CN100523038C - Polyurethane with shape memory property, composition containing it and shape memory fabric prepared therefrom - Google Patents
Polyurethane with shape memory property, composition containing it and shape memory fabric prepared therefrom Download PDFInfo
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- CN100523038C CN100523038C CNB2004100025522A CN200410002552A CN100523038C CN 100523038 C CN100523038 C CN 100523038C CN B2004100025522 A CNB2004100025522 A CN B2004100025522A CN 200410002552 A CN200410002552 A CN 200410002552A CN 100523038 C CN100523038 C CN 100523038C
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- urethane
- agent
- shape memory
- diisocyanate
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 42
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 42
- 239000004744 fabric Substances 0.000 title claims description 94
- 239000000203 mixture Substances 0.000 title claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 78
- 238000002360 preparation method Methods 0.000 claims description 55
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 49
- 239000004970 Chain extender Substances 0.000 claims description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 239000000835 fiber Substances 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 27
- 230000003472 neutralizing effect Effects 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 239000003153 chemical reaction reagent Substances 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 16
- 238000005189 flocculation Methods 0.000 claims description 16
- 230000016615 flocculation Effects 0.000 claims description 16
- 230000007704 transition Effects 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 8
- -1 aliphatic isocyanates Chemical class 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 7
- 150000003673 urethanes Chemical class 0.000 claims description 7
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004902 Softening Agent Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000012466 permeate Substances 0.000 claims description 6
- 239000004753 textile Substances 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 238000013461 design Methods 0.000 claims description 5
- FSEUPUDHEBLWJY-HWKANZROSA-N diacetylmonoxime Chemical group CC(=O)C(\C)=N\O FSEUPUDHEBLWJY-HWKANZROSA-N 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- 229960004418 trolamine Drugs 0.000 claims description 5
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 4
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 4
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- 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 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 4
- 229960004217 benzyl alcohol Drugs 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 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
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 4
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 4
- 238000007761 roller coating Methods 0.000 claims description 4
- 229960004889 salicylic acid Drugs 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 159000000013 aluminium salts Chemical group 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 159000000003 magnesium salts Chemical class 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 150000003751 zinc Chemical class 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 239000002981 blocking agent Substances 0.000 abstract 1
- 230000000903 blocking effect Effects 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000037303 wrinkles Effects 0.000 description 6
- 239000000376 reactant Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229920001610 polycaprolactone Polymers 0.000 description 4
- 239000004632 polycaprolactone Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000009775 high-speed stirring Methods 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 230000006386 memory function Effects 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003892 spreading Methods 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 230000037396 body weight Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000675 fabric finishing Substances 0.000 description 2
- 238000009962 finishing (textile) Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920000431 shape-memory polymer Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- QQLILYBIARWEIF-UHFFFAOYSA-N 2-(2-hydroxyethylsulfonyl)ethanol Chemical compound OCCS(=O)(=O)CCO QQLILYBIARWEIF-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000004855 creaseproofing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000002631 hypothermal effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical class NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000001955 polymer synthesis method Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000012781 shape memory material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009988 textile finishing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The said polyurethane is prepared through preparing polymer with diisocyanate, hydroxyl-containing oligomer, chain expander with active hydrogen radical and chain expander with carboxylic radical, neutralizer with alkali radical, blocking agent, cross-linking agent and optional catalyst in certain proportion; and subsequent reaction in water to obtain polymer. The polyurethane features the blocking diisocyanate radical and hydroxyl radical and thus shape converting temperature of -30 deg.c to 100 deg.c. In temperature higher than the shape converting temperature, the polyurethane may have its shape converted; in temperature lower than the shape converting temperature, the polyurethane is unchanged in shape; and the polyurethane heated to the temperature higher than the shape converting temperature will restore original shape.
Description
Technical field
The present invention relates to a kind of urethane and application in the preparation shape memory fabrics thereof with shape memory.More specifically, the present invention relates to have the urethane, water-based shape memory polyurethane composition and method of making the same, shape memory fabrics and preparation method thereof of shape memory.
