further leading to the formation of blood coagulation and adverse reactions of the immune system (Journal of Membrane Science 2020,606, No. 118119). So far, no report on hydrophilic modification application of organic silicon polyurethane to heart valves exists, the theory and method of hydrophilizing organic silicon polyurethane are explored, and the construction of heart valves with high mechanical performance and blood compatibility simultaneously is a main problem which is needed to be solved to replace traditional mechanical valves and organisms.
Strategies for hydrophilization modification of material surfaces have been reported to include primarily surface coating and surface grafting. The surface coating is convenient and quick, but the prepared coating layer can not be used for a long time. Although surface grafting can solve the instability of the coating layer, it requires complicated steps and severe reaction conditions, and in addition, the grafting reaction may change the original excellent properties of the material. Therefore, for practical applications, blending hydrophilic substances directly with silicone polyurethanes is one of the most promising modification methods. However, hydrophilic materials are poorly compatible with hydrophobic substrates and are very easily eluted from the substrate.
Disclosure of Invention
Aiming at the existing technical problems, the invention provides an organic silicon polyurethane material with high blood compatibility and a preparation method thereof, aiming at overcoming the defects of poor blood compatibility, low mechanical property and the like of the artificial heart valve in the prior art, and based on the functional reaction of polyaddition and unsaturated double bonds, the invention establishes a novel, simple and convenient method, can prepare organic silicon polyurethane with excellent mechanical property and blood compatibility simultaneously, and lays a solid foundation for clinical application.
The technical scheme of the invention is as follows:
the invention provides a preparation method of an organic silicon polyurethane material with high blood compatibility, which comprises the steps of mixing and homogenizing a hydrophilic monomer, an organic silicon polyurethane macromonomer, an initiator and a solvent, then initiating the polymerization reaction of the hydrophilic monomer and the organic silicon polyurethane macromonomer, and then curing to obtain the organic silicon polyurethane material, wherein the end group of the organic silicon polyurethane macromonomer contains unsaturated double bonds.
Preferably, the preparation process of the organosilicon polyurethane macromonomer with the end group containing unsaturated double bond is as follows:
s1, placing polyether polyol and polydimethylsiloxane into a reaction kettle, heating to melt and fully stirring, heating and vacuumizing to remove water and small molecular low-boiling-point substances, closing vacuum, filling nitrogen and reducing temperature; adding diisocyanate, and reacting at 0-120 deg.C for 0.5-48h to obtain polyurethane prepolymer;
s2, adding a chain extender into the polyurethane prepolymer obtained in the step S1, and reacting at 0-120 ℃ for 0.5-48 h;
s3, adding an end-capping reagent containing unsaturated double bonds into the product obtained in the step S2, and reacting at 20-120 ℃ for 0.5-48h to obtain a solution of the organosilicon polyurethane macromonomer containing unsaturated double bonds at the end group;
the solvent at least comprises a first solvent, the first solvent is a solvent without active hydrogen, and the solvent without active hydrogen is added in any step of S1 and S2.
Preferably, the solvent further includes a second solvent, and the preparation process of the silicone polyurethane material after the step of S3 is as follows:
s4, mixing the hydrophilic monomer, the organosilicon polyurethane macromonomer solution obtained in the S3, the initiator and a second solvent, homogenizing, then initiating the polymerization reaction of the hydrophilic monomer and the organosilicon polyurethane macromonomer, and then curing to obtain the organosilicon polyurethane material;
wherein the mass ratio of the hydrophilic monomer, the organic silicon polyurethane macromonomer solution, the initiator and the second solvent is (1-50): 200-1000): 0.1-5): 0-400.
Preferably, the active hydrogen-free solvent is selected from at least one of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, acetone, ethyl acetate, butyl acetate, dimethyl carbonate, toluene and xylene;
the second solvent is at least one selected from the group consisting of water, methanol, ethanol, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, in the steps S1 to S3, the mass ratio of the polyether glycol, the polydimethylsiloxane, the diisocyanate, the chain extender and the end capping agent is (0-100): (20-450): (30-160): (2-60): (2-35);
the mass of the solvent without active hydrogen accounts for 50-95% of the total mass of the reaction system for preparing the organosilicon polyurethane macromonomer with the end group containing unsaturated double bond.
Preferably, in the step S1, the polyether polyol is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, octamethylene ether glycol, and decamethylene ether glycol;
the structural formula of the polydimethylsiloxane is as follows:
wherein R is 1 、R 2 Is methyl or phenyl, R 1 And R 2 May be the same or different, R 3 Is a linear divalent alkyl radical or alkyl ether containing from 0 to 6 carbon atoms, R 4 Is amino or hydroxy;
the diisocyanate is at least one selected from isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate and lysine diisocyanate;
in the step S2, the chain extender is at least one selected from the group consisting of low molecular weight diols, low molecular weight diamines, low molecular weight bishydroxy disulfide and low molecular weight diamino disulfide;
in step S3, the capping reagent is hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, or hydroxypropyl methacrylate.
Preferably, the initiator is a photoinitiator or a thermal initiator, the photoinitiator is a free radical initiator, and the thermal initiator is an azo initiator, an organic peroxide or an inorganic peroxide;
when the photoinitiator is adopted, the corresponding polymerization reaction and curing specific processes are as follows: pouring the mixture into a mold under the irradiation of ultraviolet light for 30-1800s, and drying the mixture at 60-150 ℃ to form a film;
when a thermal initiator is used, the corresponding polymerization and curing processes are as follows: reacting in a reaction kettle at 35-120 deg.C for 0.5-48h, pouring into a mold, and oven drying at 60-150 deg.C to form film.
Preferably, the free radical type initiator is benzoin dimethyl ether, benzophenone, 1-hydroxycyclohexyl phenyl ketone or 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone; the azo initiator is azobisisobutyronitrile or azobisisoheptonitrile; the organic peroxide is dibenzoyl peroxide or diethylhexyl dicarbonate peroxide; the inorganic peroxide is potassium persulfate or ammonium persulfate.
