CN100391994C - Preparation method of chitin modified water polyurethane elastic body - Google Patents
Preparation method of chitin modified water polyurethane elastic body Download PDFInfo
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- CN100391994C CN100391994C CNB2006100403309A CN200610040330A CN100391994C CN 100391994 C CN100391994 C CN 100391994C CN B2006100403309 A CNB2006100403309 A CN B2006100403309A CN 200610040330 A CN200610040330 A CN 200610040330A CN 100391994 C CN100391994 C CN 100391994C
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- elastic body
- chitosan
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- modified water
- chitin modified
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229920002101 Chitin Polymers 0.000 title claims description 24
- 229920001661 Chitosan Polymers 0.000 claims abstract description 40
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 31
- 239000000839 emulsion Substances 0.000 claims abstract description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000004985 diamines Chemical class 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 9
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 9
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000002585 base Substances 0.000 claims description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 13
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 3
- 150000001263 acyl chlorides Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910000765 intermetallic Inorganic materials 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000012875 nonionic emulsifier Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 26
- 229920003225 polyurethane elastomer Polymers 0.000 abstract description 15
- 210000004369 blood Anatomy 0.000 abstract description 7
- 239000008280 blood Substances 0.000 abstract description 7
- 239000012567 medical material Substances 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000010276 construction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 25
- 239000010408 film Substances 0.000 description 18
- 238000010907 mechanical stirring Methods 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 10
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- 230000002429 anti-coagulating effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- -1 aryl imine Chemical class 0.000 description 6
- 230000004071 biological effect Effects 0.000 description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 6
- 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 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 230000023555 blood coagulation Effects 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 3
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229940095064 tartrate Drugs 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 2
- 239000004472 Lysine Substances 0.000 description 2
- 241001112258 Moca Species 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000010100 anticoagulation Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 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
- 239000007788 liquid Substances 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 230000035790 physiological processes and functions Effects 0.000 description 2
- 210000002381 plasma Anatomy 0.000 description 2
- 229920003224 poly(trimethylene oxide) Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241000186000 Bifidobacterium Species 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 239000002473 artificial blood Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 210000000845 cartilage Anatomy 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- WDWDWGRYHDPSDS-UHFFFAOYSA-N methanimine Chemical compound N=C WDWDWGRYHDPSDS-UHFFFAOYSA-N 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012858 resilient material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 210000003437 trachea Anatomy 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Materials For Medical Uses (AREA)
Abstract
The present invention discloses a method for preparing a chitosan modified aqueous polyurethane elastomer, which comprises the following steps that polyisocyanate firstly reacts with poly-polyatomic alcohol, glycol or diamine, and then a polyurethane prepolymer is obtained; the polyurethane prepolymer is dissolved by organic solvent, an ionized agent is added in, and then an ionized polyurethane prepolymer is obtained; the ionized polyurethane prepolymer reacts with a chitosan water solution and emulsifier, polyurethane emulsion or microemulsion is obtained, a film can be also formed. The present invention has the advantage of simple preparation method, the prepared chitosan modified embedded-section polyurethane elastomer has the good performance of good mechanical performance, easy processing, fine oil and water resistance, controllable performance, good biocompatibility, biodegradability, high bioactivity, fine blood contact performance, etc. The present invention can be applied to the field of mechanical industry, construction industry, sports, medical treatment, etc. and has a wide purpose on the aspects of life science study, medical materials and medical apparatus.
Description
One, technical field
The present invention relates to a kind of preparation method of chitin modified water polyurethane elastic body, polyurethane elastomer material by this method preparation can be applicable to fields such as mechanical industry, building industry, physical culture, medical treatment, and purposes is comparatively widely especially arranged aspect medical material.
Two, background technology
Urethane (PU) elastomerics is the macromolecular material that a class has excellent over-all properties, wear resistance is good, durometer level is wide, intensity and elongation are all high, the load support capacity is big, good damping effect, the oil resistance excellence, biocompatibility, moulding processability is good and performance is controlled, first of the present synthetic materials of Gu Juanzhidanxingtiju, wear-resisting except that being used in a large number, oil resistant, outside on shock-absorbing and the high capacity capacity, also a large amount of as artificial heart and artificial heart supplementary unit, artificial blood vessel, artificial kidney, artificial skin, the intervention diagnosis and therapy conduit, joint prosthesis, artificial cartilage, the biological bonding agent, on the medical materials such as nerve trachea and sustained release carrier.Referring to: (1) Fu Mingyuan, the intoxicated warp of grandson, " polyurethane elastomer and application thereof ". Beijing: Chemical Industry Press, 1999; (2) SandersJ.H.et al, " Polyurenthanes, Interscience Publishers " ", 1964.