Background technology
Usually, has foam materials that the urethane of shape memory makes be widely used (day flat 2-113016 of disclosure special permission communique, 1990, Mitsubishi Heavy Industry Ltd.).Shape memory polyurethane has the big and thermal insulation of deformation amount of recovery, and these characteristics are widely applied in the extensive stock.These foaies can under certain shape need and under certain model by post forming.The shape-memory polymer of moulding changes shape being higher than under its shape memory transition temperature but being lower than under the rheology temperature, when polymkeric substance is cooled to be lower than the shape memory transition temperature with the state after changing, and the shape of change just fixing.The method of utilizing of shape memory is thereby that the shape that will change is heated to above shape memory transition temperature recovery virgin state.That is to say that shape-memory polymer finalizes the design in certain model deformation in certain temperature variation.
Open WO01/07499 of PCT international application and the open CN1361799A of Chinese patent application disclose the preparation method of shape memory polyurethane or polyurethane-urea polymers, its second-order transition temperature is 20~100 ℃ of scopes, flexible polyurethane section monomer adopts the polysiloxane macromolecule dihydric alcohol, the monomer cost is higher, is mainly used in medical device.Also have the shape-memory material of some patents and bibliographical information polyurethane-base in addition, they have certain purposes at aspects such as toy, medical treatment, automobiles.
Wrinkle proofing is the important postfinishing process of fabric, and traditional crease proofing agent is mainly N-methylol amide compounds, can discharge a large amount of formaldehyde when textile finishing; Fabric after the arrangement, deposit or wearing process in, also can decompose or discharge formaldehyde.At present the formaldehydeless finishing agent of exploitation mainly contain Resins, epoxy, double hydroxyethyl sulfone, dimethyl urea oxalic dialdehyde, 1,2,3,4-tetracarboxylic acid butane (BTCA) etc.But what have application prospect most is 1,2,3,4-tetracarboxylic acid butane (BTCA), and United States Patent (USP) 4,975 has disclosed polycarboxylic acid in 209,4,820,307 and 5,221,285 and be linked to the wrinkle resistant effect of playing on the fabric under the effect of catalyzer.But crosslinked polycarboxylic acid has reduced the tear strength of fabric, and the arrangement cost is too high.
We find that water-based shape memory polyurethane composition is applied on textiles and the clothing, has shape memory effect in the research.Up to the present, go back the report of Shang Weijian so far about water-based shape memory polyurethane composition and relevant shape memory fabrics.Further, up to the present, home and overseas is not also about preparing argumentation, report and the patent of water-based shape memory polyurethane by the introduction carboxylic group.
For overcoming the limitation of prior art, and at traditional new understanding of crease-resistant notion proposition, the object of the present invention is to provide fabric with shape memory function, this shape memory fabrics has good wrinkle resistant function on the shape memory transition temperature, the various wrinkle that especially can recover to produce in water washing process promptly recover its original-shape and keep its elasticity simultaneously.This fabric is put in order or is applied and get via water-based shape memory polyurethane composition.
Summary of the invention
For achieving the above object, the present invention at first provides a kind of urethane, and its weight-average molecular weight is characterized in that between 10000 to 100000 this urethane is that the prepolymer that following component reaction prepares is continued the resulting polymkeric substance of reaction in water:
1) vulcabond;
2) hydroxyl oligopolymer;
3) contain the chainextender and the carboxylic chainextender of active hydrogen group;
4) contain the neutralizing agent of basic group;
5) end-capping reagent;
6) linking agent, and
7) Ren Xuan catalyzer,
It is characterized in that isocyano and hydroxyl (NCO/OH=0.8~1.6) end-blocking of described urethane with different molal quantities, and described component molar ratio is, vulcabond: hydroxyl oligopolymer: chainextender: neutralizing agent: end-capping reagent: linking agent: catalyzer=0.8~1.6:0.2~0.8:0.4~1:0.2~0.6:0~1.2:0~0.4:0~0.02, described urethane has the transfer of shapes temperature in-30~100 ℃ of scopes, when being higher than described shape memory transition temperature, this urethane can change shape, and finalize the design when being lower than this temperature being cooled to, when being heated to above this temperature, can recover original-shape then.