Preferably, the hydrophilic monomer is selected from the group consisting of acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, N-vinylpyrrolidone, polyethylene glycol methacrylate, 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, 2- (methacryloyloxy) ethyl-2- (trimethylamino) ethyl phosphate, trimethylamine N-oxide, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, 2-tert-butylaminoethyl acrylate, N-vinylpyrrolidone, polyethylene glycol methacrylate, 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, 2- (methacryloyloxy) ethyl ] ethyl methacrylate, 2- (meth) aminopropyl acrylate, dimethylaminoethyl acrylate, N-butylaminoethyl acrylate, N-propyl acrylate, N-methyl acrylate, N-propyl methacrylate, N-acrylate, and a salt, N-acrylate, and a salt thereof, 2-t-butylaminoethyl methacrylate, N-diethylaminoethyl acrylate and N, N-diethylaminoethyl methacrylate.
The invention also provides an organic silicon polyurethane material with high blood compatibility, which is prepared by adopting the preparation method, the organic silicon polyurethane material has a heterogeneous interlocking structure formed by free radical polymerization of hydrophilic monomers and organic silicon polyurethane macromonomers, and the terminal group of the organic silicon polyurethane macromonomers contains unsaturated double bonds.
The invention has the beneficial effects that:
(1) the organic silicon polyurethane material is prepared based on the functional reaction of polyaddition and unsaturated double bonds, the end group of the prepared organic silicon polyurethane macromonomer contains an active group unsaturated double bond, necessary conditions are provided for further free radical copolymerization of a hydrophilic monomer, and a heterogeneous interlocking structure formed by covalent bonding and hydrogen bond acting force between the organic silicon polyurethane macromonomer with the end group containing the unsaturated double bond and the hydrophilic monomer is beneficial to improving the thermodynamic compatibility of the hydrophilic organic silicon polyurethane material and simultaneously avoids the elution of a hydrophilic substance in the using process, so the obtained organic silicon polyurethane has lasting and stable mechanical property and blood compatibility, the performance of the organic silicon polyurethane in the application of heart valves is improved, and the risk of complication of a patient in the using process is reduced;
(2) the tensile strength of the prepared organic silicon polyurethane material is 19.4-41.4MPa, the elastic modulus is 11.0-25.3MPa, and the elongation at break is 412-; the mechanical properties are not obviously changed before and after the fatigue test; the adhesion amount of surface platelets is reduced by 70-99%; the surfaces have no calcification phenomenon;
(3) the organic silicon polyurethane prepared by the invention has simple process and low preparation cost, opens up a new way for replacing the traditional mechanical valve and biological valve, and has great potential in the field of medical implant materials such as heart valves and the like.
Drawings
FIG. 1 is a chart of the infrared absorption spectrum of the silicone polyurethane macromer in example 1;
FIG. 2 is a graph of the infrared absorption spectrum of the silicone polyurethane material of example 1;
FIG. 3 is a stress-strain plot of the silicone polyurethane material of example 1;
FIG. 4 is SEM images of platelet adhesion on the surface of silicone polyurethane before and after hydrophilic modification in example 1;
FIG. 5 is an EDS image of Ca element on the surface of the silicone polyurethane material in example 1;
FIG. 6 is a schematic diagram of the preparation of a silicone polyurethane material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
Test method and label
1. Platelet adhesion
Collecting fresh rabbit blood into a vacuum blood collection tube containing 3.8 wt% sodium citrate as anticoagulant (volume ratio of blood to anticoagulant is 9:1), freezing the collected blood at 1500rpm (4 ℃) and centrifuging for 10min to obtain supernatant as Platelet Rich Plasma (PRP); the area is 1 x 1cm 2 The valve was washed 3 times with saline and placed in a 24-well plate, 2mL of saline was added at 37 deg.CIncubation for 2h, then removing the saline in the well plate, dropping 500 μ Ι _ of fresh PRP to the front surface of each valve, and incubating again for 2h at 37 ℃; after the incubation is finished, the valve is lightly washed by PBS buffer solution for 3 times to remove the blood platelets with weak surface adhesion, and the blood platelets adhered to the surface of the membrane are fixed by treating the valve with 2.5 wt% glutaraldehyde aqueous solution for 4 hours at room temperature; the fixed platelets were then dehydrated for 15min using a series of gradient ethanol solutions (25%, 50%, 75%, 95%, 100%); and finally, replacing ethanol with tert-butyl alcohol for multiple times, then carrying out freeze drying, and observing the morphology and adhesion state of platelets on the surface of the membrane by using a cold field emission scanning electron microscope. Wherein the number of adherent platelets on the surface of the valve is quantified from at least five SEM images.
2. Fatigue test
Cyclic tensile testing was performed using an Instron 5565 electronic universal tester. The thickness of the dumbbell sample bar is 300-700 mu m, the length of the dumbbell sample bar is 5cm, the gauge length of the dumbbell sample bar is 3cm, the frequency of the universal tester is set to be 5Hz, and the cycle number is 3 x 10 8 Next, the amplitude is 15% of the sample length.
3. Calcification testing
(1) Preparing a calcification solution: dissolving 6.06g of Tris (hydroxymethyl) aminomethane (Tris) in 500mL of ultrapure water, and adjusting the pH value of the solution to 7.4 with 0.2M hydrochloric acid solution; the solution is divided into two parts averagely, wherein 0.5295g of monocalcium phosphate is added into one part, and 0.4295g of calcium oxide is added into the other part; and slowly adding the Tris solution containing the calcium oxide into the Tris solution containing the monocalcium phosphate to prepare the calcification solution.
(2) Placing the valve sample in a calcification solution, taking out the sample every 24h, washing the valve sample with normal saline for three times, and placing the valve sample in a reformulated calcification solution; after 30 days, the sample was taken out, and EDS images of the valve surface were observed with a cold field emission scanning electron microscope at an accelerating voltage of 1.0 kV.
Second, Experimental materials
Polydimethylsiloxane, manufactured by GELEST corporation, USA; polyether polyol, manufactured by Mitsubishi Chemical company, other reagents, obtained from shanghai sigma limited, the reagents of steps (1) - (3) of the description (corresponding to steps S1-S3 of the claims) were dehydrated, and all other reagents were used as such without further purification.
In the following examples, the percentages and parts of the components referred to are, unless otherwise specified, percentages by mass and parts by mass.