Urethane (PU) elastomerics is to be made of polyisocyanates, polymer polyatomic alcohol, different chain extenders glycol or diamines and different vulcanizing agent, filler and auxiliary agent etc.
Require much higherly at the selected macromolecular material of medical field than industrial, especially higher to the material requirements of implant into body, specific requirement is: stable chemical performance; Histocompatibility is good; Non-carcinogenesis; Anti-biological aging; Can stand various sterilizing process and unchangeability; Moulding processability is good.At present, the biological activity of polyurethane elastomer is not enough, in the application of medical field very big limitation is arranged, so need the high polyurethane elastomer material of a kind of biological activity of preparation, satisfies the demand of medical field to macromolecular material.
Chitosan contains free amine group, and energy combined acid molecule is alkaline polysaccharide unique in the natural polysaccharide, thereby has many special physicochemical character and physiological function.And because chitosan is biodegradable in human body, have no side effect, wide material sources, the biological activity height, and have antibacterial, antitumor, transfer blood fat, regulate immunity, different physiological roles such as activation intestinal bifidobacteria, the chitosan of different molecular weight ranges has different character (performance anticoagulant property during lower molecular weight, the short blood coagulation of performance during high molecular) to the activity of blood simultaneously, therefore is widely used in aspects such as fine chemistry industry, biological medicine, protective foods and agricultural herding.Referring to: (1) Jiang Tingda. " chitin [M] ". Beijing: Chemical Industry Press, 2003; (2) Rabea E.I., BadawyM.E.T., Stevens C.V., Smagghe G., Steurbaut W. " Biomacromolecules ", 4,2003,1457; (3) Badawy M.E.I., Rabea E.I., Rogge T.M., et al., " Biomacromolecules ", 5,2004,589.But the mechanical property of chitosan, anti-biological aging ability and moulding processability are obviously not enough.
So be badly in need of a kind of method, utilize the novel polyurethane material of chitin modified preparation, make material except the basic demand that meets bio-medical material, the feature that also has the physiological function of good biological activity of chitosan and multiple excellence has the advantage of the anti-biological aging of polyurethane elastomer, good mechanical property, easy processing etc. again.At present, the domestic method for preparing chitosan and compound polyurethane material, useful aqueous polyurethane solution and chitosan solution physical blending are done blood compatibility and are coated with liquid layer, Chinese patent open file CN 1306042A for example, with utilize modified chitosan and specific urethane to prepare degradable semiinterpenetrating polymer network resilient material through the row solution reaction, Chinese patent open file CN 1583853A for example, and with chitosan crosslinked gac polyurethane preparation foam biological immobilization carrier, for example Chinese patent open file CN 1587106A.The chitosan of method for preparing and the function singleness of compound polyurethane material, Application Areas is little, and raw material range is narrow.
Three, summary of the invention
1, goal of the invention: the purpose of this invention is to provide a kind of preparation method of chitin modified water polyurethane elastic body, by good, the easy processing of the mechanical property of materials of this method preparation, oil resistant water-tolerant, good biocompatibility, good, biodegradable with the base material associativity, biological activity is high, fine blood contact is arranged, the preparation method is simple.Thereby and reach final material controlled to the blood contact by the molecular weight that chitosan is introduced in control.
2, technical scheme: preparation method of chitin modified water polyurethane elastic body of the present invention is characterized in that this method may further comprise the steps:
(1) polyisocyanates (A) and polyvalent alcohol (B) and glycol or diamines (C) reaction obtain base polyurethane prepolymer for use as;
(2) with organic solvent (D) base polyurethane prepolymer for use as is dissolved, add ionization reagent (E), obtain the ionization base polyurethane prepolymer for use as;
(3) ionization base polyurethane prepolymer for use as and chitosan aqueous solution (F) reaction obtains polyaminoester emulsion or microemulsion.
In preferred version of the present invention, component polyisocyanates (A) reacts with component polymer polyvalent alcohol (B) earlier, adds functionalization component (C) reaction again, and then reacts with chitosan (F).