The present invention further provides a kind of polyurethane composition, it contains aforesaid urethane and water, and the solid content of described composition is 5%-50% (weight).
The present invention also provides the preparation method of aforesaid urethane, comprises the steps:
A) the hydroxyl oligopolymer is mixed with excessive vulcabond and the mixture of gained is heated;
B) in reaction process, add chainextender and the carboxylic chainextender that contains active hydrogen group;
C) add end-capping reagent;
D) add alkaline neutraliser and linking agent, make reacting liquid pH value between 6-7; And
E) gained prepolymer in the step d) is scattered in the water, makes it to continue reaction.
The present invention further provides a kind of preparation method of shape memory fabrics, comprised using to comprise substrate fabric is put in order as the finishing composition of aforesaid urethane.
The present invention also provides the preparation method of another shape memory fabrics, comprises using the coating-forming agent that contains aforesaid urethane that substrate fabric is applied.
The present invention further provides a kind of shape memory fabrics, it comprises substrate fabric and aforesaid urethane.
An advantage of the present invention is that described shape memory polyurethane has improved mechanical property, the transparency, biologically stable, resistance to deterioration, oxidation-resistance, anti-time property, formaldehydeless release and environmentally friendly property.
Another advantage of the present invention is, the production technique of the shape memory fabrics that adopts (comprising arrangement and coating) is compared with at present common postfinishing process, step without any complexity, and owing to do not adopt strongly acidic catalyst and long-time high temperature to bake and bank up with earth, to the brute force and the not damage of hand feel and drape of fabric.
Advantage of the present invention more is embodied in described shape memory fabrics can recover the folding line that produces in dress or the folding process in 30-100 ℃ of warm air or hot water, be returned to the original-shape of fabric.Described shape memory fabrics can the end capped isocyano of deblocking in the process of baking and banking up with earth, and makes it self to take place crosslinked or reacts the shape memory function of reinforced fabric, water-wash resistance and chemical-resistant with reactive group on the fabric fibre.Described shape memory fabrics has the characteristics of fabric form memory reservation, wrinkle resistant, shrinkproof typing, no strength loss, hand feel and drape, moisture-penetrable ventilated property, environmental friendliness, formaldehydeless release.The fabrics feel soft of arrangement can keep the primary state substantially.No matter fabric produces fold or distortion when placing or wearing for a long time, this fabric is heated to more than the shape memory transition temperature, and fabric can be relatively easy to return to the virgin state that it remembers and eliminate the fold or the distortion of generation.Therefore can be used as face, the back of the body, the sleeve of shirt through the fabric of this kind method arrangement.In a word, the fabric of handling through different arrangement prescriptions can use at the different sites of shirt, has very high using value.
Embodiment
The invention provides a kind of urethane with shape memory, its weight-average molecular weight is characterized in that between 10000 to 100000 this urethane is that the prepolymer that following component reaction prepares is continued the resulting polymkeric substance of reaction in water:
1) vulcabond;
2) hydroxyl oligopolymer;
3) contain the chainextender and the carboxylic chainextender of active hydrogen group;
4) contain the neutralizing agent of basic group;
5) end-capping reagent;
6) linking agent, and
7) Ren Xuan catalyzer,
It is characterized in that isocyano and hydroxyl (NCO/OH=0.8~1.6) end-blocking of described urethane with different molal quantities, and described component molar ratio is, vulcabond: hydroxyl oligopolymer: chainextender: neutralizing agent: end-capping reagent: linking agent: catalyzer=0.8~1.6:0.2~0.8:0.4~1:0.2~0.6:0~1.2:0~0.4:0~0.02, described urethane has the transfer of shapes temperature in-30~100 ℃ of scopes, when being higher than described shape memory transition temperature, this urethane can change shape, and finalize the design when being lower than this temperature being cooled to, when being heated to above this temperature, can recover original-shape then.
