CN117430777A - Polyurethane with photoinitiation capability and preparation method and application thereof - Google Patents
Polyurethane with photoinitiation capability and preparation method and application thereof Download PDFInfo
- Publication number
- CN117430777A CN117430777A CN202311406537.3A CN202311406537A CN117430777A CN 117430777 A CN117430777 A CN 117430777A CN 202311406537 A CN202311406537 A CN 202311406537A CN 117430777 A CN117430777 A CN 117430777A
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- Prior art keywords
- polyurethane
- formula
- product
- organic solvent
- preparation
- 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.)
- Pending
Links
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 83
- 239000004814 polyurethane Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000002791 soaking Methods 0.000 claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 40
- 239000000178 monomer Substances 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 29
- 239000003960 organic solvent Substances 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 14
- 229920000570 polyether Polymers 0.000 claims description 14
- 229920005862 polyol Polymers 0.000 claims description 14
- 150000003077 polyols Chemical class 0.000 claims description 14
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 13
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 13
- -1 2-hydroxy ethoxy Chemical group 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 12
- 238000002390 rotary evaporation Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000004970 Chain extender Substances 0.000 claims description 11
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 150000002513 isocyanates Chemical class 0.000 claims description 11
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical class C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 9
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 9
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 7
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 150000008366 benzophenones Chemical class 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 5
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229940117986 sulfobetaine Drugs 0.000 claims description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 5
- 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 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- JXYWFNAQESKDNC-BTJKTKAUSA-N (z)-4-hydroxy-4-oxobut-2-enoate;2-[(4-methoxyphenyl)methyl-pyridin-2-ylamino]ethyl-dimethylazanium Chemical compound OC(=O)\C=C/C(O)=O.C1=CC(OC)=CC=C1CN(CCN(C)C)C1=CC=CC=N1 JXYWFNAQESKDNC-BTJKTKAUSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 101100410826 Salmo salar pym1a gene Proteins 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- BWZOPYPOZJBVLQ-UHFFFAOYSA-K aluminium glycinate Chemical compound O[Al+]O.NCC([O-])=O BWZOPYPOZJBVLQ-UHFFFAOYSA-K 0.000 claims description 2
- 229960003237 betaine Drugs 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- VFRQEVIIBMUKCQ-UHFFFAOYSA-M ethyl-dimethyl-(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(C)CCOC(=O)C=C VFRQEVIIBMUKCQ-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000000017 hydrogel Substances 0.000 abstract description 26
- 238000000576 coating method Methods 0.000 abstract description 23
- 239000011248 coating agent Substances 0.000 abstract description 17
- 239000000758 substrate Substances 0.000 abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 29
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 description 10
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000008280 blood Substances 0.000 description 5
- 210000004369 blood Anatomy 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005580 one pot reaction Methods 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 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 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005316 response function Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 208000007536 Thrombosis Diseases 0.000 description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 230000010100 anticoagulation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical group [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 2
- 206010059837 Adhesion Diseases 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 208000004550 Postoperative Pain Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 208000037816 tissue injury Diseases 0.000 description 1
- ORZHVTYKPFFVMG-UHFFFAOYSA-N xylenol orange Chemical compound OC(=O)CN(CC(O)=O)CC1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(CN(CC(O)=O)CC(O)=O)C(O)=C(C)C=2)=C1 ORZHVTYKPFFVMG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
- C08J2475/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention provides polyurethane with photoinitiation capability, a preparation method and application thereof. Compared with the method of soaking the photoinitiator into the polyurethane substrate, which needs to use organic reagents, the method is simpler and more environment-friendly. The hydrogel coating of the present invention not only exhibits tissue-like softness, controlled thickness, lubricity, but also accommodates the complex geometry of the polymeric substrate.
Description
Technical Field
The invention belongs to the technical field of polyurethane catheter preparation, and relates to polyurethane with photoinitiation capability, a preparation method thereof and application thereof in preparation of a super-hydrophilic super-lubrication polyurethane catheter.
Background
Thermoplastic Polyurethane (TPU) is widely applied to the fields of implant intervention medical articles, film products, various catheter products and the like due to excellent biocompatibility and processability. Particularly Central Venous Catheters (CVCs) for venous access or drug delivery. However, the conventional polyurethane catheter causes problems such as tissue injury, postoperative pain, infection, etc. during the operation. The reason for this is generally: 1) Hydrophobic polyurethane catheter surfaces lack biological lubricating ability; 2) The Young's modulus (10-1800 MPa) of the polyurethane material is far higher than that of the soft tissue (1-100 kPa); 3) The surface of the material lacks antibacterial and antifouling functions. Thus, surface functionalization of polyurethane catheters is an effective solution to the problem.