In the methods of the invention, the hydroxyl of selected isocyanate groups and all and isocyanate reaction and the ratio of amido are 0.5-3: 1, and preferred proportion is 0.6-2: 1, more preferably ratio is 0.8-1.2: 1.
Suitable polyisocyanate component (A) is preferably the polyisocyanates that has more than or equal to 2 isocyanate functional group's degree, can be in terephthaldehyde's alkane vulcabond (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), cyclohexyl diisocyanate (THDI), the ethyl ester of lysine vulcabond (LEDI) etc. one or more.The weight of vulcabond is 0.1-80% in the reactant, preferred 0.5-70%, most preferably 1-60%.
Suitable polymers polyvalent alcohol (B) is preferably polymer diatomic alcohol, polymkeric substance diamine or polymkeric substance hydramine, can be polyether glycol, polyether diamine or polyethers hydramine, also can be polyether glycol, polyether diamine or polyethers hydramine, and general formula is:
Wherein n is 1 to 4600 integer; X, Y are respectively one or more in hydroxyl, amido or the imido grpup organic group; When X, Y comprise alkyl imido grpup such as methylene imine base, ethyl imido grpup, propyl group imido grpup etc. during for imido grpup, can also be aryl imine base such as phenyl imine base, phenmethyl imido grpup etc.; R
2Be in methylene radical, ethyl or the phenyl organic group one or more; R
1Can be alkyl C
mH
2mOr alkylene C
mH
2m-2In one or more (wherein m=2-6), also can be in the diester base one or more, general formula:
Wherein a is 0 to 10 integer, and b is 2 to 10 integer.The molecular weight of polymer polyatomic alcohol (B) can be from 62-200000, preferred 100-100000.The weight of polymer diatomic alcohol is 1-90% in the reactant, preferred 5-80%, most preferably 10-70%.
Suitable glycol or diamines (C) are small molecules glycol or diamines, can be ethylene glycol, propylene glycol, 1, the 4-butyleneglycol, hexylene glycol, glycol ether, terephthalic acid diethyl diester diol, glycol ether, quadrol, 4,4 '-diamines ditan (MDA), 3,3 '-two chloro-4,4 '-diamines ditan (MOCA), dimethylol propionic acid (DMPA), 2,2-dimethylolpropionic acid (DMBA), tartrate (2, the 3-desoxalic acid) one or more in, preferred dimethylol propionic acid (DMPA), 2,2-dimethylolpropionic acid (DMBA), in the tartrate (2, the 3-desoxalic acid) one or more.The weight of component in the reactant (C) is 0.1-40%, preferred 1-35%, most preferably 2-30%.
Appropriate organic solvent (D) is acetone (acetone), N, dinethylformamide (DMF), N, N-N,N-DIMETHYLACETAMIDE (DMAc), N, the mixed solvent of a kind of or above-mentioned solvent in N-diethylformamide, tetrahydrofuran (THF) (THF), the methyl-sulphoxide (DMSO).The weight ratio of prepolymer reaction thing and solution is 0.1-95%, preferred 1-90%, most preferably 2-80%; Reaction times is 10 minutes to 48 hours, preferred 20 minutes to 36 hours, and more preferably 30 minutes to 24 hours.
Suitable ionization reagent (E) can be in Trimethylamine 99 (TMA), triethylamine (TEA), triphenylamine (TPA), diethyl triamine (DETA), triethyl tetramine (TETA), the tetraethylenepentamine (TEPA) one or more.The weight of reactant intermediate ion reagent is 0.1-30%, preferred 0.2-25%, optimum 0.5-20%.
In the suitable chitosan aqueous solution (F), the general formula of chitosan:
Wherein n is 0 to 3100 integer; R
3Can be H atom or ethanoyl, but ethanoyl part by weight of corresponding amido in chitosan is no more than 50%, promptly the deacetylation of chitosan is 50-100%, preferred 55-99%, most preferably 60-95%; The molecular weight of chitosan is 162-1000000, preferred 324-500000, most preferably 324-100000; The concentration of chitosan aqueous solution (wt%) is 0.1-50%, preferred 0.2-40%, most preferably 0.5-30%.The weight of chitosan is 0.01-90% in the reactant, preferred 0.05-80%, most preferably 0.1-70%.