The ratio of preferred vulcabond and hydroxyl oligopolymer is 1.1-2.5.Wherein, preferably, described vulcabond can be selected from aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate and composition thereof, described aliphatic diisocyanate can be selected from isophorone diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate and 1, the 6-hexamethylene diisocyanate, described aromatic diisocyanate can be selected from 4,4 '-diphenylmethanediisocyanate, tolylene diisocyanate, xylylene diisocyanate; The optional autopolyester polyvalent alcohol of described hydroxyl oligopolymer, polyether glycol, polycarbonate, polycaprolactone and composition thereof; The described chainextender that contains active hydrogen group can be selected from 1,4-butyleneglycol, 1, ammediol, hexahydroaniline, ethylene glycol and dihydroxyphenyl propane; Described carboxylic chainextender is a dimethylol propionic acid; Described neutralizing agent can be selected from water miscible tertiary amine, alkali metal hydroxide and composition thereof, and in described neutralizing agent and the urethane ratio of contained carboxyl at 1:0.5 between the 1:1.2; Described linking agent is selected from water miscible small molecules polyvalent alcohol and polyhydric alcohol amine; Described linking agent can be selected from glycerol, diethanolamine, trolamine, TriMethylolPropane(TMP), quadrol and hexanediamine; Described end-capping reagent is selected from Diacetylmonoxime, sodium bisulfite, Potassium hydrogen sulfite, phenylcarbinol, salicylic acid and methyl aceto acetate.
The present invention also provides a kind of polyurethane composition with shape memory, it comprises aforesaid urethane and water, the solid content of described composition is 5%-50% (weight), preferred described composition do not contain surpass 30% (weight) can be miscible with water organic solvent, more preferably described composition does not contain any organic solvent.
The present invention also provides the preparation method of aforesaid urethane, comprises the steps:
A) the hydroxyl oligopolymer is mixed with excessive vulcabond and the mixture of gained is heated;
B) in reaction process, add chainextender and the carboxylic chainextender that contains active hydrogen group;
C) add end-capping reagent;
D) add alkaline neutraliser and linking agent, make reacting liquid pH value between 6-7; And
E) gained prepolymer in the step d) is scattered in the water, makes it to continue reaction.
The invention provides a kind of preparation method of shape memory fabrics, comprise and use the finishing composition that comprises aforesaid urethane that substrate fabric is put in order.
In one embodiment of the invention, described adjustment method comprises the steps: a) to pad substrate fabric with finishing composition; B) oven dry; And c) bake and bank up with earth, preferably include following steps: a) pad substrate fabric with finishing composition, two soak two rolls mangle expression 100%~150%; B) 80~90 ℃ of oven dry 1~3 minute; And c) baked and banked up with earth 1~3 minute at 140~170 ℃.
In one embodiment of the invention, described finishing composition comprises following composition: the urethane of 4-10% weight part; The softening agent of 1-3% weight part; Permeate agent with the 1-3% weight part.
The present invention also provides the preparation method of another kind of shape memory fabrics, comprise and use the coating-forming agent that contains aforesaid urethane that substrate fabric is applied, handle the substrate fabric that has applied preferred also comprising with flocculation agent, wherein carries out coated with blade coating, roller coating or impregnation method.Preferably wherein in the used coating agent solid content be 10-60 weight %, preferred 20-50 weight % counts 10-200g/m to cause on the fabric coating amount to do weightening finish
2The agent of amount applying coating, preferred 20-100g/m
2
Preferably, wherein used flocculation agent is selected from metal-salts such as aluminium salt, molysite, calcium salt, magnesium salts, zinc salt, pink salt, sodium salt, sylvite, perhaps be selected from organic or inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetate, perhaps be selected from the mixture that described material constitutes, the concentration of wherein said flocculation agent is 0.5-40% by weight, is preferably 1-20%; The substrate fabric that has wherein applied treatment time in flocculation agent is 10 seconds to 10 minutes, is preferably 1 to 5 minute.
