CN101497698A - Preparation of chitosan-polyurethane ion complex elastomer material - Google Patents
Preparation of chitosan-polyurethane ion complex elastomer material Download PDFInfo
- Publication number
- CN101497698A CN101497698A CNA2009100283531A CN200910028353A CN101497698A CN 101497698 A CN101497698 A CN 101497698A CN A2009100283531 A CNA2009100283531 A CN A2009100283531A CN 200910028353 A CN200910028353 A CN 200910028353A CN 101497698 A CN101497698 A CN 101497698A
- Authority
- CN
- China
- Prior art keywords
- chitosan
- polyurethane
- ion complex
- preparation
- elastomer material
- 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
- 239000004814 polyurethane Substances 0.000 title claims abstract description 78
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 77
- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 229920001971 elastomer Polymers 0.000 title claims description 27
- 239000000806 elastomer Substances 0.000 title claims description 27
- 229920001661 Chitosan Polymers 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000004985 diamines Chemical class 0.000 claims abstract description 24
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 11
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 11
- 125000000129 anionic group Chemical group 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 9
- 125000002091 cationic group Chemical group 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 150000002500 ions Chemical class 0.000 claims description 64
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 53
- 239000000839 emulsion Substances 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 42
- 239000007864 aqueous solution Substances 0.000 claims description 36
- 239000002585 base Substances 0.000 claims description 32
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 25
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 24
- -1 amido silicon Chemical compound 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000003921 oil Substances 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000007998 bicine buffer Substances 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- GVOHASATQPFWQW-VDQHJUMDSA-N (2s)-2-amino-4-methylsulfanylbutanoic acid;(2s)-2,6-diaminohexanoic acid Chemical compound CSCC[C@H](N)C(O)=O.NCCCC[C@H](N)C(O)=O GVOHASATQPFWQW-VDQHJUMDSA-N 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical group O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004472 Lysine Substances 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 235000018977 lysine Nutrition 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid group Chemical group C(CCCCCCC\C=C/CCCCCCCC)(=O)O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims 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 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229920013822 aminosilicone Polymers 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 claims description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 2
- 239000012875 nonionic emulsifier Substances 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 claims description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 4
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims 3
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 claims 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims 1
- 229910052754 neon Inorganic materials 0.000 claims 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 229960005222 phenazone Drugs 0.000 claims 1
- 230000004071 biological effect Effects 0.000 abstract description 8
- 239000000376 reactant Substances 0.000 abstract description 8
- 230000003385 bacteriostatic effect Effects 0.000 abstract description 5
- 210000004369 blood Anatomy 0.000 abstract description 5
- 239000008280 blood Substances 0.000 abstract description 5
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 4
- 239000012567 medical material Substances 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 150000002009 diols Chemical class 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 2
- 239000004816 latex Substances 0.000 abstract 2
- 229920000126 latex Polymers 0.000 abstract 2
- 239000013536 elastomeric material Substances 0.000 abstract 1
- 150000008040 ionic compounds Chemical class 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 238000005215 recombination Methods 0.000 abstract 1
- 230000006798 recombination Effects 0.000 abstract 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 25
- 238000010907 mechanical stirring Methods 0.000 description 25
- 239000010408 film Substances 0.000 description 23
- 230000006196 deacetylation Effects 0.000 description 13
- 238000003381 deacetylation reaction Methods 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 241000894006 Bacteria Species 0.000 description 10
- 230000002429 anti-coagulating effect Effects 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000011365 complex material Substances 0.000 description 8
- 235000018102 proteins Nutrition 0.000 description 8
- 108090000623 proteins and genes Proteins 0.000 description 8
- 102000004169 proteins and genes Human genes 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 8
- 230000003115 biocidal effect Effects 0.000 description 7
- 230000003013 cytotoxicity Effects 0.000 description 7
- 231100000135 cytotoxicity Toxicity 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 229920003225 polyurethane elastomer Polymers 0.000 description 6
- 230000023555 blood coagulation Effects 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 230000000968 intestinal effect Effects 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 235000015097 nutrients Nutrition 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920002101 Chitin Polymers 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
- 230000032683 aging Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 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
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920006264 polyurethane film Polymers 0.000 description 3
- 230000000452 restraining effect Effects 0.000 description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 229940095064 tartrate Drugs 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- 239000004793 Polystyrene 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
- 230000010100 anticoagulation Effects 0.000 description 2
- 229940098773 bovine serum albumin Drugs 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035790 physiological processes and functions Effects 0.000 description 2
- 210000002381 plasma Anatomy 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 241000186000 Bifidobacterium Species 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000012980 RPMI-1640 medium Substances 0.000 description 1
- 108090000190 Thrombin Proteins 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 239000002473 artificial blood Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 description 1
- 244000309466 calf Species 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 210000000845 cartilage Anatomy 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 230000007541 cellular toxicity Effects 0.000 description 1
- 238000007820 coagulation assay Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 210000002919 epithelial cell Anatomy 0.000 description 1
- 210000004700 fetal blood Anatomy 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
- 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
- 238000011081 inoculation Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- WDWDWGRYHDPSDS-UHFFFAOYSA-N methanimine Chemical compound N=C WDWDWGRYHDPSDS-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000013642 negative control Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 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
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 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
- 238000010992 reflux Methods 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
- 210000002966 serum Anatomy 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229960005322 streptomycin Drugs 0.000 description 1
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Natural products CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000006228 supernatant Substances 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
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229960004072 thrombin Drugs 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 210000003437 trachea Anatomy 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of chitosan-polyurethane ionic compound elastomeric material, which comprises the following steps: polyisocyanates reacts with polymer polylol and then reacts with diol or diamine, organic solvent and ionization reagent are added in the reactants to react with water for generating anionic waterborne polyurethane and further performs the ionic recombination reaction with cationic chitosan water solution to obtain the microemulsion or latex of chitosan-polyurethane ion composite, and finally the microemulsion or latex of chitosan-polyurethane ion composite is dried and solidified to obtain the chitosan-polyurethane ionic compoundelastomeric material. The chitosan-polyurethane ionic compoundelastomeric material has the advantages of good mechanical property, easy processing, good oil-water resistance property, good cohesive property with parent metal, controllable performance, good biocompatibility, biodegradable property, high biological activity, good blood contact property, good bacteriostatic property, good antibacterial property, and the like, can be applied in fields of mechanical industry, building industry, sport, medical treatment, and the like, and especially has wider purpose in aspects of life science research, medical materials and medical appliances.
Description
Technical field
The present invention relates to a kind of preparation method of elastomer material, relate in particular to a kind of preparation method of chitosan-polyurethane ion complex elastomer material.
Background technology
Urethane (PU) elastomerics is to be made of polyisocyanates, polymer polyatomic alcohol class, different chain extenders glycol or diamines and different vulcanizing agent, filler and auxiliary agent etc.
Urethane 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, so present urethane occupies first of natural materials and the synthetic materials, 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.Aqueous polyurethane mainly utilizes the ionic group self-emulsifying in glycol or the diamines, forms environmentally friendly aqueous systems emulsion, has broad application prospects.Referring to (1) Fu Mingyuan, the intoxicated warp of grandson, " polyurethane elastomer and application thereof ". Beijing: Chemical Industry Press, 1999; (2) Sanders J.H.et al, " Polyurenthanes ", Interscience Publishers, 1964.
Require much higherly, especially higher at the selected macromolecular material of medical field than industrial, comprising: 1. stable chemical performance the material requirements of implant into body; 2. histocompatibility is good; 3. non-carcinogenesis; 4. anti-biological aging; 5. can stand various sterilizing process and unchangeability; 6. moulding processability is good.At present, the biological activity of polyurethane elastomer is not enough, and biocidal property and germ resistance are bad, easily by infectation of bacteria, application at medical field has very big limitation, so need the polyurethane elastomer material that a kind of biological activity of preparation is high and have good biocidal property and germ resistance, satisfy the demand of medical field to macromolecular material.