Suitable emulsifying agent (G) can be negatively charged ion, positively charged ion, zwitter-ion or nonionic emulsifier, preferred sulfonate and quaternary ammonium salt etc., in sulfonated polystyrene, Sodium dodecylbenzene sulfonate, quaternized polyacrylamide, vinylformic acid vinylpyridine copolymer, the polyvinyl alcohol etc. one or more can be, also the self-emulsifying technology can be adopted.Can be that chitosan aqueous solution adds in base polyurethane prepolymer for use as simultaneously, also can be that base polyurethane prepolymer for use as adds in chitosan aqueous solution; Reaction times is 10 minutes to 72 hours, preferred 30 minutes to 48 hours, and more preferably 1 hour to 36 hours; What obtain can be the emulsion of polyether polyols with reduced unsaturation, also can be the microemulsion of polyether polyols with reduced unsaturation.The emulsion of base polyurethane prepolymer for use as or microemulsion can directly use, and also can the film forming post-treatment use, can room temperature film-forming, also can heat film forming, and film-forming temperature is 0-80 ℃, preferred 10-70 ℃.Polyaminoester emulsion or microemulsion stability are fine, deposit under the room temperature and do not find throw out half a year.The weight of emulsifying agent is 0-90% in the reactant, preferred 0-80%, most preferably 0-70%.
Above-mentioned urethane prepolymerization reaction can be used catalyzer, also can, catalyzer can be acid, alkali, acyl chlorides, amine or some metallic compound, preferred oleic acid, stannous octoate, dibutyltin dilaurate and triethylenediamine etc., consider the toxicity of organometallic compound, preferred triethylenediamine.The weight of catalyzer is 0-10% in the reactant, preferred 0-9%, most preferably 0-8%.
Above-mentioned urethane prepolymerization reaction condition is heating under the protection of inert gas, temperature be-and 20-100 ℃, preferably 20-90 ℃; Time is 10 minutes-48 hours, preferred 0.5-24 hour; Rare gas element comprises nitrogen, argon gas, helium, neon etc., preferred nitrogen, argon gas etc.
3, beneficial effect: preparation method of the present invention is simple, prepared chitosan modified aqueous polyurethane elastomerics has that good mechanical property, easily processing, oil resistant water-tolerant, performance are controlled, good biocompatibility, biodegradable, biological activity is high, fine blood contact is arranged superperformances such as (anticoagulation or short blood coagulation ability excellences), can be applicable to fields such as mechanical industry, building industry, physical culture, medical treatment, especially purposes is comparatively widely being arranged aspect medical material or the medical equipment.
Four, embodiment
The invention will be further described below by embodiment.
Embodiment 1: add 10g polytetrahydrofuran diol (PTMO, M in three-necked bottle successively
n=1000), 6.66g isophorone diisocyanate (IPDI), logical argon gas, mechanical stirring 75-85 ℃ of reaction 3 hours down, adds 1.34g dimethylol propionic acid (DMPA) then, continues reaction 2 hours.Cooling adds 50ML acetone and soaks into, and stirs 10 minutes, adds 1.01g triethylamine (TEA) reaction 10 minutes again, obtains colourless transparent solution, i.e. the acetone soln of base polyurethane prepolymer for use as.Mechanical stirring is under the room temperature, with the chitosan (M of 648g 1%
n=5000) aqueous solution slowly splashes in the acetone soln of base polyurethane prepolymer for use as, reacts 24 hours, obtains stable yellow urethane microemulsion.Inject polytetrafluoroethyldisk disk, film forming in 40 ℃ of baking ovens obtains the film of the yellow chitin modified polyurethane elastomer of exsiccant after one day.This young modulus of material 149.6MPa; The decomposes temperature is greater than 275 ℃; 49.1 ° of contact angles; Recalcification time 73.6 ± 8.11S, t
Sample/ t
Blank=2.25, t
Sample/ t
Silicone oil=1.43 (having good anticoagulant property); Emulsion is at room temperature placed six months sediment-frees and is separated out.
It is WO-I type electronic universal tester that the sample stress-strain analysis adopts instrument, the thin-film material of preparation thickness 0.15-0.35mm, and the material section is: long 0.5cm, wide 0.4cm, rate of extension 10cm/min, humidity: 50%, temperature: 20 ℃.
Heat resistance test, i.e. the instrument model that thermogravimetric analysis (TGA) is adopted is Pyris 1 TGA, temperature range: room temperature-1000 ℃, sensitivity: 0.1 μ g, temperature rise rate: 0.1-200 ℃/min.