In recent years, researchers design and develop various material surface modification technologies, such as surface-initiated atom transfer radical polymerization, layer-by-layer self-assembly, mussel-like and other technical means, which are ingenious in process, combine various antibacterial functions, and have certain defects at the same time, such as that the thickness of a polymer brush is generally not more than 100nm, so that the Young's modulus of the polymer surface cannot be obviously reduced. In addition, cumbersome preparation techniques severely limit their clinical application. Compared with the method, the hydrogel coating is favored by researchers due to simple operation, excellent hydrophilicity, good biomechanical properties and versatility. Conventional hydrogel coatings are often immobilized on polymer matrices by surface adsorption or topological micro/nanostructures, which are prone to mechanical dissociation and suffer from poor robustness [ Jiawei Yang, ruobing Bai and Zhigang Suo, topological adhes ion of wet material s [ J ], advanced Materials,2018,30 (25): 1800671 ]. Thus, zhao [ Yan Yu, hyunwoo Yuk, german A.Parada, you Wu, xinyue Liu, chri stock S.Nabzdyk, kamal Youcef-Toumi, jianfeng Zang and Xuanhe Zhao, mult ifunct ional "hydrogelskin" on diverse polymers wi th arbi trary shapes [ J ], advanced Material s,2019,31 (7): 1807101] et al developed an interfacial interpenetrating technique to obtain hydrogel coatings on substrates having complex shapes. The disadvantage is that this technique requires immersing the polymeric substrate in an organic solution to absorb the hydrophobic initiator, which results in the organic solvent being partially left in the polymeric substrate, with potential risks for the medical device. It is therefore still challenging to simply apply a firm hydrogel coating on a polymer substrate with complex geometry in a green and safe manner.
In the patent (CN 102947349B), hydrophilic PEG is used as a raw material to synthesize the water-based polyurethane macromolecular initiator with a benzophenone structure, and a method of ultraviolet light photo-curing after a gel component containing the macromolecular initiator is coated on the surface of the catheter is adopted to prepare the catheter with hydrophilic gel on the surface, so that the problem of poor firmness between the hydrophilic gel part on the surface of the catheter and a substrate exists. And because the synthesized polyurethane macromolecules have good hydrophilicity, and commercial polyurethane elastomers are usually hydrophobic, the problem of poor compatibility of the polyurethane elastomers and the polyurethane elastomers can occur in the process of melt blending and extrusion, so that the mechanical properties of the prepared catheter are rapidly reduced.
In the patent, a novel polyurethane (BPTPU) with photoinitiation capability is designed and synthesized through a solvent-free method, and is blended with commercial polyurethane to form a polyurethane catheter with photoinitiation capability, a firm hydrogel coating can be grown on the surface through Ultraviolet (UV) irradiation, and the hydrophilic surface has high affinity with an interface, so that the free energy of the interface is greatly reduced, the effect of the material surface on various components in blood is reduced, and therefore, the excellent anticoagulation performance is presented.
Disclosure of Invention
The invention aims at solving the problems existing in the prior art and provides a preparation method and application of a super-hydrophilic super-lubricating polyurethane catheter.
The aim of the invention can be achieved by the following technical scheme:
in a first aspect, the present invention provides a photoinitiating polyurethane of formula I,
wherein m is an integer of 10 to 60; n is an integer of 10 to 50; r is R 2 Alkylene of C2-C6; x is-O-or-NH-;
m is one of the following groups:
R 1 is one of the following groups:
preferably M isR 1 Is->R2 is a C4 alkylene group.
In a second aspect, the present invention provides a method for preparing the polyurethane with photoinitiating capability shown in the formula I, wherein the polyurethane with photoinitiating capability is prepared according to the following method:
s1: dissolving a benzophenone derivative and triethylamine in an organic solvent A, dropwise adding an organic solvent solution of acryloyl chloride (slowly) in an ice water bath, stirring at room temperature for 12 hours, and performing aftertreatment on the obtained reaction solution to obtain a product a; the diphenyl ketone derivative is at least one of 4-hydroxy diphenyl ketone, 4- (2-hydroxy ethoxy) diphenyl ketone and 4-methoxy-2-hydroxy diphenyl ketone (preferably 4-hydroxy diphenyl ketone); the molar ratio of the diphenyl ketone derivative to the acrylic chloride contained in the organic solvent solution of the triethylamine to the acrylic chloride is 1:1-2:1-2 (preferably 1:1:1.5);
s2, dropwise adding the product a and diethanolamine obtained in the step S1 into an organic solvent B under the condition of light shielding, stirring at room temperature for dissolution, carrying out water bath reaction at 30-50 ℃ for 4-6h (preferably 35 ℃ for 4 h), and removing the solvent by rotary evaporation to obtain a product B; the molar ratio of the product a to the diethanolamine is 1:1-2 (preferably 1:1);
s3: uniformly stirring polyether polyol, a chain extender shown in a formula h and a product b shown in a step S2 at 50-80 ℃ (preferably 60 ℃), (rapidly) dropwise adding isocyanate shown in a formula g, (rapidly) uniformly stirring, adding a polyurethane synthesis catalyst, (rapidly) stirring for 30S, pouring the obtained sample into a (polytetrafluoroethylene) mold, and maintaining the temperature of 60-100 ℃ for 24-72h (preferably 72h at 80 ℃) under vacuum environment to obtain polyurethane with photoinitiation shown in a formula I; the molar ratio of the total amount of the polyether polyol, the chain extender represented by formula h and the hydroxyl and amino groups contained in the product b to the isocyanate groups contained in the isocyanate represented by formula g is 1:1-1.2; the amount of the polyether polyol is 20-80mol% of the total amount of the polyether polyol, the chain extender represented by formula h and the hydroxyl and amino groups contained in the product b of step S2, based on the amount of hydroxyl groups contained; the amount of the product b is 5 to 50mol% based on the amount of hydroxyl-containing substances, based on the total amount of the polyether polyol, the chain extender represented by formula h and hydroxyl-and amino-containing substances of the product b in step S2; the mass of the polyurethane synthesis catalyst is 0.1wt% -1wt% (0.5 wt% in one embodiment of the invention) of the total mass of the polyether polyol, the chain extender represented by formula h, the product b and the isocyanate represented by formula g;
OCN—R 1 -NCO g
XH-R 2 -XH h
further, the organic solvents contained in the organic solvent A and the organic solvent solution of the acryloyl chloride are at least one of alcohol with C1 to C3, acetone, acetonitrile, dichloromethane, chloroform and tetrahydrofuran respectively.