Chitosan contains free amine group, forms cationic polymer solution, can be in conjunction with negatively charged ion, and particularly acid molecule is an 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, antibiotic, antitumor, transfer blood fat, regulate immunity, different physiological roles such as activation intestinal bifidobacteria, the chitosan of different molecular weight ranges has different character to the activity of blood simultaneously, for example: low-molecular weight chitoglycan performance anticoagulant property, the short blood coagulation of high molecular weight chitosan performance has been widely used in fields [3-5] 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.，StevensC.V.，Smagghe?G.，Steurbaut?W.《Biomacromolecules》，4，2003，1457。(3)BadawyM.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.
Need a kind of method at present, utilize the novel urethane biomaterial of chitin modified preparation, the feature that had both had the physiological function of good biological activity of chitosan and multiple excellence has again that the anti-biological aging of polyurethane elastomer, good mechanical property, adhesion property are good, an advantage of easy processing etc.At present, the domestic method for preparing chitosan and compound polyurethane material, have a lot, for example: Chinese patent CN1306042A discloses use polyurethane solution and chitosan solution physical blending and has done blood compatibility and be coated with liquid layer, Chinese patent CN1583853A, disclose and utilized modified chitosan and specific urethane to prepare degradable semiinterpenetrating polymer network resilient material, and Chinese patent CN1587106A discloses with chitosan crosslinked gac polyurethane preparation foam biological immobilization carrier through the row solution reaction.The chitosan of method for preparing and the function singleness of compound polyurethane material, Application Areas is little, and raw material range is narrow.Chinese patent ZL200610040330.9 has introduced the invention for preparing chitosan and block polymers of polyurethane elastomer material with chitosan as chainextender, the chitin modified polyurethane elastomer material of this method preparation than before chitosan and compound polyurethane material over-all properties be greatly improved, range of application is also more extensive, the underaction but preparation process also seems, the space of further modification, raising is few.
Summary of the invention
Goal of the invention: the objective of the invention is at the deficiencies in the prior art, a kind of preparation method of preparation chitosan-polyurethane ion complex elastomer material is provided, to reach the preparation method simply, flexibly, further improve biocompatibility, biological activity, biocidal property and the germ resistance of material.
Technical scheme: in order to realize the foregoing invention purpose, the technical solution used in the present invention is as follows:
The alleged weight of the present invention all refers to the ratio of quality with the quality of total reaction system of this material.
A kind of preparation method of chitosan-polyurethane ion complex elastomer material may further comprise the steps:
(1) in container, add polyisocyanates, polymer polyatomic alcohol and glycol or diamines ,-20～120 ℃, gas shield, stir or ultra-sonic dispersion, carry out prepolymerization reaction, reacted 10 minutes～48 hours, make base polyurethane prepolymer for use as, wherein, the weight of polyisocyanates is 0.1-80%, and the weight of polymer polyatomic alcohol is 1-90%, and the weight of glycol or diamines is 0.1-90%; With organic solvent it is dissolved then, add ionization reagent again, gas shield, 0～120 ℃, stir or ultra-sonic dispersion, carry out ion reaction, reacted 10 minutes～48 hours, make the ionization base polyurethane prepolymer for use as; Adding weight is 1～99% water, 0～100 ℃, carry out chain extending reaction, and reacted 1 minute～72 hours, make the emulsion or the microemulsion of anionic aqueous polyurethane;
(2) water or dilute acid solution, under stirring or the ultra-sonic dispersion, the dissolving chitosan makes the cationic chitosan aqueous solution; Wherein the weight of chitosan is 0.01-90%; The concentration of the described cationic chitosan aqueous solution (wt%) is 0.01-50%; Described dilute acid solution is aqueous solutions of organic acids or hydrochloric acid, and described dilute acid solution concentration (wt%) is 0.01-10%.
(3) with anion polyurethane emulsion or microemulsion and cationic chitosan aqueous solution, reacted 1 minute～72 hours, promptly make the emulsion or the microemulsion of chitosan-polyurethane ion complex;
(4) 0～100 ℃, emulsion or microemulsion dry solidification with chitosan-polyurethane ion complex promptly make chitosan-polyurethane ion complex elastomer material.
In the step (1), polyisocyanate component 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 preferred 0.5-70% of the weight of vulcabond, most preferably 1-60% in the reactant.
In the step (1), polymer polyatomic alcohol is preferably polymer diatomic alcohol, polymkeric substance diamine or polymkeric substance hydramine, can be polyether glycol, polyether diamine or polyethers hydramine, also can be hydroxy silicon oil, amido silicon oil or hydroxyl amino silicone oil.Its general formula is:
N=1,2,3,4 wherein X, Y are respectively hydroxyl, amido or imido grpup, when X, Y can be the alkyl imido grpups during for imido grpup, as methylene imine base, ethyl imido grpup, propyl group imido grpup, can also be the aromatic series imido grpups, as phenyl imine base, phenmethyl imido grpup; R
2Be in methylene radical, ethyl or the phenyl organic group one or more; R
1Can be alkyl-(C
mH
2m)-, cycloalkyl group or alkylene-(C
mH
2m-2)-, or-(R
3SiR
4)-in one or more, wherein, any positive integer between m=2～6; R
3, R
4Can be the same, also can be different, can be aliphatic group, also can be aryl radical; R
1Also can be in the diacid diester diol base one or more, diacid diester diol base general formula is:
Any positive integer between a=0～10 wherein, any positive integer between b=2～10.The molecular weight of polymer polyatomic alcohol (B) can be from 62-200000, preferred 100-100000.The preferred 5-80% of the weight of polymer polyatomic alcohol, most preferably 10-70% in the reactant.
In the step (1), glycol or diamines can be glycol or the diamines that contains ionizable one-tenth anionic group, as contain the glycol or the diamines of carboxyl, contain sulfonic glycol or diamines etc., can be dimethylol propionic acid (DMPA), 2,2-dimethylolpropionic acid (DMBA), tartrate (2, the 3-desoxalic acid), N, two (2-hydroxyl-3-sulfonic group propyl group) Padils (BHSPA) of N-, N, N-bicine N-(Bicine), L-Methionin (L-Lysine), 2,4-two amido Phenylsulfonic acids, 2, in 5-two amido Phenylsulfonic acids one or more, preferred dimethylol propionic acid (DMPA), N, N-bicine N-(Bicine), L-Methionin (L-Lysine), tartrate (2, the 3-desoxalic acid) one or more in, it also can be the above-mentioned glycol that contains ionizable one-tenth anionic group, in the diamines one or more add the small molecules glycol, diamines or hydramine are as quadrol, butyleneglycol etc.The preferred 0.5-80% of the weight of glycol or diamines, most preferably 1-70% in the reactant.
In the step (1), organic solvent is acetone (acetone), N, dinethylformamide (DMF), N, N-N,N-DIMETHYLACETAMIDE (DMAc), N, a kind of or above-mentioned solvent mixed solvent by a certain percentage in N-diethylformamide, tetrahydrofuran (THF) (THF), methyl-sulphoxide (DMSO), methyl alcohol, the ethanol.The weight ratio of prepolymer reaction thing and solution is 0.1-95%, preferred 1-90%, most preferably 2-80%.
In the step (1), ionization reagent 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 step (1), can add emulsifying agent in the described chain extending reaction, this emulsifying agent 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 without emulsifying agent.The weight of emulsifying agent is 0-90% in the reactant, preferred 0-80%, most preferably 0-70%.
In the step (1), polyaminoester emulsion for preparing or microemulsion can directly use, and also can steam or methods such as dialysis with revolving, and use after removing organic solvent, ionization reagent and emulsifying agent.
In the step (1), the amino mol ratio in anionic group in selected glycol or the diamines and the chitosan is 0.01-100:1, and preferred proportion is 0.02-90:1, and more preferably ratio is 0.05-80:1.
In the step (1), the reaction of preparation base polyurethane prepolymer for use as 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%.