Example 1
(1) Placing 17 parts (17g) of polytetramethylene ether glycol (molecular weight is 1000Da) and 100 parts of alpha, omega-dihydroxyethoxy propyl polydimethylsiloxane (molecular weight is 1000Da) in a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and small molecular low-boiling-point substances, closing vacuum, introducing nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then adding 70 parts of diphenylmethane diisocyanate and 1000 parts of N, N-dimethylacetamide, and reacting at 45 ℃ for 6 hours;
(2) cooling the temperature of the reaction kettle to 4 ℃, and adding 7 parts of ethylenediamine into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 15 parts of hydroxyethyl methacrylate into the product obtained in the step (2), and reacting at 45 ℃ for 6 hours to obtain an organosilicon polyurethane macromonomer solution;
(4) mixing 5 parts of acrylic acid, 5 parts of 2-acrylamide-2-methylpropanesulfonic acid, 480 parts of an organic silicon polyurethane macromonomer solution, 3.5 parts of benzoin dimethyl ether and 100 parts of N, N-dimethylacetamide, homogenizing, irradiating for 200s by ultraviolet light, pouring into a PTFE (polytetrafluoroethylene) mold, and drying at 120 ℃ to form a film, thereby obtaining the organic silicon polyurethane material.
FIG. 1 is a chart of the infrared absorption spectrum of the silicone polyurethane macromonomer obtained in step 3 of this example, which is 3315cm -1 The absorption peak is the stretching vibration peak of N-H; is positioned at 1700cm -1 And 1580cm -1 The stretching vibration peaks of (A) are the absorption peaks of C ═ O and C-N respectively; at 1017cm -1 The absorption peak of (A) is generated by Si-O-Si; located 1620cm -1 The stretching vibration peak of the double bond C ═ C group provides a necessary condition for further free radical copolymerization of the hydrophilic monomer.
FIG. 2 is a chart of the infrared absorption spectrum of the organosilicon polyurethane material obtained in step 4 of this example,located at 1650cm -1 COO of (A) - And 1080m -1 To SO 3 - The stretching vibration peak of the group proves the successful synthesis of the hydrophilized organic silicon polyurethane material.
The stress-strain curve diagram of the organic silicon polyurethane material is shown in fig. 3, the tensile strength of the organic silicon polyurethane material is 32.5MPa, the elastic modulus is 20.8MPa, and the elongation at break is 883%;
SEM images of the surface platelet adhesion of the organosilicon polyurethane macromonomer (left) in the step 3 and the organosilicon polyurethane (right) in the step 4 are shown in FIG. 4, and the surface platelet adhesion is reduced by 99%;
the surface of the organosilicon polyurethane material has no calcification after 30 days, and an EDS image of Ca element on the surface of the organosilicon polyurethane is shown in figure 5.
Example 2
(1) Placing 17 parts (17g) of polytetramethylene ether glycol (with the molecular weight of 1000Da) and 100 parts of alpha, omega-dihydroxyethoxy propyl polydimethylsiloxane (with the molecular weight of 1000Da) in a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and small molecular low-boiling-point substances, closing vacuum, filling nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then 88 parts of diphenylmethane diisocyanate and 1000 parts of N, N-dimethylacetamide are added to react for 6 hours at the temperature of 45 ℃;
(2) cooling the temperature of the reaction kettle to 4 ℃, and adding 7 parts of ethylenediamine into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 30 parts of hydroxyethyl methacrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain an organic silicon polyurethane macromonomer solution;
(4) mixing 5 parts of acrylic acid, 5 parts of 2-acrylamide-2-methylpropanesulfonic acid, 480 parts of an organic silicon polyurethane macromonomer solution, 3.5 parts of benzoin dimethyl ether and 400 parts of N, N-dimethylacetamide, homogenizing, irradiating for 200s by ultraviolet light, pouring into a PTFE (polytetrafluoroethylene) mold, and drying at 120 ℃ to form a film, thereby obtaining the organic silicon polyurethane material.
The tensile strength of the organic silicon polyurethane material is 41.4MPa, the elastic modulus is 25.3MPa, and the elongation at break is 730%; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 99%; after 30 days there was no calcification of the surface.
Example 3
(1) Putting 450 parts (450g) of alpha, omega-dihydroxyethoxy propyl polydimethylsiloxane (with the molecular weight of 1000Da) into a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2 hours to remove water and micromolecular low-boiling-point substances, closing the vacuum, filling nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then adding 30 parts of hexamethylene diisocyanate and 1000 parts of N, N-dimethylacetamide, and reacting for 6 hours at 45 ℃;
(2) cooling the temperature of the reaction kettle to 4 ℃, and adding 2 parts of ethylenediamine into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 2 parts of hydroxyethyl methacrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain an organosilicon polyurethane macromonomer solution;
(4) mixing 5 parts of acrylic acid, 5 parts of 2-acrylamide-2-methylpropanesulfonic acid, 480 parts of an organic silicon polyurethane macromonomer solution, 3.5 parts of benzoin dimethyl ether and N, N-dimethylacetamide, homogenizing, irradiating for 200s by ultraviolet light, pouring into a PTFE (Polytetrafluoroethylene) mold, and drying at 120 ℃ to form a film, thereby obtaining the organic silicon polyurethane material.
The tensile strength of the organic silicon polyurethane material is 20.0MPa, the elastic modulus is 18.2MPa, and the elongation at break is 430%; the mechanical properties are not obviously changed before and after the fatigue test; the adhesion amount of surface platelets is reduced by 99%; after 30 days there was no calcification of the surface.
Example 4
(1) Placing 100 parts (100g) of polyethylene glycol (molecular weight 6000Da) and 20 parts of alpha, omega-dihydroxyethoxy propyl polydimethylsiloxane (molecular weight 200Da) in a reaction kettle, heating to melt and fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and micromolecule low-boiling-point substances, closing vacuum, filling nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then adding 70 parts of diphenylmethane diisocyanate and 1000 parts of N, N-dimethylacetamide, and reacting for 6 hours at 45 ℃;
(2) cooling the temperature of the reaction kettle to 4 ℃, and adding 7 parts of ethylenediamine into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 15 parts of hydroxyethyl methacrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain an organosilicon polyurethane macromonomer solution;
(4) mixing 5 parts of acrylic acid, 5 parts of 2-acrylamide-2-methylpropanesulfonic acid, 480 parts of an organic silicon polyurethane macromonomer solution, 3.5 parts of azobisisobutyronitrile and 100 parts of N, N-dimethylacetamide, homogenizing, reacting at 60 ℃ for 12 hours, pouring into a PTFE (polytetrafluoroethylene) mold, and drying at 120 ℃ to form a film, thereby obtaining the organic silicon polyurethane material.