Further, the total volume of the organic solvents contained in the organic solvent A and the organic solvent solution of acryloyl chloride is 5-20mL/g based on the mass of the benzophenone derivative. In one embodiment of the invention, the volume of the organic solvent a is 5mL/g based on the mass of the benzophenone derivative; the volume of the organic solvent contained in the organic solvent solution of acryloyl chloride was 5mL/g based on the mass of the benzophenone derivative.
Further, in step S1, the post-processing is: the reaction solution was washed with saturated sodium bicarbonate and saturated sodium chloride solution in this order (twice), and the obtained organic phase was dried over anhydrous sodium sulfate and distilled off to obtain a product a.
In step S2, the organic solvent B is at least one of a C1 to C3 alcohol, acetone, acetonitrile, dichloromethane, chloroform, and tetrahydrofuran. Still further, in step S2, the volume of the organic solvent B is 5-20mL/g based on the mass of the product a.
Further, in step S3, the polyether polyol is polytetrahydrofuran (molecular weight is 800-4000).
Further, in step S3, the chain extender is one of 1, 4-Butanediol (BDO), 1, 6-hexanediol, diethylene glycol (DEG), and ethylenediamine (DA). The general formula is as follows:
XH-R 2 -XH
further in step S3, the isocyanate may be Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI) or Hexamethylene Diisocyanate (HDI), preferably hexamethylene diisocyanate. The general formula is as follows:
OCN-R 1 -NCO
further in step S3, the polyurethane synthesis catalyst is dibutyltin dilaurate, stannous iso-octoate, pentamethyldiethylenetriamine or dimethylcyclohexylamine, preferably dibutyltin dilaurate.
In a third aspect, the present invention provides the use of the above polyurethane with photoinitiating capability for the preparation of a superhydrophilic superlubricious polyurethane catheter.
Specifically, the application is: uniformly mixing commercial medical polyurethane with the mass ratio of 9:1-6 with polyurethane shown in the formula I, and extruding a catheter in a double-screw extruder; immersing the catheter in a solution of vinyl functional monomer with the concentration of 5-30wt% (preferably 20wt%) and irradiating with ultraviolet for 2-30min to obtain the super-hydrophilic super-lubricating polyurethane catheter;
the vinyl functional monomer is one or more than two of methyl acryloyloxyethyl trimethyl ammonium chloride, dimethyl aminoethyl methacrylate, methacrylic acid, fluorescent monomer PyMA, fluorescent monomer NDBCB, fluorescent monomer SPMA, N-isopropyl acrylamide, dimethyl- (4-vinyl phenyl) ammonium propane sulfonate, hydroxyethyl methacrylate (HEMA), N-hydroxyethyl acrylamide (HEAA), sulfobetaine methacrylate (SBMA), carboxyl betaine methyl methacrylate (CBMA), polyethylene glycol methacrylate (POEGMA) and Acrylamide (AM) (preferably N-hydroxyethyl acrylamide, sulfobetaine methacrylate, hydroxyethyl methacrylate or acrylamide).
Preferably, the commercial medical polyurethane is a thermoplastic polyurethane elastomer resin (TPU), preferably Korschun RxT A, basoff C85A10 or Lubo AC-4075A.
Further, the screw speed of the double screw extruder is 150-400rpm/min, and the temperature is 150-200 ℃.
The invention recommends that the raw materials such as polyurethane and the like are put into a conduit extruder for extruding a conduit after being dehydrated at 80 ℃.
In the preparation method of the polyurethane catheter with super hydrophilicity and super lubrication, the vinyl functional monomer can be methacryloxyethyl trimethyl ammonium chloride (METAC) with sterilization function, dimethylaminoethyl methacrylate (DMAEMA) with pH response function, methacrylic acid (MAA), fluorescent monomer PyMA, NDBCB, SPMA and the like, N-isopropyl acrylamide (NIPAM) with temperature response function, dimethyl- (4-vinylphenyl) ammonium propane sulfonate (DVBAPS) with salt response function, and monomers with functional double bonds such as hydroxyethyl methacrylate (HEMA), N-hydroxyethyl acrylamide (HEAA), sulfobetaine methacrylate (SBMA), carboxybetaine methyl methacrylate (CBMA), polyethylene glycol methacrylate (POE), acrylamide (AM) and the like; the vinyl functional monomer concentration may be 5-30wt%; the ultraviolet power is 20-100w, and the illumination time is 2-30min.