In the step (1), preparation base polyurethane prepolymer for use as reaction: preferred 0～100 ℃ of temperature, more preferably 10～90 ℃; Preferred 20 minutes～36 hours of time, more preferably 0.5 to 24 hour; Shielding gas preferred nitrogen, argon gas; Can mechanical stirring, can stir by magnetic, also can ultra-sonic dispersion etc.
In the step (1), the optimum condition of ion reaction is: preferred 0 to 100 ℃ of temperature, more preferably 0 to 90 ℃; Preferred 20 minutes to 36 hours of time, more preferably 30 minutes to 24 hours; Shielding gas preferred nitrogen, argon gas; Can mechanical stirring, can stir by magnetic, also can ultra-sonic dispersion etc.
In the step (1), when preparing the emulsion of anionic aqueous polyurethane or microemulsion, can be that water adds in base polyurethane prepolymer for use as, also can be that base polyurethane prepolymer for use as adds in water; Preferred 10 minutes to 48 hours of reaction times; Can react under the room temperature, also can reacting by heating, temperature of reaction is 0 to 100 ℃; Can mechanical stirring, can stir by magnetic, also can ultra-sonic dispersion etc.
In the step (2), the general formula of chitosan is:
Wherein n=0,1,2,3,4 ..., 3085; R
5Can be H atom or ethanoyl, when being ethanoyl, ethanoyl ratio of corresponding amido in chitosan is no more than 50%, and 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.
In the step (2), the concentration of chitosan aqueous solution (wt%) is 0.01-50%, preferred 0.02-40%, most preferably 0.05-30%.The weight of chitosan is preferably 0.05-80% in the reactant, most preferably 0.1-70%.The pH value of chitosan aqueous solution can be for neutral, acid and alkaline.
In the step (2), during the chitosan aqueous solution preparation, directly water dissolves, can also prepare dilute acid solution and dissolve, diluted acid is organic acid and hydrochloric acid, preferred small molecular organic acid and hydrochloric acid, most preferably formic acid, acetate, propionic acid and hydrochloric acid, the concentration of diluted acid (wt%) is 0.01-10%, preferred 0.02-9%, most preferably 0.05-5%;
Can room temperature dissolving, also can heating for dissolving; Can mechanical stirring, can stir by magnetic, also can ultra-sonic dispersion etc.
In the step (3), the ion complex reaction of urethane microemulsion or emulsion and chitosan aqueous solution can be that chitosan aqueous solution adds in urethane microemulsion or emulsion, also can be that urethane microemulsion or emulsion add in chitosan aqueous solution; Reaction times is preferably 10 minutes to 24 hours; Can react under the room temperature, also can reacting by heating, temperature of reaction is 0 to 100 ℃; Can mechanical stirring, can stir by magnetic, can not stir yet, can also be with ultra-sonic dispersion etc.
In the step (3), can in the emulsion of chitosan-polyurethane ion complex, add additive, as Ag
+Deng, further improve the biocidal property and the germ resistance of material; Also can in the emulsion of chitosan-polyurethane ion complex, add suitable crosslinking agent,, further improve the mechanical property and the thermodynamic stability of material as glutaraldehyde, silane coupling agent etc.
In the step (4), the emulsion of described chitosan-polyurethane ion complex or microemulsion directly use or solidify the back and use; Describedly be cured as that spin coating is solidified or spraying is solidified; Solidification value is preferably 10 to 80 ℃.
This kind method can design the anionic aqueous polyurethane emulsion that synthetic different soft and hard section is formed as required, to carry out ion compound with the cationic chitosan aqueous solution of different concns, different molecular weight again, the preparation method flexibly, simply, the biological activity of chitosan and chemically reactive height, further modification is convenient, as: can in the emulsion of chitosan-polyurethane ion complex, add additive, as Ag
+Deng, further improve the biocidal property and the germ resistance of material; Also can in the emulsion of chitosan-polyurethane ion complex, add suitable crosslinking agent,, further improve the mechanical property and the thermodynamic stability of material as glutaraldehyde, silane coupling agent etc.Molecular designing is flexible, is easy to regulate, and the preparation method is simple, and material property is controlled.
Beneficial effect: preparation method of the present invention is simple, flexible, and step is few, easy handling.Molecular designing is flexible, is easy to regulate, and the preparation method is simple, and material property is controlled.Prepared chitosan-polyurethane ion complex elastomer material has that good mechanical property, easily processing, oil resistant water-tolerant, performance are controlled, good biocompatibility, biodegradable, performances such as biological activity is high, good blood contact is arranged (anticoagulation or short blood coagulation ability excellence), biocidal property and germ resistance, 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.The complete organic solvent-free of its chitosan-aqueous emulsion of polyurethane, environmentally friendly, the energy fast filming can directly use as coating or tackiness agent, particularly be applied to the biologic medical field.
Embodiment
The invention will be further described below by embodiment.
Embodiment 1:
In three-necked bottle, add 10g polytetrahydrofuran diol (Mn=1000), 6.66g isophorone diisocyanate successively, logical argon gas, mechanical stirring was reacted 3 hours down at 75 ℃-85 ℃, added the 1.34g dimethylol propionic acid then, continued reaction 2 hours.Cooling adds 25ml acetone and soaks into, and stirs 20 minutes, adds 1.01g triethylamine reaction 20 minutes again, obtains colourless transparent solution, i.e. the acetone soln of base polyurethane prepolymer for use as.Mechanical stirring under the room temperature, slowly splashes into 50ml distilled water in the acetone soln of base polyurethane prepolymer for use as, reacts 1 hour, obtains stable colourless urethane microemulsion.Microemulsion is at room temperature placed 12 months sediment-frees and is separated out.
Embodiment 2:
In three-necked bottle, add 30g amido silicon oil (Mn=3000), 5.22g tolylene diisocyanate, 30ml tetrahydrofuran (THF) successively, logical argon gas, mechanical stirring was reacted 2 hours down at 80 ℃-90 ℃, added 1.50g tartrate then, continue reaction 1 hour, cooling also adds the infiltration of 30ml tetrahydrofuran (THF), stirs 30 minutes, adds 2.06g diethyl triamine reaction 1 hour again, obtain colourless transparent solution, i.e. the tetrahydrofuran solution of base polyurethane prepolymer for use as.Mechanical stirring, 20 ℃ of oil baths slowly splash into 100ml distilled water in the tetrahydrofuran solution of base polyurethane prepolymer for use as, react 36 hours, obtain stable colourless polyaminoester emulsion.Emulsion is at room temperature placed 12 months sediment-frees and is separated out.
Embodiment 3:
In three-necked bottle, add 200g polyethylene oxide glycol (Mn=20000), 5.36g terephthaldehyde alkane vulcabond successively, logical nitrogen, mechanical stirring, reacted 6 hours down at 50 ℃-60 ℃, add 1.63g N then, the N-bicine N-continues reaction 4 hours.Cooling adds 100ml DMSO and soaks into, and stirs 30 minutes, adds 0.59g Trimethylamine 99 reaction 30 minutes again, obtains colourless transparent solution, i.e. the DMSO solution of base polyurethane prepolymer for use as.Mechanical stirring, 89 ℃ of oil baths slowly splash into the DMSO solution of base polyurethane prepolymer for use as in the 100ml distilled water, react 10 minutes, obtain stable colourless urethane microemulsion.Microemulsion is at room temperature placed 12 months sediment-frees and is separated out.
Embodiment 4:
In three-necked bottle, add 0.2g dibutyltin dilaurate, 4g polybutene glycol (Mn=400), 8.30g cyclohexyl diisocyanate successively, logical nitrogen, mechanical stirring, reacted 24 hours down at 60 ℃-70 ℃, add 2.48g quadrol and 1.21g2 then, 4-sodium p-phenylenediamine continues reaction 12 hours.Cooling adds 1000ml DMAc and soaks into, and stirs 2 hours, adds 6.70g triethyl tetramine reaction 2 hours again, obtains colourless transparent solution, i.e. the DMAc solution of base polyurethane prepolymer for use as.Mechanical stirring, 40 ℃ of water-baths, the DMAc solution of base polyurethane prepolymer for use as adds the 50g Sodium dodecylbenzene sulfonate, slowly adds in the distilled water of 500ml again, reacts 72 hours, obtains stable colourless polyaminoester emulsion.Emulsion is at room temperature placed 12 months sediment-frees and is separated out.