The tensile strength of the organic silicon polyurethane material is 24.7MPa, the elastic modulus is 13.1MPa, and the elongation at break is 490 percent; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 99%; after 30 days there was no calcification of the surface.
Example 5
(1) Putting 34 parts (34g) of polyhexamethylene ether glycol (molecular weight 2000Da) and 100 parts of alpha, omega-diaminohexyl polydimethylsiloxane (molecular weight 500Da) into a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2 hours to remove water and micromolecular low-boiling-point substances, closing vacuum, filling nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then 160 parts of dicyclohexylmethane diisocyanate and 1000 parts of N, N-dimethylacetamide are added to react for 6 hours at the temperature of 45 ℃;
(2) cooling the temperature of the reaction kettle to 4 ℃, and adding 60 parts of 3,3' -dihydroxy diphenyl disulfide into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 35 parts of hydroxypropyl methacrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain an organosilicon polyurethane macromonomer solution;
(4) mixing 5 parts of acrylic acid, 5 parts of 2-acrylamide-2-methylpropanesulfonic acid, 480 parts of an organic silicon polyurethane macromonomer solution, 3.5 parts of azobisisobutyronitrile and 400 parts of N, N-dimethylacetamide, homogenizing, reacting at 60 ℃ for 12 hours, pouring into a PTFE (polytetrafluoroethylene) mold, and drying at 120 ℃ to form a film, thereby obtaining the organic silicon polyurethane material.
The tensile strength of the organic silicon polyurethane material is 35.7MPa, the elastic modulus is 21.3MPa, and the elongation at break is 940%; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 99%; after 30 days there was no calcification of the surface.
Example 6
(1) Placing 17 parts (17g) of poly (octamethylene ether glycol) (molecular weight 1000Da) and 100 parts of alpha, omega-dihydroxyethoxy propyl polydimethylsiloxane (molecular weight 1000Da) in a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and small molecular low-boiling-point substances, closing vacuum, introducing nitrogen and reducing the temperature of the reaction kettle to 0 ℃; then adding 70 parts of diphenylmethane diisocyanate and 1000 parts of N, N-dimethylacetamide, and reacting for 48 hours at the temperature of 0 ℃;
(2) keeping the temperature of the reaction kettle at 0 ℃, adding 7 parts of ethylenediamine into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 15 parts of hydroxyethyl methacrylate into the product obtained in the step (2) to react for 48 hours at 0 ℃ to obtain an organic silicon polyurethane macromonomer solution;
(4) 5 parts of acrylic acid, 5 parts of 2-acrylamide-2-methylpropanesulfonic acid, 480 parts of an organic silicon polyurethane macromonomer solution, 3.5 parts of azobisisobutyronitrile and 100 parts of N, N-dimethylacetamide are reacted at 60 ℃ for 12 hours, and then poured into a PTFE (polytetrafluoroethylene) mold to be dried at 120 ℃ to form a film, so that the organic silicon polyurethane material is obtained.
The tensile strength of the organic silicon polyurethane material is 24.9MPa, the elastic modulus is 15.3MPa, and the elongation at break is 566%; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 99%; after 30 days there was no calcification of the surface.
Example 7
(1) Placing 34 parts (34g) of polydecamethylene ether glycol (molecular weight 2000Da) and 100 parts of alpha, omega-dihydroxyamyl polydimethylsiloxane (molecular weight 1000Da) in a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and small molecular low-boiling-point substances, closing vacuum, filling nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then 70 parts of diphenylmethane diisocyanate are added to react for 6 hours at the temperature of 45 ℃;
(2) after the temperature of the reaction kettle is reduced to 4 ℃, 7 parts of ethylenediamine and 378 parts of N, N-dimethylformamide are added into the product obtained in the step (1) to react for 2 hours;
(3) adding 15 parts of hydroxyethyl methacrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain an organosilicon polyurethane macromonomer solution;
(4) mixing 5 parts of acrylic acid, 5 parts of 2-acrylamide-2-methylpropanesulfonic acid, 200 parts of an organic silicon polyurethane macromonomer solution, 3.5 parts of benzoin dimethyl ether and 200 parts of N, N-dimethylformamide, homogenizing, irradiating for 200s by ultraviolet light, pouring into a PTFE (Polytetrafluoroethylene) mold, and drying at 120 ℃ to form a film, thereby obtaining the organic silicon polyurethane material.
The tensile strength of the organic silicon polyurethane material is 31.1MPa, the elastic modulus is 19.9MPa, and the elongation at break is 800%; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 99%; after 30 days there was no calcification of the surface.
Example 8
(1) Placing 17 parts (17g) of polytetramethylene ether glycol (molecular weight is 1000Da) and 100 parts of alpha, omega-dihydroxyhexyl polydimethylsiloxane (molecular weight is 1000Da) in a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and micromolecular low-boiling-point substances, closing vacuum, filling nitrogen and keeping the temperature of the reaction kettle at 120 ℃; then 70 parts of diphenylmethane diisocyanate and 3640 parts of N, N-dimethylacetamide are added to react for 0.5h at 120 ℃;
(2) continuously keeping the temperature of the reaction kettle at 120 ℃, adding 10 parts of 1, 2-butanediol into the product obtained in the step (1) for reaction for 0.5 h;
(3) adding 18 parts of hydroxypropyl methacrylate into the product obtained in the step (2) to react for 0.5h at 120 ℃ to obtain an organosilicon polyurethane macromonomer solution;
(4) mixing 5 parts of acrylic acid, 5 parts of 2-acrylamide-2-methylpropanesulfonic acid, 800 parts of an organic silicon polyurethane macromonomer solution, 3.5 parts of azobisisobutyronitrile and 100 parts of N, N-dimethylacetamide, homogenizing, reacting at 60 ℃ for 12 hours, pouring into a PTFE (polytetrafluoroethylene) mold, and drying at 120 ℃ to form a film, thereby obtaining the organic silicon polyurethane material.
The tensile strength of the organic silicon polyurethane material is 24.5MPa, the elastic modulus is 13.1MPa, and the elongation at break is 520%; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 99%; after 30 days there was no calcification of the surface.