Measurement of contact angle adopts CAM200 contact instrument (KSV Instrument Ltd.Finland) to survey the water static contact angle of material surface at room temperature.
Anticoagulation test, measure the blood plasma recalcification time: get the glass test tube of clean dried, evenly be coated with to measure with each sample liquid of 1% concentration and manage, the sample hose after coating is inverted on the filter paper, in 0 ℃ of-4 ℃ of refrigerator overnight.In sample hose, add Sodium Citrate anticoagulate plasma 0.1ml, add 0.025mol/L CaCl again
20.1ml, open stopwatch, the time of oyster white floss appears in record, and compares with coating methyl-silicone oil test tube and blank test tube.
Embodiment 2: add 200g polyethylene oxide glycol (PEG, M in three-necked bottle successively
n=20000), 5.36g terephthaldehyde alkane vulcabond (MDI), logical nitrogen, mechanical stirring 50-60 ℃ of reaction 6 hours down, adds 1.48g 2 then, 2-dimethylolpropionic acid (DMBA) continues reaction 4 hours.Cooling adds 100mL DMF and soaks into, and stirs 30 minutes, adds 0.59g Trimethylamine 99 (TMA) reaction 30 minutes again, obtains colourless transparent solution, i.e. the acetone soln of base polyurethane prepolymer for use as.Mechanical stirring is under the room temperature, with the chitosan (M of 81g 2%
n=10000) aqueous solution slowly splashes in the DMF solution of base polyurethane prepolymer for use as, reacts 1 hour, obtains stable faint yellow urethane microemulsion.Polytetrafluoroethyldisk disk, film forming in 20 ℃ of baking ovens obtains the film of the faint yellow chitin modified polyurethane elastomer of exsiccant after one day.This young modulus of material 36.7MPa; The decomposes temperature is greater than 275 ℃; 20.7 ° of contact angles; Recalcification time 49.4 ± 7.44S, t
Sample/ t
Blank=1.51, t
Sample/ t
Silicone oil=0.96 (having anticoagulant property preferably); Emulsion is at room temperature placed six months sediment-frees and is separated out.
Testing method is with embodiment 1.
Embodiment 3: add 30g polytetrahydrofuran diol (PTMO, M in three-necked bottle successively
n=3000), 5.22g tolylene diisocyanate (TDI), logical argon gas, mechanical stirring was reacted 2 hours down at 80 ℃-90 ℃, add 1.50g tartrate (2 then, the 3-desoxalic acid), continue reaction 1 hour, cooling also adds the infiltration of 30ml tetrahydrofuran (THF), stirred 30 minutes, add 2.06g diethyl triamine (DETA) reaction 1 hour again, obtain colourless transparent solution, i.e. the tetrahydrofuran solution of base polyurethane prepolymer for use as.Mechanical stirring is under the room temperature, with the chitosan (M of 162g 10%
n=1000) aqueous solution slowly splashes in the tetrahydrofuran solution of base polyurethane prepolymer for use as, reacts 12 hours, obtains stable yellow polyaminoester emulsion.Polytetrafluoroethyldisk disk, film forming in 60 ℃ of baking ovens obtains the film of the yellow chitin modified polyurethane elastomer of exsiccant after one day.This young modulus of material 67.8MPa; The decomposes temperature is greater than 275 ℃; 67.5 ° of contact angles; Recalcification time 78.1 ± 13.9S, t
Sample/ t
Blank=2.39, t
Sample/ t
Silicone oil=1.52 (having good anticoagulant property); Emulsion is at room temperature placed six months sediment-frees and is separated out.
Testing method is with embodiment 1.
Embodiment 4: add 0.1g stannous octoate, 1000g polyethylene glycol adipate glycol (M in three-necked bottle successively
n=100000), 6.72g hexamethylene diisocyanate (HDI), logical argon gas, mechanical stirring 40 ℃-50 ℃ reactions 10 hours down, adds the 3.00g propylene glycol then, continues reaction 5 hours.Cooling adds 100ml DMAc and soaks into, and stirs 1 hour, adds 5.84g triethyl tetramine (TETA) reaction 1 hour again, obtains colourless transparent solution, i.e. the DMAc solution of base polyurethane prepolymer for use as.Mechanical stirring, under the room temperature, the DMAc solution of base polyurethane prepolymer for use as adds the 10g polyvinyl alcohol, slowly adds the chitosan (M of 1620g 0.2% again
n=100000) aqueous solution reacted 18 hours, obtained stable yellow polyaminoester emulsion.Polytetrafluoroethyldisk disk, film forming in 30 ℃ of baking ovens obtains the film of the yellow chitin modified polyurethane elastomer of exsiccant after one day.This material decomposes temperature has well short blood coagulation greater than 275 ℃; Emulsion is at room temperature placed six months sediment-frees and is separated out.