Embodiment 5:
In three-necked bottle, add 0.1g stannous octoate, the poly-methyl oxirane diamines (Mn=5000) of 50g, 6.72g hexamethylene diisocyanate successively, helium injection gas, mechanical stirring, the salt ice bath ,-20 ℃ were reacted 48 hours down, add 1.48g2 then, the 2-dimethylolpropionic acid continues reaction 36 hours.Be warmed up to room temperature, add 50ml DMF and soak into, stirred 48 hours; Be warming up to 120 ℃, add 0.65g Trimethylamine 99 reaction 10 minutes, obtain colourless transparent solution, i.e. the DMF solution of base polyurethane prepolymer for use as.Mechanical stirring, 100 ℃ of oil baths slowly splash into the DMF solution of base polyurethane prepolymer for use as in the 10ml distilled water, react 1 minute, obtain stable colourless urethane microemulsion.Microemulsion is at room temperature placed 12 months sediment-frees and is separated out.
Embodiment 6:
In three-necked bottle, add 0.1g triethylenediamine, 6g polycaprolactone glycol (M successively
n=600), 6.78g ethyl ester of lysine vulcabond, logical argon gas, mechanical stirring, ice-water bath, 0 ℃ of reaction 36 hours down adds 1.80g butyleneglycol and 2.56gN then, two (2-hydroxyl-3-sulfonic group propyl group) Padils of N-continue reaction 36 hours.Be warming up to 60 ℃, add 50ml DMSO and 25ml methyl alcohol and soak into, stirred 16 hours, add 1.65g triphenylamine reaction 60 minutes again, obtain the solution of base polyurethane prepolymer for use as.Mechanical stirring, 40 ℃ of water-baths slowly splash into 40ml distilled water in the solution of base polyurethane prepolymer for use as, react 15 minutes, obtain stable polyaminoester emulsion.Microemulsion is at room temperature placed 12 months sediment-frees and is separated out.
Embodiment 7:
In three-necked bottle, add 0.1g oleic acid and 0.2g triethylenediamine, 2000g poly adipate succinic acid ester glycol (M successively
n=200000), 5.36g terephthaldehyde alkane vulcabond, 5.22g tolylene diisocyanate, helium injection gas, mechanical stirring, oil bath, 120 ℃ were reacted 12 hours down, add 2.31gN-methyldiethanolamine and 5.12g2 then, 4-two amido Phenylsulfonic acids continue reaction 12 hours.Add 150ml ethanol and soak into, stirred 2 hours; Ice-water bath adds 5.79g tetraethylenepentamine reaction 2 hours, obtains the solution of base polyurethane prepolymer for use as.Mechanical stirring slowly splashes into the solution of base polyurethane prepolymer for use as in the 500ml distilled water that has added the quaternized polyacrylamide of 15g, reacts 12 hours, obtains stable polyaminoester emulsion.Microemulsion is at room temperature placed 12 months sediment-frees and is separated out.
Embodiment 8:
In three-necked bottle, add 0.62g ethylene glycol (M successively
n=62), the 22.2g isophorone diisocyanate, mechanical stirring, oil bath, 75 ℃ of down reactions 2 hours add 4.38gL-Methionin then, continue reaction 3 hours.Add 50ml acetone and soak into, stir 10min, add 0.51g triethylamine and 0.30g Trimethylamine 99 reaction 11 hours again, obtain the solution of base polyurethane prepolymer for use as.Mechanical stirring slowly splashes into the solution of base polyurethane prepolymer for use as in the 160ml distilled water that has added 0.5g sulfonated polystyrene and 1.0g Sodium dodecylbenzene sulfonate, reacts 20 hours, obtains stable polyaminoester emulsion.Microemulsion is at room temperature placed 12 months sediment-frees and is separated out.
Embodiment 9:
Magnetic stirs, and under the room temperature, 10g chitosan (Mn=5000, deacetylation are 90%) is dissolved in the 990g distilled water, stirs 1 hour, obtains 1000g concentration and be 1% chitosan (Mn=5000) aqueous solution.
Embodiment 10:
10g chitosan (Mn=1000, deacetylation are 90%) is dissolved in the 90g distilled water, and reflux 2 hours obtains chitosan (Mn=1000, deacetylation the are 90%) aqueous solution of 100g10%.
Embodiment 11:
10g chitosan (Mn=500000, deacetylation are 80%) is dissolved in the acetic acid aqueous solution of 9990g1%, ultrasonic 30 minutes, obtains chitosan (Mn=500000) aqueous solution of 10000g0.1%.
Embodiment 12:
Synthesizing of urethane microemulsion referring to embodiment 1; The preparation of 1% chitosan (Mn=5000, deacetylation the are 90%) aqueous solution is referring to embodiment 6.Mechanical stirring under the room temperature, slowly splashes into chitosan (Mn=5000) aqueous solution of 324g1% in the urethane microemulsion, reacts 24 hours, obtains stable yellow chitosan-polyurethane ion complex microemulsion.Inject polytetrafluoroethyldisk disk, film forming in 40 ℃ of baking ovens obtains the film of the yellow chitosan-polyurethane ion complex elastomer of exsiccant after one day.This young modulus of material 62.8MPa; The decomposes temperature is greater than 300 ℃; 30.7 ° of contact angles; Recalcification time 87.3 ± 11.5S, t
Sample/ t
Blank=2.67, t
Sample/ t
Silicone oil=1.70 (having good anticoagulant property); Activated partial thrombin time (APTT) is 126.9 ± 0.87S, and urethane film originally is 35.6 ± 0.31S, and polystyrene (PS) is 40.2 ± 0.37S, illustrates that equally chitosan-polyurethane ion complex material has good anticoagulant property; Emulsion is at room temperature placed 12 months sediment-frees and is separated out.In cytotoxicity experiment, discovery chitosan-polyurethane ion complex film obviously is more conducive to adhering to of human cord blood epithelial cell (HUVECs) than original urethane film and breeds, and cytotoxicity is very low, even also lower than PS; The protein adsorption experiment shows that the introducing of chitosan can reduce the protein adsorption of polyurethane film; In bacteriostatic experiment, chitosan-polyurethane ion complex material has shown the good restraining effect for intestinal bacteria and staphylococcus aureus.
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.APTT is that (Helena Laboratories USA) tests with automatic blood coagulation assay instrument in the Nanjing drum tower hospital.
Cytotoxicity experiment, HUVECs cell cultures and are positioned over 37 ℃, 5%CO in containing the RPMI1640 nutrient solution of 10% new-born calf serum (containing 100U/ml penicillin and 100 μ g/ml Streptomycin sulphates)
2Incubator in grow.In 96 orifice plates, every pore volume is 200 μ l with 2.0 * 104 cell inoculations in every hole.Utilize the number of cell counter and tetrazolium salts (MTT) colorimetric method for determining cell to come thinner cellular toxicity.
The protein adsorption experiment, the PBS solution (PH=7.4) of preparation 3-5mg/ml bovine serum albumin (BSA).Each sample adds 1mlBSA solution in 3cm culture dish film forming in each culture dish, 37 ℃, hatched 12 hours.Remove supernatant liquid then, clean with a small amount of PBS.Add 2-4% sodium laurylsulfonate (SDS) solution, 37 ℃, hatched 8 hours.After solution siphoned away, with a small amount of SDS drip washing, the solution merging shook up, and is added dropwise to determination of protein concentration test kit (BCA), and 37 ℃, hatched 30 minutes, the 562nm place, (Safire, Tecan Switzerland) measure microplate reader.