Example 9
(1) Putting 34 parts (34g) of polypropylene glycol (molecular weight 2000Da) and 200 parts of alpha, omega-diaminopropyl polymethylphenylsiloxane (molecular weight 2000Da) into a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and micromolecular low-boiling-point substances, closing vacuum, filling nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then adding 70 parts of diphenylmethane diisocyanate and 1000 parts of dimethyl sulfoxide, and reacting for 6 hours at 45 ℃;
(2) cooling the temperature of the reaction kettle to 4 ℃, and adding 7 parts of ethylenediamine into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 15 parts of hydroxyethyl methacrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain an organosilicon polyurethane macromonomer solution;
(4) mixing 5 parts of acrylic acid, 5 parts of 2-acrylamide-2-methylpropanesulfonic acid, 480 parts of an organic silicon polyurethane macromonomer solution, 3.5 parts of azobisisobutyronitrile and 100 parts of dimethyl sulfoxide, homogenizing, reacting at 60 ℃ for 12 hours, pouring into a PTFE (polytetrafluoroethylene) mold, and drying at 120 ℃ to form a film, thereby obtaining the organic silicon polyurethane material.
The tensile strength of the organic silicon polyurethane material is 26.4MPa, the elastic modulus is 13.9MPa, and the elongation at break is 510%; the mechanical properties are not obviously changed before and after the fatigue test; the adhesion amount of surface platelets is reduced by 99%; after 30 days there was no calcification of the surface.
Example 10
(1) Placing 17 parts (17g) of polyhexamethylene ether glycol (molecular weight 1000Da) and 100 parts of alpha, omega-dihydroxypropyl polydimethylsiloxane (molecular weight 1000Da) in a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and small molecular low-boiling-point substances, closing vacuum, introducing nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then adding 70 parts of diphenylmethane diisocyanate, 500 parts of tetrahydrofuran and 500 parts of N, N-dimethylacetamide, and reacting at 45 ℃ for 6 hours;
(2) cooling the temperature of the reaction kettle to 4 ℃, and adding 7 parts of ethylenediamine into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 15 parts of hydroxyethyl methacrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain an organosilicon polyurethane macromonomer solution;
(4) mixing 5 parts of acrylic acid, 5 parts of 2-acrylamide-2-methylpropanesulfonic acid, 480 parts of an organic silicon polyurethane macromonomer solution, 5 parts of benzophenone and 100 parts of N, N-dimethylacetamide, homogenizing, irradiating for 30s by ultraviolet light, pouring into a PTFE (polytetrafluoroethylene) mold, and drying at 150 ℃ to form a film, thereby obtaining the organic silicon polyurethane material.
The tensile strength of the organic silicon polyurethane material is 29.4MPa, the elastic modulus is 18.8MPa, and the elongation at break is 715%; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 99%; after 30 days there was no calcification of the surface.
Example 11
(1) Putting 10.2 parts (10.2g) of polytetramethylene ether glycol (with the molecular weight of 600Da) and 100 parts of alpha, omega-dihydroxyethoxy propyl polydimethylsiloxane (with the molecular weight of 1000Da) into a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and small molecular low-boiling-point substances, closing the vacuum, introducing nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then adding 68 parts of isophorone diisocyanate and 1000 parts of N, N-dimethylacetamide, and reacting for 6 hours at 45 ℃;
(2) after the temperature of the reaction kettle is reduced to 4 ℃, 8 parts of 1, 4-butanediamine is added into the product obtained in the step (1) to react for 2 hours;
(3) adding 15 parts of hydroxyethyl methacrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain an organosilicon polyurethane macromonomer solution;
(4) mixing 5 parts of acrylic acid, 5 parts of 2-acrylamide-2-methylpropanesulfonic acid, 480 parts of an organic silicon polyurethane macromonomer solution, 0.1 part of dibenzoyl peroxide and 100 parts of dimethyl sulfoxide, homogenizing, reacting at 120 ℃ for 0.5h, pouring into a PTFE (polytetrafluoroethylene) mold, and drying at 60 ℃ to form a film, thereby obtaining the organic silicon polyurethane material.
The tensile strength of the organic silicon polyurethane material is 30.0MPa, the elastic modulus is 19.1MPa, and the elongation at break is 775%; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 99%; after 30 days there was no calcification of the surface.
Example 12
(1) Putting 34 parts (34g) of polytetramethylene ether glycol (molecular weight 2000Da) and 100 parts of alpha, omega-dihydroxypropyl polydimethylsiloxane (molecular weight 1000Da) into a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and small molecular low-boiling-point substances, closing vacuum, introducing nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then adding 50 parts of toluene diisocyanate, 500 parts of acetone and 500 parts of N-methyl pyrrolidone, and reacting for 6 hours at 45 ℃;
(2) cooling the temperature of the reaction kettle to 4 ℃, and adding 30 parts of 4,4' -diaminodiphenyl disulfide into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 15 parts of hydroxypropyl acrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain an organosilicon polyurethane macromonomer solution;
(4) mixing 5 parts of acrylic acid, 5 parts of 2-acrylamide-2-methylpropanesulfonic acid, 480 parts of an organic silicon polyurethane macromonomer solution, 3.5 parts of benzoin dimethyl ether and 200 parts of N-methyl pyrrolidone, homogenizing, irradiating for 1800s by ultraviolet light, pouring into a PTFE (polytetrafluoroethylene) mold, and drying at 120 ℃ to form a film to obtain the organic silicon polyurethane material.
The tensile strength of the organosilicone polyurethane material is 31.2MPa, the elastic modulus is 19.9MPa, and the elongation at break is 878%; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 99%; after 30 days there was no calcification of the surface.
Example 13
(1) Placing 17 parts (17g) of polytetramethylene ether glycol (molecular weight is 1000Da) and 200 parts of alpha, omega-dihydroxyhexyl polydimethylsiloxane (molecular weight is 2000Da) in a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and small molecular low-boiling-point substances, closing vacuum, introducing nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then adding 68 parts of lysine diisocyanate and 2000 parts of N, N-dimethylacetamide, and reacting for 6 hours at 45 ℃;
(2) keeping the temperature of the reaction kettle at 45 ℃, and adding 11 parts of 1, 4-butanediol into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 15 parts of hydroxyethyl methacrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain an organosilicon polyurethane macromonomer solution;
(4) mixing 5 parts of acrylic acid, 5 parts of 2-acrylamide-2-methylpropanesulfonic acid, 600 parts of organic silicon polyurethane macromonomer solution and 3.5 parts of benzoin dimethyl ether, homogenizing, irradiating for 200s by ultraviolet light, pouring into a PTFE (polytetrafluoroethylene) mold, and drying at 120 ℃ to form a film to obtain the organic silicon polyurethane material.