Embodiment 5: add 0.2g dibutyltin dilaurate, 4g polybutene glycol (M in three-necked bottle successively
n=400), 8.30g cyclohexyl diisocyanate (THDI), logical nitrogen, mechanical stirring 60 ℃-70 ℃ reactions 24 hours down, adds the 2.48g quadrol then, continues reaction 12 hours.Cooling adds 1000MLDMF and soaks into, and stirs 2 hours, adds 6.70g triethylamine (TEA) reaction 2 hours again, obtains colourless transparent solution, i.e. the DMAc solution of base polyurethane prepolymer for use as.Mechanical stirring, under the room temperature, the DMF solution of base polyurethane prepolymer for use as adds the 50g Sodium dodecylbenzene sulfonate, slowly adds the chitosan (M of 5000g 0.1% again
n=500000) aqueous solution reacted 48 hours, obtained stable yellow polyaminoester emulsion.Polytetrafluoroethyldisk disk, film forming in 50 ℃ of baking ovens obtains the film of the yellow chitin modified polyurethane elastomer of exsiccant after one day.This material decomposes temperature has well short blood coagulation greater than 275 ℃; Emulsion is at room temperature placed six months sediment-frees and is separated out.
Embodiment 6: add 50g polyethylene oxide glycol (PEG, M in three-necked bottle successively
n=5000), 6.78g ethyl ester of lysine vulcabond (LEDI), helium injection gas, mechanical stirring, the salt ice bath ,-20 ℃ of down reactions 48 hours add the 1.34g glycol ether then, continue reaction 36 hours.Cooling adds 50MLDMSO and soaks into, and stirs 48 hours, adds 0.65g Trimethylamine 99 (TMA) reaction 10 minutes again, obtains colourless transparent solution, i.e. the DMSO solution of base polyurethane prepolymer for use as.Mechanical stirring is under the room temperature, with the chitosan (M of 1296g 1%
n=1000) aqueous solution slowly splashes in the DMSO solution of base polyurethane prepolymer for use as, reacts 72 hours, obtains stable yellow urethane microemulsion.Inject polytetrafluoroethyldisk disk, film forming in 0 ℃ of baking oven obtains the film of the yellow chitin modified polyurethane elastomer of exsiccant two days later.This material decomposes temperature has good anticoagulant property greater than 275 ℃; Emulsion is at room temperature placed six months sediment-frees and is separated out.
Embodiment 7: add 0.1g stannous octoate, 0.64g ethylene glycol (M=64), 5.22g tolylene diisocyanate (TDI) in three-necked bottle successively, logical neon, mechanical stirring was reacted 10 minutes down at 100 ℃, add 3.48g terephthalic acid diethyl diester diol then, continue reaction 30 minutes.Cooling adds 100MLDMF and soaks into, and stirs 10 minutes, adds 2.45g triphenylamine (TPA) reaction 10 minutes again, obtains colourless transparent solution, i.e. the DMF solution of base polyurethane prepolymer for use as.Mechanical stirring is under the room temperature, with the chitosan (M of 324g 0.5%
n=2000) aqueous solution slowly splashes in the DMF solution of base polyurethane prepolymer for use as, reacts 10 minutes, obtains stable yellow urethane microemulsion.Inject polytetrafluoroethyldisk disk, film forming in 80 ℃ of baking ovens obtains the film of the yellow chitin modified polyurethane elastomer of exsiccant after one day.This material decomposes temperature has good anticoagulant property greater than 275 ℃; Emulsion is at room temperature placed six months sediment-frees and is separated out.