Compared with the prior art, the invention has the following beneficial effects:
1. the polyurethane with photoinitiation capability in the invention contains a benzophenone structure, and a layer of hydrogel coating is formed on the surface of a polyurethane substrate in a mode of ultraviolet initiation by soaking a monomer solution. Compared to the method of soaking the photoinitiator into the polyurethane substrate, which requires the use of organic reagents, such as oil-soluble initiators like benzophenone, etc., into the polymer, the method is simpler and more environment-friendly.
2. The hydrogel coating of the present invention not only exhibits tissue-like softness, controlled thickness, lubricity, but also accommodates the complex geometry of the polymeric substrate.
3. The polyurethane with photoinitiation capability prepared by the invention has better compatibility with commercial polyurethane, a catheter containing BPTPU can be prepared by melt extrusion, and a hydrophilic hydrogel coating is formed on the inner wall, so that the polyurethane is applied to antifouling and anticoagulation. The antibacterial hydrogel coating, the fluorescent hydrogel coating and the stimulus response type functional hydrogel coating can be constructed, and the method has wide application scenes.
4. Compared with the common way of light curing the gel precursor liquid on the surface of the elastomer substrate, the gel coating provided by the invention has better firmness and better durability.
5. By selecting different types of isocyanate raw materials, the photoinitiation capability of polyurethane synthesized by different isocyanates is compared, and polyurethane with the best initiation capability is optimized.
Drawings
FIG. 1 is a chemical equation for testing free radical content;
FIG. 2 is a schematic diagram of a bond strength test;
FIG. 3 shows the number of radicals generated, the thickness of the hydrogel coating, and the bond strength between the coating and the polyurethane in examples 1-5, which were synthesized from different isocyanate species, by immersing the same monomer solution at the same concentration, at the same time of UV photography;
FIG. 4 is a scanning electron microscope image (a), a thickness image (b), a water contact angle image (c) and a friction coefficient image (d) of hydrogel coatings under different illumination times in comparative examples 1 to 5;
FIG. 5 is a graph of water contact angle (a) and coefficient of friction (b) for hydrogel coatings at different monomer concentrations in comparative examples 6-8;
FIG. 6 is a graph of the coefficient of friction (a) of hydrogel coatings of different hydrophilic monomer species and a graph of a dynamic circulation model (b) of calcified whole blood in comparative examples 9-11.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention are further described, but the present invention is not limited to these examples.
Example 1
S1, 4-hydroxybenzophenone (1.98 g,10 mmol) and triethylamine (1.4 mL,10 mmol) were dissolved in a round bottom flask containing 10mL of dichloromethane, 10mL of a solution of acryloyl chloride (1.2 mL,15 mmol) in dichloromethane was slowly added dropwise under ice-water bath and stirred at room temperature for 12h. After the reaction was completed, the reaction solution was treated with saturated sodium bicarbonate (NaHCO 3 ) And saturated sodium chloride (NaCl) are washed twice respectively, the organic layer is extracted, and then the anhydrous Na is used 2 SO 4 After drying, the solvent was removed by rotary evaporation to give the product a1.
S2, dropwise adding a product a1 (1.0 g,3.96 mmol) and diethanolamine (0.4 g,3.96 mmol) into 10mL of ethanol under a dark condition, stirring at room temperature for 30min for dissolution, heating to 35 ℃ in a water bath, reacting for 4h, and removing an ethanol solvent by rotary evaporation at room temperature to obtain a product b1.
S3, preparing polyurethane with photoinitiation function by adopting a one-pot method, adding polytetrahydrofuran (16 g,16 mmol), 1, 4-butanediol (0.18 g,2 mmol) and a product b1 (0.714 g,2 mmol) with the molecular weight of 1000 after water removal into a round-bottomed flask, stirring at 60 ℃ for 30min, then rapidly dropwise adding Hexamethylene Diisocyanate (HDI) (3.264 g,20 mmol), rapidly stirring, then adding a catalyst dibutyltin dilaurate (DBTDL) accounting for 0.5% of the total weight of each component of the system, rapidly stirring for 30S, pouring a sample into a polytetrafluoroethylene mold, vacuumizing in a vacuum oven at 80 ℃ for 72h, and obtaining the polyurethane with photoinitiation function (BPTPU), wherein the weight average molecular weight of the polyurethane is about 6 ten thousand.
S4, placing the commercial polyurethane (Basoff C85A10 in Germany) and the BPTPU mixture (the mass ratio is 6:4) into a double-screw extruder with the screw rotating speed of 300rpm/min and the processing temperature of 185 ℃ for extruding the guide pipe.
S5, soaking the catheter in a 20wt% hydrophilic monomer Acrylamide (AM) monomer aqueous solution, and irradiating with ultraviolet for 10min at 20 w.
Example 2
S1, 4-hydroxybenzophenone (1.98 g,10 mmol) and triethylamine (1.4 mL,10 mmol) were dissolved in a round bottom flask containing 10mL of dichloromethane, 10mL of a solution of acryloyl chloride (1.2 mL,15 mmol) in dichloromethane was slowly added dropwise under ice-water bath and stirred at room temperature for 12h. After the reaction was completed, the reaction solution was treated with saturated sodium bicarbonate (NaHCO 3 ) And saturated sodium chloride (NaCl) are washed twice respectively, the organic layer is extracted, and then the anhydrous Na is used 2 SO 4 After drying, the solvent was removed by rotary evaporation to give the product a1.