The tensile strength of the organic silicon polyurethane material is 28.8MPa, the elastic modulus is 17.6MPa, and the elongation at break is 782%; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 99%; after 30 days there was no calcification of the surface.
Example 14
(1) Placing 17 parts (17g) of polyhexamethylene ether glycol (with the molecular weight of 1000Da) and 100 parts of alpha, omega-dihydroxyethoxy propyl polydimethylsiloxane (with the molecular weight of 1000Da) in a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and small molecular low-boiling-point substances, closing vacuum, filling nitrogen, and reducing the temperature of the reaction kettle to 45 ℃; then adding 70 parts of diphenylmethane diisocyanate and 1000 parts of N, N-dimethylacetamide, and reacting at 45 ℃ for 6 hours;
(2) cooling the temperature of the reaction kettle to 4 ℃, and adding 7 parts of ethylenediamine into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 15 parts of hydroxyethyl methacrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain an organosilicon polyurethane macromonomer solution;
(4) mixing 10 parts of N-vinyl pyrrolidone, 480 parts of organic silicon polyurethane macromonomer solution and 3.5 parts of benzoin dimethyl ether, homogenizing, irradiating for 200s by ultraviolet light, pouring into a PTFE (Polytetrafluoroethylene) mold, and drying at 120 ℃ to form a film, thereby obtaining the organic silicon polyurethane material.
The tensile strength of the organic silicon polyurethane material is 32.0MPa, the elastic modulus is 20.5MPa, and the elongation at break is 860 percent; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 93%; after 30 days there was no calcification of the surface.
Example 15
(1) Placing 17 parts (17g) of polytetramethylene ether glycol (molecular weight is 1000Da) and 100 parts of alpha, omega-dihydroxyethoxy propyl polydimethylsiloxane (molecular weight is 1000Da) in a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and small molecular low-boiling-point substances, closing vacuum, introducing nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then adding 70 parts of diphenylmethane diisocyanate and 3880 parts of N, N-dimethylacetamide, and reacting at 45 ℃ for 6 hours;
(2) cooling the temperature of the reaction kettle to 4 ℃, and adding 7 parts of ethylenediamine into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 15 parts of hydroxyethyl methacrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain a polyurethane macromonomer solution;
(4) mixing 25 parts of acrylic acid, 25 parts of 2-acrylamide-2-methylpropanesulfonic acid, 1000 parts of polyurethane macromonomer solution and 5 parts of benzophenone, homogenizing, irradiating by ultraviolet light for 200s, pouring into a PTFE (polytetrafluoroethylene) mold, and drying at 120 ℃ to form a film, thereby obtaining the organosilicone polyurethane material.
The tensile strength of the organic silicon polyurethane material is 19.4MPa, the elastic modulus is 11.0MPa, and the elongation at break is 412%; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 99%; after 30 days there was no calcification of the surface.
Example 16
(1) Placing 17 parts (17g) of polytetramethylene ether glycol (molecular weight is 1000Da) and 100 parts of alpha, omega-dihydroxyethoxy propyl polydimethylsiloxane (molecular weight is 1000Da) in a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and small molecular low-boiling-point substances, closing vacuum, introducing nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then adding 70 parts of diphenylmethane diisocyanate and 388 parts of N, N-dimethylacetamide, and reacting at 45 ℃ for 6 hours;
(2) cooling the temperature of the reaction kettle to 4 ℃, and adding 7 parts of ethylenediamine into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 15 parts of hydroxyethyl methacrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain an organosilicon polyurethane macromonomer solution;
(4) mixing 0.5 part of acrylic acid, 0.5 part of 2-acrylamide-2-methylpropanesulfonic acid, 280 parts of an organic silicon polyurethane macromonomer solution, 1.5 parts of azobisisobutyronitrile and 400 parts of N, N-dimethylacetamide, homogenizing, reacting at 70 ℃ for 12 hours, pouring into a PTFE (polytetrafluoroethylene) mold, and drying at 100 ℃ to form a film, thereby obtaining the organic silicon polyurethane material.
The tensile strength of the organic silicon polyurethane material is 34.5MPa, the elastic modulus is 23.7MPa, and the elongation at break is 992%; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 70%; after 30 days there was no calcification of the surface.
Example 17
(1) Placing 17 parts (17g) of polytetramethylene ether glycol (molecular weight is 1000Da) and 100 parts of alpha, omega-dihydroxypropyl polydimethylsiloxane (molecular weight is 1000Da) in a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and micromolecular low-boiling-point substances, closing vacuum, filling nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then adding 70 parts of diphenylmethane diisocyanate, 800 parts of tetrahydrofuran and 200 parts of acetone, and reacting at 45 ℃ for 6 hours;
(2) cooling the temperature of the reaction kettle to 4 ℃, and adding 7 parts of ethylenediamine into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 15 parts of hydroxyethyl methacrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain an organosilicon polyurethane macromonomer solution;
(4) mixing 10 parts of 2- (methacryloyloxy) ethyl-2- (trimethyl amino) ethyl phosphate, 480 parts of an organic silicon polyurethane macromonomer solution, 3.5 parts of azobisisobutyronitrile and 100 parts of ethanol, homogenizing, reacting at 50 ℃ for 12 hours, pouring into a PTFE (polytetrafluoroethylene) mold, and drying at 120 ℃ to form a film, thereby obtaining the organic silicon polyurethane material.
The tensile strength of the organic silicon polyurethane material is 30.2MPa, the elastic modulus is 18.4MPa, and the elongation at break is 720 percent; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 99%; after 30 days there was no calcification of the surface.