Embodiment 8: add 0.1g triethylenediamine, 2000g polyethylene oxide glycol (PEG, M in three-necked bottle successively
n=200000), 5.04g hexamethylene diisocyanate (HDI), logical argon gas, mechanical stirring 93-97 ℃ of reaction 1 hour down, adds 6.74g3 then, 3 '-two chloro-, 4,4 '-diamines ditan (MOCA) continues reaction 2 hours.Cooling adds 100MLDMF and soaks into, and stirs 30 minutes, adds 2.45g triphenylamine (TPA) reaction 30 minutes again, obtains colourless transparent solution, i.e. the DMF solution of base polyurethane prepolymer for use as.Mechanical stirring is under the room temperature, with the chitosan (M of 1620g 0.05%
n=4000) aqueous solution slowly splashes in the DMF solution of base polyurethane prepolymer for use as, reacts 36 hours, obtains stable yellow urethane microemulsion.Inject polytetrafluoroethyldisk disk, film forming in 70 ℃ of baking ovens obtains the film of the yellow chitin modified polyurethane elastomer of exsiccant after one day.This material decomposes temperature has good anticoagulant property greater than 275 ℃; Emulsion is at room temperature placed six months sediment-frees and is separated out.
Claims (9)
1. preparation method of chitin modified water polyurethane elastic body is characterized in that this method may further comprise the steps:
(1) polyisocyanates (A) and polyvalent alcohol (B) and glycol or diamines (C) are reacted under-20 to 100 ℃ of temperature and protection of inert gas, obtain base polyurethane prepolymer for use as;
(2) with organic solvent (D) base polyurethane prepolymer for use as is dissolved, add ionization reagent (E), obtain the ionization base polyurethane prepolymer for use as;
(3) ionization base polyurethane prepolymer for use as and chitosan aqueous solution (F) reaction obtains polyaminoester emulsion or micro emulsion;
Reacting the hydroxyl of described isocyanate groups and all and isocyanate reaction and the ratio of amido is 0.5-3: 1.
2. preparation method of chitin modified water polyurethane elastic body according to claim 1, it is characterized in that in the step (1), in described reaction, add catalyzer, catalyzer is acid, alkali, acyl chlorides, amine or metallic compound, the weight of catalyzer is the 0-10% of reactant gross weight, and the reaction times is 10 minutes to 48 hours.
3. preparation method of chitin modified water polyurethane elastic body according to claim 1, it is characterized in that in the step (2), described organic solvent (D) is acetone, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N, the mixed solvent of a kind of or above-mentioned solvent in N-diethylformamide, tetrahydrofuran (THF), the methyl-sulphoxide, the reaction times is 10 minutes to 48 hours.
4. preparation method of chitin modified water polyurethane elastic body according to claim 1, it is characterized in that in the step (3), in described reaction, add emulsifying agent (G), described emulsifying agent (G) is negatively charged ion, positively charged ion, zwitter-ion or nonionic emulsifier, reaction times is 10 minutes to 72 hours, and the weight of emulsifying agent is 0-90% in the reactant.
5. according to claims 1 described preparation method of chitin modified water polyurethane elastic body, it is characterized in that in the step (1), described polyisocyanate component (A) is for having the polyisocyanates more than or equal to 2 isocyanate functional group's degree, and the weight of vulcabond is 0.1-80% in the reactant.
6. according to claims 1 described preparation method of chitin modified water polyurethane elastic body, it is characterized in that in the step (1) that described polymer polyatomic alcohol (B) is polymer diatomic alcohol, polymkeric substance diamine or polymkeric substance hydramine.
7. according to claims 1 described preparation method of chitin modified water polyurethane elastic body, it is characterized in that in the step (1), described glycol or diamines (C) are small molecules glycol or diamines, and the weight of small molecules glycol or diamines is 0.01-90% in the reactant.
8. according to claims 1 described preparation method of chitin modified water polyurethane elastic body, it is characterized in that in the step (2), described ionization reagent (E) be in Trimethylamine 99, triethylamine, triphenylamine, diethyl triamine, triethyl tetramine, the tetraethylenepentamine (TEPA) one or more, the weight of reactant intermediate ion reagent is 0.01-90%.
9. according to claims 1 described preparation method of chitin modified water polyurethane elastic body, it is characterized in that in the step (3) general formula of the chitosan in the described chitosan aqueous solution (F):
Wherein n is 0 to 3100 integer; R
3Can be H atom or ethanoyl, the ratio of the weight of ethanoyl corresponding amido in chitosan is no more than 50%, and the concentration of chitosan aqueous solution (wt%) is 0.1-50%, and the weight of chitosan is 0.01-90% in the reactant.
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| CN113461899A (en) * | 2021-07-19 | 2021-10-01 | 青岛邦皓环境科技有限公司 | Wear-resistant hydrophilic polyurethane and preparation process thereof |
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