S2, dropwise adding a product a1 (1.0 g,3.96 mmol) and diethanolamine (0.4 g,3.96 mmol) into 10mL of ethanol under a dark condition, stirring at room temperature for 30min for dissolution, heating to 35 ℃ in a water bath, reacting for 4h, and removing an ethanol solvent by rotary evaporation at room temperature to obtain a product b1.
S3, preparing polyurethane with photoinitiation function by adopting a one-pot method, adding polytetrahydrofuran (16 g,16 mmol), 1, 4-butanediol (0.18 g,2 mmol) and a product b1 (0.714 g,2 mmol) with the molecular weight of 1000 after water removal into a round-bottomed flask, stirring at 60 ℃ for 30min, then rapidly dripping Toluene Diisocyanate (TDI) (3.48 g,20 mmol), rapidly stirring, then adding a catalyst dibutyltin dilaurate (DBTDL) accounting for 0.5% of the total weight of each component of the system, rapidly stirring for 30S, pouring a sample into a polytetrafluoroethylene mold, vacuumizing and maintaining for 72h in a vacuum oven at 80 ℃ to obtain polyurethane (BPTPU) with photoinitiation function, wherein the weight average molecular weight of the polyurethane is about 6.5 ten thousand.
S4, placing the commercial polyurethane (Basoff C85A10 in Germany) and the BPTPU mixture (the mass ratio is 6:4) into a double-screw extruder with the screw rotating speed of 300rpm/min and the processing temperature of 185 ℃ for extruding the guide pipe.
S5, soaking the catheter in a 20wt% hydrophilic monomer Acrylamide (AM) monomer aqueous solution, and irradiating with ultraviolet for 10min at 20 w.
Example 3
S1, 4-hydroxybenzophenone (1.98 g,10 mmol) and triethylamine (1.4 mL,10 mmol) were dissolved in a round bottom flask containing 10mL of dichloromethane, 10mL of a solution of acryloyl chloride (1.2 mL,15 mmol) in dichloromethane was slowly added dropwise under ice-water bath and stirred at room temperature for 12h. After the reaction was completed, the reaction solution was treated with saturated sodium bicarbonate (NaHCO 3 ) And saturated sodium chloride (NaCl) are washed twice respectively, the organic layer is extracted, and then the anhydrous Na is used 2 SO 4 After drying, the solvent was removed by rotary evaporation to give the product a1.
S2, dropwise adding a product a1 (1.0 g,3.96 mmol) and diethanolamine (0.4 g,3.96 mmol) into 10mL of ethanol under a dark condition, stirring at room temperature for 30min for dissolution, heating to 35 ℃ in a water bath, reacting for 4h, and removing an ethanol solvent by rotary evaporation at room temperature to obtain a product b1.
S3, preparing polyurethane with photoinitiation function by adopting a one-pot method, adding polytetrahydrofuran (16 g,16 mmol), 1, 4-butanediol (0.18 g,2 mmol) and a product b1 (0.714 g,2 mmol) with the molecular weight of 1000 after water removal into a round-bottomed flask, stirring at 60 ℃ for 30min, then rapidly dropwise adding isophorone diisocyanate (IPDI) (4.4475 g,20 mmol), rapidly stirring, then adding a catalyst dibutyltin dilaurate (DBTDL) with the total weight of each component of the system, rapidly stirring for 30S, pouring the sample into a polytetrafluoroethylene mold, vacuumizing in a vacuum oven at 80 ℃ for 72h to obtain polyurethane (BPTPU) with photoinitiation function, wherein the weight average molecular weight of the polyurethane is about 5.6 ten thousand.
S4, placing the commercial polyurethane (Basoff C85A10 in Germany) and the BPTPU mixture (the mass ratio is 6:4) into a double-screw extruder with the screw rotating speed of 300rpm/min and the processing temperature of 185 ℃ for extruding the guide pipe.
S5, soaking the catheter in a 20wt% hydrophilic monomer Acrylamide (AM) monomer aqueous solution, and irradiating with ultraviolet for 10min at 20 w.
Example 4
S1, 4-hydroxybenzophenone (1.98 g,10 mmol) and triethylamine (1.4 mL,10 mmol) were dissolved in a round bottom flask containing 10mL of dichloromethane, 10mL of a solution of acryloyl chloride (1.2 mL,15 mmol) in dichloromethane was slowly added dropwise under ice-water bath and stirred at room temperature for 12h. After the reaction was completed, the reaction solution was treated with saturated sodium bicarbonate (NaHCO 3 ) And saturated sodium chloride (NaCl) are washed twice respectively, the organic layer is extracted, and then the anhydrous Na is used 2 SO 4 After drying, the solvent was removed by rotary evaporation to give the product a1.
S2, dropwise adding a product a1 (1.0 g,3.96 mmol) and diethanolamine (0.4 g,3.96 mmol) into 10mL of ethanol under a dark condition, stirring at room temperature for 30min for dissolution, heating to 35 ℃ in a water bath, reacting for 4h, and removing an ethanol solvent by rotary evaporation at room temperature to obtain a product b1.