Example 18
(1) Placing 17 parts (17g) of polytetramethylene ether glycol (molecular weight is 1000Da) and 100 parts of alpha, omega-dihydroxy butyl polymethylphenylsiloxane (molecular weight is 1000Da) in a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and small molecular low-boiling-point substances, closing vacuum, filling nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then adding 70 parts of diphenylmethane diisocyanate, 200 parts of ethyl acetate, 200 parts of butyl acetate and 1000 parts of dimethyl carbonate, and reacting for 6 hours at 45 ℃;
(2) cooling the temperature of the reaction kettle to 4 ℃, and adding 7 parts of ethylenediamine into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 15 parts of hydroxyethyl methacrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain an organic silicon polyurethane macromonomer solution;
(4) mixing 10 parts of polyethylene glycol methacrylate, 500 parts of organic silicon polyurethane macromonomer solution and 3.5 parts of benzoin dimethyl ether, homogenizing, irradiating for 200s by ultraviolet light, pouring into a PTFE (polytetrafluoroethylene) mold, and drying at 120 ℃ to form a film, thereby obtaining the organic silicon polyurethane material.
The tensile strength of the organic silicon polyurethane material is 31.4MPa, the elastic modulus is 20.2MPa, and the elongation at break is 812%; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 90%; after 30 days there was no calcification of the surface.
Example 19
(1) Placing 17 parts (17g) of polytetramethylene ether glycol (molecular weight is 1000Da) and 100 parts of alpha, omega-dihydroxyethoxy propyl polydimethylsiloxane (molecular weight is 1000Da) in a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and small molecular low-boiling-point substances, closing vacuum, introducing nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then adding 70 parts of diphenylmethane diisocyanate and 800 parts of N, N-dimethylacetamide, and reacting at 45 ℃ for 6 hours;
(2) keeping the temperature of the reaction kettle at 45 ℃, and adding 7 parts of ethylene glycol into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 15 parts of hydroxyethyl methacrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain an organosilicon polyurethane macromonomer solution;
(4) mixing 5 parts of 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, 5 parts of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, 470 parts of an organosilicon polyurethane macromonomer solution, 3.5 parts of potassium persulfate and 200 parts of water, homogenizing, reacting at 70 ℃ for 12 hours, pouring into a PTFE (polytetrafluoroethylene) mold, and drying at 120 ℃ to form a film, thereby obtaining the organosilicon polyurethane material.
The tensile strength of the organic silicon polyurethane material is 28.8MPa, the elastic modulus is 18.4MPa, and the elongation at break is 805%; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 99%; after 30 days there was no calcification of the surface.
Example 20
(1) Placing 17 parts (17g) of polytetramethylene ether glycol (molecular weight is 1000Da) and 100 parts of alpha, omega-diaminohexyl polydimethylsiloxane (molecular weight is 1000Da) in a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and micromolecular low-boiling-point substances, closing vacuum, filling nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then adding 72 parts of dicyclohexylmethane diisocyanate and 1000 parts of N, N-dimethylacetamide, and reacting for 6 hours at 45 ℃;
(2) cooling the temperature of the reaction kettle to 4 ℃, and adding 7 parts of ethylenediamine into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 15 parts of hydroxyethyl acrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain an organic silicon polyurethane macromonomer solution;
(4) mixing 5 parts of hydroxymethyl methacrylate, 5 parts of hydroxyethyl methacrylate, 480 parts of organic silicon polyurethane macromonomer solution, 3.5 parts of benzoin dimethyl ether and 100 parts of methanol, homogenizing, irradiating for 200s by ultraviolet light, pouring into a PTFE (polytetrafluoroethylene) mold, and drying at 120 ℃ to form a film to obtain the organic silicon polyurethane material.
The tensile strength of the organic silicon polyurethane material is 29.7MPa, the elastic modulus is 17.8MPa, and the elongation at break is 895%; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 88%; after 30 days there was no calcification of the surface.
Example 21
(1) Placing 17 parts (17g) of polytetramethylene ether glycol (molecular weight is 1000Da) and 100 parts of alpha, omega-dihydroxyethoxy propyl polydimethylsiloxane (molecular weight is 1000Da) in a reaction kettle, heating to melt, fully stirring, heating to 120 ℃, vacuumizing for 2h to remove water and small molecular low-boiling-point substances, closing vacuum, introducing nitrogen and reducing the temperature of the reaction kettle to 45 ℃; then adding 70 parts of diphenylmethane diisocyanate and 400 parts of N, N-dimethylacetamide, and reacting at 45 ℃ for 6 hours;
(2) cooling the temperature of the reaction kettle to 4 ℃, and adding 7 parts of ethylenediamine into the product obtained in the step (1) for reaction for 2 hours;
(3) adding 15 parts of hydroxyethyl methacrylate into the product obtained in the step (2) to react for 6 hours at 45 ℃ to obtain an organosilicon polyurethane macromonomer solution;
(4) mixing 10 parts of trimethylamine N-oxide monomer, 240 parts of organosilicon polyurethane macromonomer solution, 3.5 parts of 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone and 400 parts of water, homogenizing, irradiating for 200 seconds by ultraviolet light, pouring into a PTFE (polytetrafluoroethylene) mold, and drying at 120 ℃ to form a film, thereby obtaining the organosilicon polyurethane material.
The tensile strength of the organic silicon polyurethane material is 30.3MPa, the elastic modulus is 19.5MPa, and the elongation at break is 855%; the mechanical properties are not obviously changed before and after the fatigue test; the surface platelet adhesion amount is reduced by 99%; after 30 days there was no calcification of the surface.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (10)
1. A preparation method of an organic silicon polyurethane material with high blood compatibility is characterized in that a hydrophilic monomer, an organic silicon polyurethane macromonomer, an initiator and a solvent are mixed and homogenized, then the hydrophilic monomer and the organic silicon polyurethane macromonomer are initiated to carry out polymerization reaction, and then the mixture is solidified to obtain the organic silicon polyurethane material, wherein the end group of the organic silicon polyurethane macromonomer contains unsaturated double bonds.
2. The method according to claim 1, wherein the silicone polyurethane macromonomer having an unsaturated double bond at the terminal is prepared by the following steps:
s1, placing polyether polyol and polydimethylsiloxane into a reaction kettle, heating for melting and fully stirring, heating, vacuumizing to remove water and low-boiling-point micromolecules, closing vacuum, filling nitrogen and reducing temperature; adding diisocyanate, and reacting at 0-120 deg.C for 0.5-48h to obtain polyurethane prepolymer;
s2, adding a chain extender into the polyurethane prepolymer obtained in the step S1, and reacting at 0-120 ℃ for 0.5-48 h;
s3, adding an end capping reagent containing unsaturated double bonds into the product obtained in the step S2, and reacting at 20-120 ℃ for 0.5-48h to obtain a solution containing the end group of the organosilicon polyurethane macromonomer containing unsaturated double bonds;
the solvent at least comprises a first solvent, the first solvent is a solvent without active hydrogen, and the solvent without active hydrogen is added in any step of S1 and S2.