Bacteriostatic experiment is selected intestinal bacteria and staphylococcus aureus.For emulsion, get the LB nutrient solution and the 20 μ l bacterium liquid of 4ml sterilization in the test tube.Add the 1ml sample emulsion again.Positive control is to add 20 μ l bacterium liquid in the 5mlLB nutrient solution, and negative control is got 4ml LB nutrient solution and added 20 μ l bacterium liquid and 1ml 200 μ g/ml penbritins, hatches 10 hours on shaking table for 37 ℃.Measuring bacterial concentration with mtt assay changes.For film, the LB substratum in the 9cm culture dish after the impouring 10ml sterilization is done base plate, and aseptic condition adds the bacterium liquid of 100 μ l down, uses the glass spreading rod through sterilization to be coated with evenly, and bacterium liquid uniformly penetrating is gone in the base plate.Make the circular sample film of 6mm with punch tool, sterilization.Under aseptic condition, with inoculating needle sample film is forwarded on the base plate, be placed in 37 ℃ of baking ovens, 18 hours, measure its antibacterial circle diameter.
Embodiment 13:
Synthesizing of polyaminoester emulsion referring to embodiment 2.The preparation of 10% chitosan (Mn=1000, deacetylation the are 90%) aqueous solution is referring to embodiment 7.Mechanical stirring, 40 ℃ of oil baths slowly splash into chitosan (Mn=1000) aqueous solution of 16.2g10% in the polyaminoester emulsion, react 12 hours, obtain stable yellow chitosan-polyurethane ion complex emulsion.Polytetrafluoroethyldisk disk, film forming in 60 ℃ of baking ovens obtains the film of the yellow chitosan-polyurethane ion complex elastomer of exsiccant after one day.This young modulus of material 33.3MPa; The decomposes temperature is greater than 300 ℃; 55.8 ° of contact angles; Recalcification time 58.1 ± 10.9S, t
Sample/ t
Blank=1.78, t
Sample/ t
Silicone oil=1.13 (having anticoagulant property preferably); APTT is 91.6 ± 0.59S, illustrates that chitosan-polyurethane ion complex material has good anticoagulant property; Emulsion is at room temperature placed 12 months sediment-frees and is separated out.Cytotoxicity experiment demonstration chitosan-polyurethane ion complex material is more conducive to adhering to of HUVECs cell and breeds, and cytotoxicity is low; The protein adsorption experiment shows that the introducing of chitosan can reduce the protein adsorption of polyurethane film; In bacteriostatic experiment, chitosan-polyurethane ion complex material has shown the good restraining effect for intestinal bacteria and staphylococcus aureus.
Testing method is with embodiment 12.
Embodiment 14:
Synthesizing of urethane microemulsion referring to embodiment 3.The preparation of 1% chitosan (Mn=10000, deacetylation the are 87%) aqueous solution is with embodiment 6, and the chitosan that the chitosan of molecular weight 5000 is changed into molecular weight 10000 gets final product.Utilize the method for dialysis, remove organic solvent and ionization reagent in the urethane microemulsion, obtain aqueous emulsion of polyurethane.Magnetic stirs, and 60 ℃ of water-baths slowly splash into chitosan (Mn=10000) aqueous solution of 486g1% in the aqueous emulsion of polyurethane, react 1 hour, obtain stable yellow chitosan-polyurethane ion complex water miscible liquid.Polytetrafluoroethyldisk disk, film forming in 20 ℃ of baking ovens obtains the film of the yellow chitosan-polyurethane ion complex elastomer of exsiccant after one day.This young modulus of material 111.7MPa; The decomposes temperature is greater than 300 ℃; 20.7 ° of contact angles; Recalcification time 93.4 ± 13.44S, t
Sample/ t
Blank=2.86, t
Sample/ t
Silicone oil=1.82 (having good anticoagulant property); APTT is 147.2 ± 1.31S, illustrates that chitosan-polyurethane ion complex material has good anticoagulant property; Water miscible liquid is at room temperature placed 12 months sediment-frees and is separated out.Cytotoxicity experiment demonstration chitosan-polyurethane ion complex material is more conducive to adhering to of HUVECs cell and breeds, and cytotoxicity is low; The protein adsorption experiment shows that the introducing of chitosan can reduce the protein adsorption of polyurethane film; In bacteriostatic experiment, chitosan-polyurethane ion complex material has shown the good restraining effect for intestinal bacteria and staphylococcus aureus.
Testing method is with embodiment 12.
Embodiment 15:
Synthesizing of polyaminoester emulsion referring to embodiment 4.The preparation of 0.1% chitosan (Mn=500000, deacetylation the are 80%) aqueous solution is referring to embodiment 8.Mechanical stirring, 80 ℃ of oil baths, the chitosan of 5000g0.1% (Mn=500000) aqueous solution slowly adds in the polyaminoester emulsion, and back flow reaction 48 hours obtains stable yellow chitosan-polyurethane ion complex emulsion.Under the room temperature, spin-coating film obtains the film of the yellow chitosan-polyurethane ion complex elastomer of exsiccant.This material decomposes temperature has well short blood coagulation greater than 300 ℃; Emulsion is at room temperature placed 12 months sediment-frees and is separated out.
Embodiment 16:
Synthesizing of urethane microemulsion referring to embodiment 5.The preparation of 1% chitosan (Mn=2000, deacetylation the are 90%) aqueous solution is with embodiment 6, and the chitosan that the chitosan of molecular weight 5000 is changed into molecular weight 2000 gets final product.Magnetic stirs, under the room temperature, with the chitosan (M of 1296g1%
n=2000) aqueous solution slowly splashes in the urethane microemulsion, reacts 72 hours, obtains stable yellow chitosan-polyurethane ion complex emulsion.Inject polytetrafluoroethyldisk disk, film forming in 0 ℃ of baking oven obtains the film of the yellow chitosan-polyurethane ion complex elastomer of exsiccant two days later.This material decomposes temperature has good anticoagulant property greater than 300 ℃; Emulsion is at room temperature placed 12 months sediment-frees and is separated out.
Embodiment 17:
Synthesizing of urethane microemulsion referring to embodiment 1.The preparation of 0.1% chitosan (Mn=100000, deacetylation the are 80%) aqueous solution is with embodiment 8, and the chitosan that the chitosan of molecular weight 500000 is changed into molecular weight 100000 gets final product.Magnetic stirs, and 30 ℃ of water-baths slowly splash into chitosan (Mn=100000) aqueous solution of 3240g0.1% with the urethane microemulsion, react 18 hours, obtain stable yellow chitosan-polyurethane ion complex emulsion.Under the room temperature, spray film forming, obtain the film of the yellow chitosan-polyurethane ion complex elastomer of exsiccant.This material decomposes temperature has well short blood coagulation greater than 300 ℃; Emulsion is at room temperature placed 12 months sediment-frees and is separated out.
Embodiment 18:
Synthesizing of urethane microemulsion referring to embodiment 5.The preparation of 1% chitosan (Mn=4000, deacetylation the are 90%) aqueous solution is with embodiment 6, and the chitosan that the chitosan of molecular weight 5000 is changed into molecular weight 4000 gets final product.Ultrasonic, under the room temperature, chitosan (Mn=4000) aqueous solution of 162g1% is slowly splashed in the urethane microemulsion, reacted 10 minutes, obtain stable yellow chitosan-polyurethane ion complex microemulsion.Then, with the AgNO of 10ML0.5%
3The aqueous solution slowly splashes in chitosan-polyurethane ion complex microemulsion, ultrasonic 10 minutes.Inject polytetrafluoroethyldisk disk, film forming in 80 ℃ of baking ovens obtains the film of the yellow chitosan-polyurethane ion complex elastomer of exsiccant after one day.This material decomposes temperature has good anticoagulant property and antibacterial, germ resistance greater than 300 ℃; Emulsion is at room temperature placed 12 months sediment-frees and is separated out.