The present invention also provides a kind of shape memory fabrics, and it comprises substrate fabric and aforesaid urethane.
Used substrate fabric is textile fibres or non-woven fibre in aforesaid method and fabric, and described fiber is preferably the mixed fibre of natural fiber, regenerated fiber, synthon or these fibers.
The shape memory polyurethane that has elasticity with conventional shape-memory urethane more than the shape memory transition point and generally obtain is with hydroxy-end capped different, shape memory polyurethane of the present invention is with the isocyano and hydroxyl (NCO/OH=0.8~1.6) end-blocking of different molal quantities, weight-average molecular weight is between 10000 to 100000, has the transfer of shapes temperature in-30~100 ℃ of scopes, when being higher than described shape memory transition temperature, this urethane can change shape, and finalize the design when being lower than this temperature being cooled to, when being heated to above this temperature, can recover original-shape then.The tensional modulus of the tensional modulus of this shape memory polyurethane when being higher than 10 ℃ of shape memory transition temperatures when being lower than 10 ℃ of shape memory transition temperatures is than being 50-400.
The present invention comprises the solid content of water-based shape memory polyurethane composition of described shape memory polyurethane between 5%-50% (weight).Said composition preferably do not contain surpass 30% (weight) can be miscible with water organic solvent, for example methylformamide, acetone etc. more preferably do not contain any organic solvent.
The preparation method of shape memory polyurethane of the present invention comprises following reactions steps:
A) the hydroxyl oligopolymer is mixed with excessive vulcabond and the mixture of gained is heated;
B) in reaction process, add the chainextender that contains active hydrogen group;
C) add end-capping reagent;
D) add alkaline neutraliser and linking agent, make reacting liquid pH value between 6-7; And
E) make products therefrom homodisperse in water in the step d) by under high-speed stirring, adding deionized water, preferably use 5 ℃ of-80 ℃ of deionized waters.
This method adopts the performed polymer synthesis method to prepare shape memory polyurethane, and at first, vulcabond and polyvalent alcohol are by certain mole proportioning A=[NCO]/[OH] reaction prepolymer.Then add chainextender.After the several hrs reaction, add end-capping reagent to react unreacted isocyano, add neutralizing agent and linking agent then, ionomeric polymer generates the negatively charged ion shape memory polyurethane.In the process of reaction, isocyanic acid (NCO) foundation group can react with carboxylic group, but the speed of its reaction is slower than the reaction of isocyanic acid (NCO) foundation group and oh group.Yet isocyanic acid under the certain reaction condition (NCO) foundation group reacts with carboxylic group, produces some amino chemical combination keys, forms cross-link bond in the molecule.In fact cross-link bond just produced in the stage of synthetic prepolymer.The aqueous dispersion of shape memory polyurethane can be prepared to obtain by the performed polymer of aforesaid urethane with comparalive ease.Generally include several steps: 1) use in the neutralizing agent and carboxylic group; 2) add protective material protection isocyano; 3) adding the Ionized performed polymer of water-dispersion, 4) prepolymer of chain extension adds the water that entry or adding contain polyamine (functionality is at 2.2-4) under condition of stirring.This several steps can once be finished.
Comprise excessive relatively vulcabond at the employed reactant reaction raw material of the preparation method of described shape memory polyurethane; oligomeric polyols; chainextender; end-capping reagent; linking agent; neutralizing agent and protective material can also add a spot of catalyzer such as dibutyltin dilaurate etc. in case of necessity in reaction process.