S3, preparing polyurethane with photoinitiation function by adopting a one-pot method, adding polytetrahydrofuran (16 g,16 mmol), 1, 4-butanediol (0.18 g,2 mmol) and a product b1 (0.714 g,2 mmol) with the molecular weight of 1000 after water removal into a round-bottomed flask, stirring at 60 ℃ for 30min, then rapidly dripping diphenylmethane diisocyanate (MDI) (5.05 g,20 mmol), rapidly stirring, then adding a catalyst dibutyltin dilaurate (DBTDL) with the total weight of each component of the system, rapidly stirring for 30S, pouring a sample into a polytetrafluoroethylene mold, vacuumizing in a vacuum oven at 80 ℃ for 72h, and obtaining polyurethane (BPTPU) with photoinitiation function, wherein the weight average molecular weight of the polyurethane is about 7.4 ten thousand.
S4, placing the commercial polyurethane (Basoff C85A10 in Germany) and the BPTPU mixture (the mass ratio is 6:4) into a double-screw extruder with the screw rotating speed of 300rpm/min and the processing temperature of 185 ℃ for extruding the guide pipe.
S5, soaking the catheter in a 20wt% hydrophilic monomer Acrylamide (AM) monomer aqueous solution, and irradiating with ultraviolet for 10min at 20 w.
Example 5
S1, 4-hydroxybenzophenone (1.98 g,10 mmol) and triethylamine (1.4 mL,10 mmol) were dissolved in a round bottom flask containing 10mL of dichloromethane, 10mL of a solution of acryloyl chloride (1.2 mL,15 mmol) in dichloromethane was slowly added dropwise under ice-water bath and stirred at room temperature for 12h. After the reaction was completed, the reaction solution was treated with saturated sodium bicarbonate (NaHCO 3 ) And saturated sodium chloride (NaCl) are washed twice respectively, the organic layer is extracted, and then the anhydrous Na is used 2 SO 4 After drying, the solvent was removed by rotary evaporation to give the product a1.
S2, dropwise adding a product a1 (1.0 g,3.96 mmol) and diethanolamine (0.4 g,3.96 mmol) into 10mL of ethanol under a dark condition, stirring at room temperature for 30min for dissolution, heating to 35 ℃ in a water bath, reacting for 4h, and removing an ethanol solvent by rotary evaporation at room temperature to obtain a product b1.
S3, preparing polyurethane with photoinitiation function by adopting a one-pot method, and adding polytetrahydrofuran (16 g,16 mmol), 1, 4-butanediol (0.18 g,2 mmol) and a product b with molecular weight of 1000 after water removal 1 (0.714 g,2 mmol) was added to a round bottom flask and stirred at 60℃for 30min, followed by rapid dropwise addition of dicyclohexylmethane diisocyanate (HMDI) (5.247 g,20 mmol), rapid stirring, followed by addition of dibutyltin dilaurate (DBTDL) as a catalyst in an amount of 0.5% by weight based on the total weight of the components of the system, rapid stirring for 30s, pouring the sample into a polytetrafluoroethylene mold, and placing into a vacuum oven at 80℃and vacuum-maintaining for 72h to obtain a polyurethane with photoinitiation (BPTPU) having a weight average molecular weight of about 7.3 ten thousand.
S4, placing the commercial polyurethane (Basoff C85A10 in Germany) and the BPTPU mixture (the mass ratio is 6:4) into a double-screw extruder with the screw rotating speed of 300rpm/min and the processing temperature of 185 ℃ for extruding the guide pipe.
S5, soaking the catheter in a 20wt% hydrophilic monomer Acrylamide (AM) monomer aqueous solution, and irradiating with ultraviolet for 10min at 20 w.
Comparative examples 1 to 5
Other operations are the same as in example 1, except that the illumination time in step S5 is changed, and comparative examples 1 to 5 correspond to the ultraviolet illumination times of 0, 2, 4, 6 and 8 minutes, respectively;
comparative examples 6 to 8
Other operations were the same as in example 1, except that the concentration of the immersion monomer in step S5 was changed, and comparative examples 6 to 8 correspond to the monomer concentrations of 0wt%, 10wt% and 30wt%, respectively;
comparative examples 9 to 11
The other procedures were as in example 1, except that the hydrophilic monomer species in step S5 was changed, and comparative examples 9 to 11 correspond to sulfobetaine methacrylate (SBMA), hydroxyethyl methacrylate (HEMA), N-hydroxyethyl acrylamide (HEAA), respectively.
The free radical test method comprises the following steps: the Fenton reaction (Fenton reaction) is adopted to quantitatively detect the content of free radicals, and under the irradiation of ultraviolet light, the free radicals generated by the BPTPU react with water to generate hydrogen peroxide (H) 2 O 2 )，H 2 O 2 Ferrous ions (Fe 2+ ) Oxidation to ferric ion (Fe) 3+ ) Fe produced 3+ The concentration is proportional to the radical generated and can then be determined by the action of xylenol orange (XO, fe 3+ Indicator of (c) pair of production of Fe 3+ Quantitative detection can be performed reflecting the amount of free radical formation (FIG. 1). Characterized by an ultraviolet-visible-near infrared spectrometer, the XO indicator has an ultraviolet absorption peak at 430nm, and the XO indicator is mixed with Fe 3+ The bound product has an ultraviolet absorption peak at 550nm. We will have different concentrations of Fe 3+ Mixing the solution with quantitative XO indicator to obtain uniform solution, and obtaining Fe with different concentrations by ultraviolet-visible-near infrared spectrometer 3+ Standard curve of absorbance after combination with XO, fe 3+ The concentration is proportional to the absorbance, and the standard curve is: y=0.02162x+0.0078. The amount of radical generated was measured by a standard curve.