3. The method of claim 2, wherein the solvent further comprises a second solvent, and the silicone polyurethane material after the step of S3 is prepared as follows:
s4, mixing the hydrophilic monomer, the organic silicon polyurethane macromonomer solution obtained in the step S3, the initiator and a second solvent, homogenizing, then initiating the polymerization reaction of the hydrophilic monomer and the organic silicon polyurethane macromonomer, and then curing to obtain the organic silicon polyurethane material;
wherein the mass ratio of the hydrophilic monomer, the organic silicon polyurethane macromonomer solution, the initiator and the second solvent is (1-50): 200-1000): 0.1-5): 0-400.
4. The production method according to claim 3, wherein the active hydrogen-free solvent is at least one selected from the group consisting of dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, acetone, ethyl acetate, butyl acetate, dimethyl carbonate, toluene, and xylene;
the second solvent is at least one selected from the group consisting of water, methanol, ethanol, dimethyl sulfoxide, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
5. The method according to claim 2, wherein in the steps S1 to S3, the mass ratio of the polyether polyol, the polydimethylsiloxane, the diisocyanate, the chain extender and the end-capping agent is (0-100): (20-450): (30-160): (2-60): (2-35);
the mass of the solvent without active hydrogen accounts for 50-95% of the total mass of the reaction system for preparing the organosilicon polyurethane macromonomer with the end group containing unsaturated double bond.
6. The method according to claim 2, wherein in the step S1, the polyether polyol is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, octamethylene ether glycol, and decamethylene ether glycol;
the structural formula of the polydimethylsiloxane is as follows:
wherein R is 1 、R 2 Is methyl or phenyl, R 3 Is a linear divalent alkyl radical or alkyl ether containing from 0 to 6 carbon atoms, R 4 Is amino or hydroxyl;
the diisocyanate is selected from at least one of isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate and lysine diisocyanate;
in the step S2, the chain extender is at least one selected from the group consisting of low molecular weight diols, low molecular weight diamines, low molecular weight bishydroxy disulfide and low molecular weight diamino disulfide;
in step S3, the capping reagent is hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, or hydroxypropyl methacrylate.
7. The method according to claim 1, wherein the initiator is a photoinitiator or a thermal initiator, the photoinitiator is a radical initiator, and the thermal initiator is an azo initiator, an organic peroxide or an inorganic peroxide;
when the photoinitiator is adopted, the corresponding specific processes of polymerization reaction and curing are as follows: pouring the mixture into a mold under the irradiation of ultraviolet light for 30-1800s, and drying the mixture at 60-150 ℃ to form a film;
when a thermal initiator is used, the corresponding polymerization and curing processes are as follows: reacting in a reaction kettle at 35-120 deg.C for 0.5-48h, pouring into a mold, and oven drying at 60-150 deg.C to form film.
8. The method of claim 7, wherein the radical initiator is benzoin dimethyl ether, benzophenone, 1-hydroxycyclohexyl phenyl ketone, or 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl phenyl propanone; the azo initiator is azobisisobutyronitrile or azobisisoheptonitrile; the organic peroxide is dibenzoyl peroxide or diethylhexyl dicarbonate peroxide; the inorganic peroxide is potassium persulfate or ammonium persulfate.
9. The method of claim 1, wherein the hydrophilic monomer is selected from the group consisting of acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, N-vinylpyrrolidone, polyethyleneglycol methacrylate, 3- [ [2- (methacryloyloxy) ethyl ] dimethylammonium ] propionate, [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, 2- (methacryloyloxy) ethyl-2- (trimethylamino) ethyl phosphate, trimethylamine N-oxide, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, dimethylaminoethyl acrylate, and mixtures thereof, At least one of dimethylaminoethyl methacrylate, 2-tert-butylaminoethyl acrylate, 2-tert-butylaminoethyl methacrylate, N-diethylaminoethyl acrylate and N, N-diethylaminoethyl methacrylate.
10. An organosilicon polyurethane material having high blood compatibility, which is prepared by the method of any one of claims 1 to 9, wherein the organosilicon polyurethane material has a hetero-interlocking structure formed by radical polymerization of a hydrophilic monomer and an organosilicon polyurethane macromonomer having an unsaturated double bond at a terminal thereof.
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|---|---|---|---|---|
| US4543398A (en) * | 1983-04-28 | 1985-09-24 | Minnesota Mining And Manufacturing Company | Ophthalmic devices fabricated from urethane acrylates of polysiloxane alcohols |
| JP2002037842A (en) * | 2000-05-18 | 2002-02-06 | Dainichiseika Color & Chem Mfg Co Ltd | Ultraviolet curing siloxane modified polyurethane, and its production method |
| CN101602846A (en) * | 2009-07-03 | 2009-12-16 | 烟台德邦科技有限公司 | A kind of three-functionality-degree organosilicon polyurethane acrylate and synthetic method thereof |
| CN111978476A (en) * | 2020-08-25 | 2020-11-24 | 青岛大学 | Sulfonic acid/carboxylic acid type silicon-containing polyurethane acrylate water repellent agent and preparation and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4543398A (en) * | 1983-04-28 | 1985-09-24 | Minnesota Mining And Manufacturing Company | Ophthalmic devices fabricated from urethane acrylates of polysiloxane alcohols |
| JP2002037842A (en) * | 2000-05-18 | 2002-02-06 | Dainichiseika Color & Chem Mfg Co Ltd | Ultraviolet curing siloxane modified polyurethane, and its production method |
| CN101602846A (en) * | 2009-07-03 | 2009-12-16 | 烟台德邦科技有限公司 | A kind of three-functionality-degree organosilicon polyurethane acrylate and synthetic method thereof |
| CN111978476A (en) * | 2020-08-25 | 2020-11-24 | 青岛大学 | Sulfonic acid/carboxylic acid type silicon-containing polyurethane acrylate water repellent agent and preparation and application thereof |
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