The molecular formula general formula that can be used for vulcabond of the present invention is: OCN-R-NCO, R represents one or two phenyl ring or only contains a plurality of methylene radical and cycloaliphatic ring, include, but not limited to aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate and composition thereof.The object lesson of suitable aliphatic diisocyanate comprise isophorone diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate and 1, the 6-hexamethylene diisocyanate.The object lesson of suitable aromatic isocyanate comprises 4,4 '-diphenylmethanediisocyanate, tolylene diisocyanate, xylylene diisocyanate.
What can be used for hydroxyl oligopolymer of the present invention includes, but not limited to polyester polyol, polyether glycol, polycarbonate, polycaprolactone and composition thereof.The object lesson of suitable hydroxyl oligopolymer comprises: polyvalent alcohols such as polypropylene glycol or polyoxytrimethylene ether glycol, polytetramethylene glycol, polytetramethylene glycol, polyvinyl alcohol, polycaprolactone (glycol), poly bisphenol.
The ratio of described vulcabond and hydroxyl oligopolymer is generally 1.1-2.5.
Can be used for the general molecular formula that contains the chainextender of active hydrogen group of the present invention is: OH-R "-OH; R " represent 2-12 methylene radical, 1-2 six-ring or contain the carboxylate radical of 1-2, comprise, but be not limited to, carboxylic glycol, 1,4-butyleneglycol, 1, ammediol, hexahydroaniline, ethylene glycol and dihydroxyphenyl propane.Preferred chainextender is a dimethylol propionic acid.
Can be used for neutralizing agent of the present invention and be selected from water miscible tertiary amine, alkali metal hydroxide and composition thereof, comprise trolamine, triethylamine, sodium hydroxide, potassium hydroxide and their mixture.
Can be used for linking agent of the present invention and include, but not limited to water miscible small molecules polyvalent alcohol and polyhydric alcohol amine.The object lesson of suitable linking agent comprises glycerol, diethanolamine, trolamine, TriMethylolPropane(TMP), quadrol and hexanediamine.
Can be used for end-capping reagent of the present invention and include, but not limited to weakly acidic salt or other organic end-capping reagent.The object lesson of suitable end-capping reagent comprises Diacetylmonoxime, sodium bisulfite, Potassium hydrogen sulfite, phenylcarbinol, salicylic acid and methyl aceto acetate.
In neutralization reaction, the consumption of neutralizing agent want can in and the carboxylic group that contained in the performed polymer.The mol ratio of institute's carboxyl group and neutralizing agent is at 1:(0.5-1.2 in the urethane).
The preparation method of a kind of shape memory fabrics provided by the present invention comprises and uses the finishing composition comprise water-based shape memory polyurethane composition of the present invention that substrate fabric is put in order.Finishing composition can adopt following prescription: the urethane of 4-10% weight; The softening agent of 1-3% weight; Permeate agent with 1-3% weight.Adjustment method can adopt following steps to carry out:
A) fabric padding finishing agent (two soak two rolls mangle expression 100%~150%);
B) oven dry (80~90 ℃, 1~3 minute); With
C) bake and bank up with earth (140~170 ℃, 1~3 minute).
The preparation method of another kind of shape memory fabrics provided by the present invention comprises and uses the coating-forming agent comprise water-based shape memory polyurethane composition of the present invention that substrate fabric is applied.Coating procedure can carry out with blade coating, roller coating or impregnation method.Solid content is for being generally 10-60% (weight) in the used coating agent, and preferred solid content is 20-50% (weight), to guarantee that the coating amount is generally 10-200g/m to do weightening finish on fabric
2, be preferably 20-100g/m
2
In described method, further comprise and handle coated fabric with flocculation agent.The available flocculation agent comprises in the present invention, but be not limited to, organic or inorganic acid such as metal-salt such as aluminium salt, molysite, calcium salt, magnesium salts, zinc salt, pink salt, sodium salt, sylvite and hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetate, and the mixture that constitutes of these materials.In use, the concentration of described flocculation agent is generally 0.5-40% by weight, is preferably 1-20%.Coated substrate fabric treatment time in flocculation agent was generally 10 seconds to 10 minutes, was preferably 1 to 5 minute.