The method for testing the adhesive strength of the hydrogel-polyurethane comprises the following steps: hydrogel-forming polymersThe urethane sheet was cut into a rectangle of a certain size, two sides of the urethane sheet with hydrogel were attached with glass sheets coated with glue, and then two sides of the glass sheets were clamped in clamps at the upper and lower ends of a stretcher, and stretched at a speed of 50mm/min, and the binding force between the hydrogel and the urethane interface was tested (fig. 2). Interface combination calculation formula: sigma=f/a 0 (F: load, A) 0 : cross-sectional area, unit: n/m). All samples were tested at 25 ℃.
As can be seen from FIG. 3, the difference in photoinitiating ability of the polyurethanes synthesized from the different isocyanate types in examples 1-5, preferably BPTPU synthesized using hexamethylene diisocyanate, is probably due to the aromatic or aliphatic ring structure contained in the isocyanate structures of examples 2-4, has greater rigidity than the aliphatic hydrocarbon structure isocyanate of example 1, and prevents the generated small molecule free radicals from contacting with the monomer solution, and a certain cyclic conjugated structure may affect the activity of the free radicals. The difference in bond strength is probably the most radical generated in example 1, the most interfacial chain entanglement, and the strongest binding capacity.
As can be seen from FIG. 4, the difference between example 1 and comparative examples 1 to 5 is that the thickness of the hydrogel coating layer is continuously reduced due to the reduction of the irradiation time of ultraviolet light, which means that the content of free radicals generated by polyurethane is increased with the increase of the irradiation time, and the thickness of the hydrogel coating layer is also reduced due to the reduction of the irradiation time, resulting in the decrease of hydrophilicity and the increase of friction coefficient, which are also found in the experiments of contact angle and friction coefficient.
As is clear from FIG. 5, the difference between example 1 and comparative examples 1 and 7-8 is that the change of the monomer concentration is changed, the surface gradually changes from hydrophobic to hydrophilic as the monomer concentration increases, the surface hydrophilic-hydrophobic property changes after the hydrogel coating is formed by the surface initiation, but the change of the surface hydrophilic-hydrophobic property is not greatly affected after the certain monomer concentration (more than or equal to 20 wt%) is reached, in terms of friction, when the hydrogel coating is not formed on the polyurethane surface, the friction coefficient is 0.75, when the monomer concentration is 10wt%, the friction coefficient is remarkably reduced by 0.15, when the monomer concentration is increased to 20wt%, the friction coefficient is further reduced to 0.05, but then even if the monomer concentration is increased to 30wt%, the friction coefficient changes slightly, which means that when the acrylamide monomer concentration is 20wt%, the thicker hydrogel coating is formed on the polyurethane surface, and the friction can be effectively reduced.
As can be seen from fig. 6, the change of different hydrophilic monomers, first of all, is available in terms of friction coefficient, the coating layer containing hydrophilic hydrogel has a smaller friction coefficient than the control group, and furthermore, by establishing a dynamic circulation model of calcified whole blood, it was found that the catheter of the control group was severely blocked after circulating 1h of blood, forming many adherent clots on the inner wall. In contrast, catheters with hydrogel coatings remained unobstructed and no significant thrombus was observed, with only a small amount of blood clots, and the poor quality of blood indicated that the hydrogel coating could help the catheter to anticoagulate.
The point values in the technical scope of the present invention are not exhaustive, and the new technical solutions formed by equivalent substitution of single or multiple technical features in the technical solutions of the embodiments are also within the scope of the present invention; meanwhile, in all the listed or unrecited embodiments of the present invention, each parameter in the same embodiment represents only one example of the technical scheme (i.e. a feasibility scheme), and no strict coordination and limitation relation exists between each parameter, wherein each parameter can be replaced with each other without violating axiom and the requirement of the present invention, except what is specifically stated.