Embodiment 19:
Synthesizing of urethane microemulsion referring to embodiment 1.The preparation of 10% chitosan (Mn=2000, deacetylation the are 90%) aqueous solution is with embodiment 7, and the chitosan that the chitosan of molecular weight 1000 is changed into molecular weight 2000 gets final product.The method of steaming is revolved in utilization, removes organic solvent and ionization reagent in the urethane microemulsion, obtains aqueous emulsion of polyurethane.Mechanical stirring under the room temperature, slowly splashes into aqueous emulsion of polyurethane in chitosan (Mn=2000) aqueous solution of 8.1g 10%, reacts 36 hours; Add the 10ML1% glutaraldehyde water solution again, reacted 3 hours, obtain stable faint yellow chitosan-polyurethane ion complex water miscible liquid.Spin-coating film obtains the film of the faint yellow chitosan-polyurethane ion complex elastomer of exsiccant.This material decomposes temperature has good anticoagulant property greater than 370 ℃; Water miscible liquid is at room temperature placed 12 months sediment-frees and is separated out.
Claims (10)
1, a kind of preparation method of chitosan-polyurethane ion complex elastomer material is characterized in that: this method may further comprise the steps:
(1) in container, add polyisocyanates, polymer polyatomic alcohol and glycol or diamines ,-20～120 ℃, gas shield, stir or ultra-sonic dispersion, carry out prepolymerization reaction, reacted 10 minutes～48 hours, make base polyurethane prepolymer for use as, wherein, the weight of polyisocyanates is 0.1-80%, and the weight of polymer polyatomic alcohol is 1-90%, and the weight of glycol or diamines is 0.1-90%; With organic solvent it is dissolved then, add ionization reagent again, gas shield, 0～120 ℃, carry out ion reaction, reacted 10 minutes～48 hours, make the ionization base polyurethane prepolymer for use as; Adding weight is 1～99% water, 0～100 ℃, carry out chain extending reaction, and reacted 1 minute～72 hours, make the emulsion or the microemulsion of anionic aqueous polyurethane;
(2) water or dilute acid solution stir or ultra-sonic dispersion, and the dissolving chitosan makes the cationic chitosan aqueous solution; Wherein cationic chitosan concentration of aqueous solution (wt%) is 0.01-50%; The weight of chitosan is 0.01-90%;
(3) with anion polyurethane emulsion or microemulsion and cationic chitosan aqueous solution, reacted 1 minute～72 hours, promptly make the emulsion or the microemulsion of chitosan-polyurethane ion complex;
(4) 0～100 ℃, emulsion or microemulsion dry solidification with chitosan-polyurethane ion complex promptly make chitosan-polyurethane ion complex elastomer material.
2, the preparation method of chitosan-polyurethane ion complex elastomer material according to claim 1 is characterized in that: in the step (1), described polyisocyanates is the polyisocyanates that contains more than or equal to 2 isocyanate functional groups; Described glycol or diamines are glycol or the diamines that contains ionizable one-tenth anionic group; Described organic solvent is acetone, N, dinethylformamide, N,N-dimethylacetamide, N, the mixture of one or more in N-diethylformamide, tetrahydrofuran (THF), methyl-sulphoxide, methyl alcohol, the ethanol; Described ionization reagent is one or more a mixture in Trimethylamine 99, triethylamine, triphenylamine, diethyl triamine, triethyl tetramine, the tetraethylenepentamine; Described polymer polyatomic alcohol is polyether glycol, polyether diamine, polyethers hydramine, hydroxy silicon oil, amido silicon oil or hydroxyl amino silicone oil, and its molecular weight is 62～2000000.
3, the preparation method of chitosan-polyurethane ion complex elastomer material according to claim 2 is characterized in that: described polyisocyanates is one or more the mixture in terephthaldehyde's alkane vulcabond, tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, the ethyl ester of lysine vulcabond; Described glycol or diamines are dimethylol propionic acid, 2,2-dimethylolpropionic acid, 2,3-desoxalic acid, N, two (2-hydroxyl-3-sulfonic group propyl group) Padils of N-, N, N-bicine N-, L-Methionin (L-Lysine), 2, in 4-two amido Phenylsulfonic acids, 2,5-two amido Phenylsulfonic acids one or more perhaps add small molecules glycol, diamines or hydramine for above-mentioned glycol, in the diamines one or more; Described polymer polyatomic alcohol is polymer diatomic alcohol, polymkeric substance diamine or polymkeric substance hydramine, and its general formula is:
N=1,2,3,4 wherein X is hydroxyl, amido or imido grpup, and Y is hydroxyl, amido or imido grpup, R
2Be in methylene radical, ethyl or the phenyl one or more, R
1Be alkyl-(C
mH
2m)-, cycloalkyl group, alkylene-(C
mH
2m-2)-,-(R
3SiR
4)-or diacid diester diol base in one or more, wherein, any positive integer between m=2～6; R
3And R
4Be in aliphatic group, the aryl radical one or more; Described diacid diester diol base general formula is:
Any positive integer between a=0～10 wherein, any positive integer between b=2～10.
4, the preparation method of chitosan-polyurethane ion complex elastomer material according to claim 1, it is characterized in that: in the step (1), add catalyzer in the described prepolymer reaction, described catalyzer is oleic acid, stannous octoate, dibutyltin dilaurate or triethylenediamine.
5, the preparation method of chitosan-polyurethane ion complex elastomer material according to claim 1, it is characterized in that: in the step (1), add emulsifying agent in the described chain extending reaction, described emulsifying agent is negatively charged ion, positively charged ion, zwitter-ion or nonionic emulsifier, is one or more the mixture in sulfonated polystyrene, Sodium dodecylbenzene sulfonate, quaternized polyacrylamide, vinylformic acid vinylpyridine copolymer, the polyvinyl alcohol.
6, the preparation method of chitosan-polyurethane ion complex elastomer material according to claim 1; it is characterized in that: in the step (1); in described prepolymerization reaction and the ion reaction: temperature is 0～100 ℃; time is 20 minutes～36 hours, and shielding gas is nitrogen, argon gas, helium or neon.
7, the preparation method of chitosan-polyurethane ion complex elastomer material according to claim 1 is characterized in that: in the step (1), described chain extending reaction: temperature is 0～80 ℃, and the time is 30 minutes～36 hours.
8, the preparation method of chitosan-polyurethane ion complex elastomer material according to claim 1 is characterized in that: in the step (2), the general formula of described chitosan is:
The arbitrary integer between n=0～3085 wherein; R
5Be H atom or ethanoyl, the ratio of the amount of this ethanoyl in the chitosan nitrogen-containing group is no more than 50%; The molecular weight of chitosan is 162-1000000.
9,, it is characterized in that in the step (2), described dilute acid solution is aqueous solutions of organic acids or hydrochloric acid according to the preparation method of claims 1 described chitosan-polyurethane ion complex elastomer material; Described dilute acid solution concentration (wt%) is 0.01-10%; Described organic acid is formic acid, acetate or propionic acid.