The technical means disclosed by the scheme of the invention is not limited to the technical means disclosed by the technical means, and also comprises the technical scheme formed by any combination of the technical features. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, and such changes and modifications are intended to be included within the scope of the invention.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (10)
1. A polyurethane of the formula (I),
wherein m is an integer of 10 to 60; n is an integer of 10 to 50; r is R 2 Alkylene of C2-C6; x is-O-or-NH-;
m is one of the following groups:
R 1 is one of the following groups:
2. the process for preparing the polyurethane of formula I as claimed in claim 1, wherein the polyurethane is prepared as follows:
s1: dissolving a benzophenone derivative and triethylamine in an organic solvent A, dropwise adding an organic solvent solution of acryloyl chloride in an ice water bath, stirring at room temperature for 12 hours, and performing aftertreatment on the obtained reaction solution to obtain a product a; the diphenyl ketone derivative is at least one of 4-hydroxy diphenyl ketone, 4- (2-hydroxy ethoxy) diphenyl ketone and 4-methoxy-2-hydroxy diphenyl ketone; the molar ratio of the diphenyl ketone derivative to the acrylic chloride contained in the organic solvent solution of the triethylamine to the acrylic chloride is 1:1-2:1-2;
s2, dropwise adding the product a and diethanolamine obtained in the step S1 into an organic solvent B under the condition of light shielding, stirring at room temperature for dissolution, reacting in a water bath at 30-50 ℃ for 4-6h, and removing the solvent by rotary evaporation to obtain a product B; the molar ratio of the product a to the diethanolamine is 1:1-2;
s3: uniformly stirring polyether polyol, a chain extender shown in a formula h and a product b shown in a step S2 at 50-80 ℃, dropwise adding isocyanate shown in a formula g, uniformly stirring, adding a polyurethane synthesis catalyst, stirring for 30S, pouring the obtained sample into a mold, and maintaining the temperature at 60-100 ℃ for 24-72h under a vacuum environment to obtain polyurethane shown in a formula I and having photoinitiation; the molar ratio of the total amount of the polyether polyol, the chain extender represented by formula h and the hydroxyl and amino groups contained in the product b to the isocyanate groups contained in the isocyanate represented by formula g is 1:1-1.2; the amount of the polyether polyol is 20-80mol% of the total amount of the polyether polyol, the chain extender represented by formula h and the hydroxyl and amino groups contained in the product b of step S2, based on the amount of hydroxyl groups contained; the amount of the product b is 5 to 50mol% based on the amount of hydroxyl-containing substances, based on the total amount of the polyether polyol, the chain extender represented by formula h and hydroxyl-and amino-containing substances of the product b in step S2; the mass of the polyurethane synthesis catalyst is 0.1-1 wt% of the total mass of the polyether polyol, the chain extender shown in the formula h, the product b and the isocyanate shown in the formula g;
OCN-R 1 -NCO g
XH-R 2 -XH h
3. a process for the preparation of a polyurethane of formula I as claimed in claim 2, wherein: the organic solvents contained in the organic solvent A and the organic solvent solution of the acryloyl chloride are at least one of alcohol with C1-C3, acetone, acetonitrile, methylene dichloride, chloroform and tetrahydrofuran respectively and independently;
the total volume of the organic solvent contained in the organic solvent A and the organic solvent solution of the acryloyl chloride is 5-20mL/g based on the mass of the benzophenone derivative.
4. A process for the preparation of a polyurethane of formula I as claimed in claim 2, wherein: in step S1, the post-processing is: the reaction solution is washed by saturated sodium bicarbonate and saturated sodium chloride solution in sequence, and the obtained organic phase is dried by anhydrous sodium sulfate and is distilled in a rotary way to obtain a product a.
5. A process for the preparation of a polyurethane of formula I as claimed in claim 2, wherein: in the step S2, the organic solvent B is at least one of alcohol, acetone, acetonitrile, methylene dichloride, chloroform and tetrahydrofuran with the carbon number of C1-C3;
in step S2, the volume of the organic solvent B is 5-20mL/g based on the mass of the product a.
6. A process for the preparation of a polyurethane of formula I as claimed in claim 2, wherein: in step S3, the polyether polyol is polytetrahydrofuran.
7. A process for the preparation of a polyurethane of formula I as claimed in claim 2, wherein: in step S3, the polyurethane synthesis catalyst is dibutyltin dilaurate, stannous isooctanoate, pentamethyldiethylenetriamine or dimethylcyclohexylamine.
8. Use of the polyurethane according to claim 1 for the preparation of a super hydrophilic super lubricious polyurethane catheter.
9. The application according to claim 8, characterized in that the application is: uniformly mixing commercial medical polyurethane with the mass ratio of 9:1-6 with polyurethane shown in the formula I, and extruding a catheter in a double-screw extruder; soaking the catheter in a solution of vinyl functional monomer with the concentration of 5-30wt% and irradiating for 2-30min by ultraviolet to obtain the super-hydrophilic super-lubricating polyurethane catheter;
the vinyl functional monomer is one or more than two of methyl acryloyloxyethyl trimethyl ammonium chloride, dimethylaminoethyl methacrylate, methacrylic acid, fluorescent monomer PyMA, fluorescent monomer NDBCB, fluorescent monomer SPMA, N-isopropyl acrylamide, dimethyl- (4-vinylphenyl) ammonium propane sulfonic acid inner salt, hydroxyethyl methacrylate, N-hydroxyethyl acrylamide, sulfobetaine methacrylate, carboxyl betaine methyl methacrylate, polyethylene glycol methacrylate and acrylamide.
10. The use according to claim 9, wherein: the commercial medical polyurethane is thermoplastic polyurethane elastomer resin; the screw speed of the double screw extruder is 150-400rpm/min, and the temperature is 150-200 ℃.
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| CN202311406537.3A CN117430777A (en) | 2023-10-27 | 2023-10-27 | Polyurethane with photoinitiation capability and preparation method and application thereof |
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| CN202311406537.3A CN117430777A (en) | 2023-10-27 | 2023-10-27 | Polyurethane with photoinitiation capability and preparation method and application thereof |
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