10, the preparation method of chitosan-polyurethane ion complex elastomer material according to claim 1 is characterized in that: in the step (3), add additive or linking agent in the emulsion of chitosan-polyurethane ion complex; Described additive is Ag
+, described linking agent is glutaraldehyde or silane coupling agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100283531A CN101497698A (en) | 2009-01-22 | 2009-01-22 | Preparation of chitosan-polyurethane ion complex elastomer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100283531A CN101497698A (en) | 2009-01-22 | 2009-01-22 | Preparation of chitosan-polyurethane ion complex elastomer material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101497698A true CN101497698A (en) | 2009-08-05 |
Family
ID=40944979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100283531A Pending CN101497698A (en) | 2009-01-22 | 2009-01-22 | Preparation of chitosan-polyurethane ion complex elastomer material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101497698A (en) |
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254401A (en) * | 2013-04-28 | 2013-08-21 | 杭州纳美科技有限公司 | Antimicrobial thermoplastic polyurethane for toothbrush and preparation method for antimicrobial thermoplastic polyurethane |
| CN103436155A (en) * | 2013-09-09 | 2013-12-11 | 段宝荣 | Preparation method of light-resistant water-based polyurethane coating |
| CN104151505A (en) * | 2014-08-12 | 2014-11-19 | 东南大学 | Method for performing modification of chitosan or derivative thereof on surface of medical polyurethane material |
| CN104474588A (en) * | 2014-11-25 | 2015-04-01 | 苏州市贝克生物科技有限公司 | Polyurethane medical antibacterial material and preparation method thereof |
| CN104628989A (en) * | 2015-02-15 | 2015-05-20 | 佛山市柏杰油墨科技有限公司 | Aqueous jet ink for cotton fabric and preparation method thereof |
| CN104841285A (en) * | 2015-05-12 | 2015-08-19 | 中南大学 | Citric acid-chitosan-modified anticoagulation polyurethane blood dialysis membrane and preparation method thereof |
| CN105062036A (en) * | 2015-07-31 | 2015-11-18 | 大禹节水（天津）有限公司 | Rodent-resistant drip irrigation tube master batch |
| CN105461884A (en) * | 2015-12-22 | 2016-04-06 | 上海韬鸿化工科技有限公司 | Antibacterial and scratch-resistant children furniture and preparation method thereof |
| CN106174814A (en) * | 2016-07-15 | 2016-12-07 | 青岛明药堂医疗股份有限公司 | A kind of antibacterial gloves and preparation method thereof |
| CN106317363A (en) * | 2016-08-18 | 2017-01-11 | 深圳市汉华热管理科技有限公司 | Solid-solid phase change material as well as preparation method and application thereof |
| CN106307645A (en) * | 2015-07-07 | 2017-01-11 | 何斌 | Improved bra underwires, processing method thereof and bra product provided with same |
| CN104356330B (en) * | 2014-09-28 | 2017-02-08 | 陕西科技大学 | Carboxylic acid waterborne polyurethane chain extender and preparation method thereof |
| CN106693077A (en) * | 2017-01-22 | 2017-05-24 | 包磊 | Electronic skin base, preparation method thereof and electronic skin |
| CN106700021A (en) * | 2017-01-18 | 2017-05-24 | 中国科学院长春应用化学研究所 | Chitosan modified cationic waterborne polyurethane resin and preparation method and application thereof |
| CN106947047A (en) * | 2017-03-31 | 2017-07-14 | 福建师范大学泉港石化研究院 | A kind of antibacterial aqueous polyurethane and its synthetic method |
| CN106967206A (en) * | 2017-04-12 | 2017-07-21 | 沈坤 | Hydrophilic lubrication medical polyurethane material and its preparation method and application |
| CN107216439A (en) * | 2017-06-28 | 2017-09-29 | 重庆工商大学 | A kind of polyurethane-urea chitin copolymer and its preparation method and application |
| CN107236109A (en) * | 2017-07-19 | 2017-10-10 | 陕西科技大学 | Citrated chitin modified water polyurethane and preparation method thereof |
| CN107359364A (en) * | 2017-07-19 | 2017-11-17 | 湖北工程学院 | Alkaline polyelectrolyte film and its preparation method and application |
| CN107987710A (en) * | 2017-11-15 | 2018-05-04 | 张军志 | A kind of preparation method of polyurea waterproof coating material applied to concrete surface |
| CN109400841A (en) * | 2018-11-07 | 2019-03-01 | 中南大学 | A kind of sulfonation dihydroxypropylchitosan modified polyurethane and preparation method thereof |
| CN109776754A (en) * | 2017-11-13 | 2019-05-21 | 湖南大学 | A kind of preparation method of cation-type water-thinned UV urethane acrylate from antibacterial resin |
| CN110964205A (en) * | 2018-09-30 | 2020-04-07 | 天津大学 | Application of chitosan guanidine cation waterborne polyurethane in preparation of antibacterial coating |
| CN111019082A (en) * | 2019-12-16 | 2020-04-17 | 东南大学 | Nonionic photo-curing polyurethane aqueous dispersion resin composition with excellent compatibility and preparation method and application thereof |
| WO2020087896A1 (en) * | 2018-10-28 | 2020-05-07 | 凯斯蒂南京医疗器械有限公司 | Medical degradable polyurethane having antibacterial activity and application thereof |
| CN111115650A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Zeolite molecular sieve modification method |
| CN111889025A (en) * | 2020-09-01 | 2020-11-06 | 山东大学 | Acid-alkali-resistant salt-resistant super-amphiphilic molecule emulsifier, preparation method thereof and emulsion |
| CN112542296A (en) * | 2020-12-04 | 2021-03-23 | 刚和石油(营口)有限公司 | Biodegradable high-ignition-point insulating fluid |
| CN113683804A (en) * | 2021-10-13 | 2021-11-23 | 山东天铭医药科技有限公司 | Double-crosslinked chitosan poly (ester-urethane) modified oxidized starch and preparation method thereof |
| CN115160538A (en) * | 2022-07-09 | 2022-10-11 | 四川大学 | Crosslinked PDMS/chitosan composite material and preparation method thereof |
| WO2023092750A1 (en) * | 2021-11-29 | 2023-06-01 | 浙江大学台州研究院 | Tpu medical catheter with outer surface modified by antibacterial polysaccharide and preparation method therefor |
-
2009
- 2009-01-22 CN CNA2009100283531A patent/CN101497698A/en active Pending
Cited By (43)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254401A (en) * | 2013-04-28 | 2013-08-21 | 杭州纳美科技有限公司 | Antimicrobial thermoplastic polyurethane for toothbrush and preparation method for antimicrobial thermoplastic polyurethane |
| CN103436155A (en) * | 2013-09-09 | 2013-12-11 | 段宝荣 | Preparation method of light-resistant water-based polyurethane coating |
| CN104151505B (en) * | 2014-08-12 | 2016-11-23 | 东南大学 | A kind of method carrying out chitosan or derivatives thereof modification on medical polyurethane material surface |
| CN104151505A (en) * | 2014-08-12 | 2014-11-19 | 东南大学 | Method for performing modification of chitosan or derivative thereof on surface of medical polyurethane material |
| CN104356330B (en) * | 2014-09-28 | 2017-02-08 | 陕西科技大学 | Carboxylic acid waterborne polyurethane chain extender and preparation method thereof |
| CN104474588A (en) * | 2014-11-25 | 2015-04-01 | 苏州市贝克生物科技有限公司 | Polyurethane medical antibacterial material and preparation method thereof |
| CN104628989A (en) * | 2015-02-15 | 2015-05-20 | 佛山市柏杰油墨科技有限公司 | Aqueous jet ink for cotton fabric and preparation method thereof |
| CN104628989B (en) * | 2015-02-15 | 2017-05-17 | 佛山市柏杰油墨科技有限公司 | Aqueous jet ink for cotton fabric and preparation method thereof |
| CN104841285B (en) * | 2015-05-12 | 2017-01-25 | 中南大学 | Citric acid-chitosan-modified anticoagulation polyurethane blood dialysis membrane and preparation method thereof |
| CN104841285A (en) * | 2015-05-12 | 2015-08-19 | 中南大学 | Citric acid-chitosan-modified anticoagulation polyurethane blood dialysis membrane and preparation method thereof |
| CN106307645A (en) * | 2015-07-07 | 2017-01-11 | 何斌 | Improved bra underwires, processing method thereof and bra product provided with same |
| CN105062036A (en) * | 2015-07-31 | 2015-11-18 | 大禹节水（天津）有限公司 | Rodent-resistant drip irrigation tube master batch |
| CN105062036B (en) * | 2015-07-31 | 2017-09-12 | 大禹节水（天津）有限公司 | A kind of mouse bite preventing drip irrigation tube mother material |
| CN105461884A (en) * | 2015-12-22 | 2016-04-06 | 上海韬鸿化工科技有限公司 | Antibacterial and scratch-resistant children furniture and preparation method thereof |
| CN105461884B (en) * | 2015-12-22 | 2018-05-29 | 佛山市顺德区福利来酒店傢具有限公司 | Children's antibacterial damage resistant furniture and preparation method thereof |
| CN106174814A (en) * | 2016-07-15 | 2016-12-07 | 青岛明药堂医疗股份有限公司 | A kind of antibacterial gloves and preparation method thereof |
| CN106317363A (en) * | 2016-08-18 | 2017-01-11 | 深圳市汉华热管理科技有限公司 | Solid-solid phase change material as well as preparation method and application thereof |
| CN106317363B (en) * | 2016-08-18 | 2019-10-25 | 深圳市汉华热管理科技有限公司 | Solid-solid phase transition material and its preparation method and application |
| CN106700021A (en) * | 2017-01-18 | 2017-05-24 | 中国科学院长春应用化学研究所 | Chitosan modified cationic waterborne polyurethane resin and preparation method and application thereof |
| CN106693077A (en) * | 2017-01-22 | 2017-05-24 | 包磊 | Electronic skin base, preparation method thereof and electronic skin |
| CN106947047A (en) * | 2017-03-31 | 2017-07-14 | 福建师范大学泉港石化研究院 | A kind of antibacterial aqueous polyurethane and its synthetic method |
| CN106947047B (en) * | 2017-03-31 | 2020-03-10 | 福建师范大学泉港石化研究院 | Antibacterial waterborne polyurethane and synthesis method thereof |
| CN106967206A (en) * | 2017-04-12 | 2017-07-21 | 沈坤 | Hydrophilic lubrication medical polyurethane material and its preparation method and application |
| CN107216439A (en) * | 2017-06-28 | 2017-09-29 | 重庆工商大学 | A kind of polyurethane-urea chitin copolymer and its preparation method and application |
| CN107359364A (en) * | 2017-07-19 | 2017-11-17 | 湖北工程学院 | Alkaline polyelectrolyte film and its preparation method and application |
| CN107236109A (en) * | 2017-07-19 | 2017-10-10 | 陕西科技大学 | Citrated chitin modified water polyurethane and preparation method thereof |
| CN107236109B (en) * | 2017-07-19 | 2020-09-08 | 陕西科技大学 | Citric acid chitosan modified waterborne polyurethane and preparation method thereof |
| CN109776754B (en) * | 2017-11-13 | 2022-02-08 | 湖南大学 | Preparation method of cationic waterborne UV polyurethane acrylate self-antibacterial resin |
| CN109776754A (en) * | 2017-11-13 | 2019-05-21 | 湖南大学 | A kind of preparation method of cation-type water-thinned UV urethane acrylate from antibacterial resin |
| CN107987710A (en) * | 2017-11-15 | 2018-05-04 | 张军志 | A kind of preparation method of polyurea waterproof coating material applied to concrete surface |
| CN107987710B (en) * | 2017-11-15 | 2019-10-01 | 上海途灏实业有限公司 | A kind of preparation method of the polyurea waterproof coating material applied to concrete surface |
| CN110964205A (en) * | 2018-09-30 | 2020-04-07 | 天津大学 | Application of chitosan guanidine cation waterborne polyurethane in preparation of antibacterial coating |
| WO2020087896A1 (en) * | 2018-10-28 | 2020-05-07 | 凯斯蒂南京医疗器械有限公司 | Medical degradable polyurethane having antibacterial activity and application thereof |
| CN111115650A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Zeolite molecular sieve modification method |
| CN109400841A (en) * | 2018-11-07 | 2019-03-01 | 中南大学 | A kind of sulfonation dihydroxypropylchitosan modified polyurethane and preparation method thereof |
| CN111019082A (en) * | 2019-12-16 | 2020-04-17 | 东南大学 | Nonionic photo-curing polyurethane aqueous dispersion resin composition with excellent compatibility and preparation method and application thereof |
| CN111889025A (en) * | 2020-09-01 | 2020-11-06 | 山东大学 | Acid-alkali-resistant salt-resistant super-amphiphilic molecule emulsifier, preparation method thereof and emulsion |
| CN112542296A (en) * | 2020-12-04 | 2021-03-23 | 刚和石油(营口)有限公司 | Biodegradable high-ignition-point insulating fluid |
| CN112542296B (en) * | 2020-12-04 | 2021-10-29 | 刚和石油(营口)有限公司 | Biodegradable high-ignition-point insulating fluid |
| CN113683804A (en) * | 2021-10-13 | 2021-11-23 | 山东天铭医药科技有限公司 | Double-crosslinked chitosan poly (ester-urethane) modified oxidized starch and preparation method thereof |
| CN113683804B (en) * | 2021-10-13 | 2022-12-02 | 山东天铭医药科技有限公司 | Double-crosslinked chitosan poly (ester-urethane) modified oxidized starch and preparation method thereof |
| WO2023092750A1 (en) * | 2021-11-29 | 2023-06-01 | 浙江大学台州研究院 | Tpu medical catheter with outer surface modified by antibacterial polysaccharide and preparation method therefor |
| CN115160538A (en) * | 2022-07-09 | 2022-10-11 | 四川大学 | Crosslinked PDMS/chitosan composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101497698A (en) | Preparation of chitosan-polyurethane ion complex elastomer material | |
| CN100391994C (en) | Preparation method of chitin modified water polyurethane elastic body | |
| Sarasam et al. | Blending chitosan with polycaprolactone: effects on physicochemical and antibacterial properties | |
| CN103420868B (en) | Biquaternary ammonium salt-containing diamine or diol monomer, preparation method of monomer, water-based non-toxic antibacterial polyurethane emulsion prepared by monomer, and preparation method of emulsion | |
| Wang et al. | Zwitterionic polyurethanes with tunable surface and bulk properties | |
| Zhang et al. | Gemini quaternary ammonium salt waterborne biodegradable polyurethanes with antibacterial and biocompatible properties | |
| EP1773399B1 (en) | Hydrogels of hyaluronic acid and alpha, beta-polyaspartylhydrazide and their biomedical and pharmaceutical uses | |
| Sun et al. | Covalently crosslinked hyaluronic acid‐chitosan hydrogel containing dexamethasone as an injectable scaffold for soft tissue engineering | |
| CN101905034B (en) | Method for preparing biological polysaccharide self-assembly modificatory chitosan antibacterial biological material | |
| Javaid et al. | Evaluation of cytotoxicity, hemocompatibility and spectral studies of chitosan assisted polyurethanes prepared with various diisocyanates | |
| CN107789677B (en) | Preparation method and application of hyperbranched polyimide anticoagulant antibacterial material | |
| Marcano et al. | Designing biodegradable PHA-based 3D scaffolds with antibiofilm properties for wound dressings: optimization of the microstructure/nanostructure | |
| Zia et al. | Chitin based polyurethanes using hydroxyl terminated polybutadiene, part III: Surface characteristics | |
| TW201323026A (en) | Brush polymer and medical use thereof | |
| CN113801264B (en) | Precursor polymer of intelligent antibacterial functional coating and preparation method and application thereof | |
| CN101343346A (en) | Chitosan polyurethane material and preparation thereof | |
| Liu et al. | A mild method for surface-grafting MPC onto poly (ester-urethane) based on aliphatic diurethane diisocyanate with high grafting efficiency | |
| CN114262455B (en) | Starch/epsilon-polylysine/poly (L-lactic acid) double-crosslinking material and preparation method and application thereof | |
| Chen et al. | Heparin-mimetic polyurethane hydrogels with anticoagulant, tunable mechanical property and controllable drug releasing behavior | |
| CN113956437A (en) | Polyurethane sponge and preparation method and application thereof | |
| CN106693054A (en) | Bacterial cellulose/heparin medical composite material and preparation method thereof | |
| Zhang et al. | Preparation, physicochemical properties and biocompatibility of biodegradable poly (ether-ester-urethane) and chitosan oligosaccharide composites | |
| Zhang et al. | Injectable and self‐healing hydrogels with tissue adhesiveness and antibacterial activity as wound dressings for infected wound healing | |
| JP2007537168A (en) | Polymer coupling agents and pharmaceutically active polymers made therefrom | |
| CN105504190B (en) | A kind of photo-crosslinking biomim betatic and its preparation and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20090805 |