The substrate fabric that can be used for shape memory fabrics preparation method of the present invention includes, but not limited to nonwoven fabric and textile fabric, is preferably natural fiber, regenerated fiber or synthon or mixed fibre.
Shape memory fabrics provided by the present invention is characterized in that, contains shape memory polyurethane of the present invention through arrangement or coating on it.End capped isocyano can baked and banked up with earth deblocking under the temperature on the wherein said water-based shape memory polyurethane, self takes place crosslinked or reacts with reactive group on the fabric fibre, has strengthened shape memory function and the water tolerance and the chemical-resistant of fabric.
Below in conjunction with specific embodiment the present invention is further detailed.
Embodiment
The preparation of water-based shape memory polyurethane
In a four-hole boiling flask of being furnished with the protection of mechanical stirrer, drying nitrogen, prolong, add low poly-dihydric alcohol, vulcabond, a spot of solvent dimethyl formamide or do not need solubilizing agent.Under nitrogen protection, be heated to 80 ℃-90 ℃ and also reacted with this understanding 2-3 hour, obtain the performed polymer of urethane.Add chainextender then and comprise that the chainextender that contains carboxyl also continues reaction 2 hours, adds a certain amount of end-capping reagent again to react remaining isocyano.
In above-mentioned reaction mixture, add neutralizing agent and linking agent, the quantity of neutralizing agent in theory can be fully in chainextender in carboxylic group.Neutralizing agent reacted 10-20 minute with reaction mixture about 50 ℃.The hypothermic response thing adds protective material for 0 ℃-5 ℃ to room temperature, under the effect of high speed agitator (1000-2000rpm), adds entry lentamente in polymkeric substance.For dispersed polymeres better, can add a spot of acetone sometimes.The content of final polymkeric substance is at 20%-60%.The solvent that contains in the solution is removed by underpressure distillation.
Embodiment 1
Polycaprolactone (the PLACCEL240 that adds 120g, DacielChemicalIndustries, LTD.) (molecular weight 4000, dry), with the diphenylmethanediisocyanate of 30g in 500 milliliters, band mechanical stirring, be connected in the four-hole glass flask of nitrogen port.Feed drying nitrogen, mechanical stirring remains under 80 ℃~90 ℃ temperature and reacted 3 hours.Add 1 of 2.7g dimethylol propionic acid and 4.5g then successively, the 4-butyleneglycol continues reaction 2 hours as under the condition of chainextender between keeping 80 ℃~90 ℃.Can add a spot of dimethyl formamide in this reaction process.Then reduce the temperature to 50 ℃ of reactant, the triethylamine that adds 2.2g is with the carboxyl in the neutralization reactant.At last add 250 milliliters of deionized waters that contain 4.2g sulfurous hydracid sodium down, obtain solid content and be 25% water white water-based shape memory polyurethane in the high-speed stirring (1000rpm) of agitator.In the present embodiment, vulcabond: hydroxyl oligopolymer: chainextender: neutralizing agent: the mol ratio=120:30:70:22:40 of end-capping reagent.The thin film shape memory transition temperature that makes through present embodiment is 45 ℃.Shape-memory properties test: the film that obtains with this polyurethane preparation stretches one times through 55 ℃, is cooled to 35 ℃ of typings then, returns to original shape in 45 ℃ water-bath fully.
Embodiment 2
The polypropylene glycol (molecular weight 2000, dry) that adds 48g is with the diphenylmethanediisocyanate to 500 of 20g milliliter, band mechanical stirring, be connected in the four-hole glass flask of nitrogen port.Feed exsiccant nitrogen, under the effect of agitator, keep 80 ℃~90 ℃ reactions of temperature 3 hours.Add 1 of 3.2g dimethylol propionic acid and 1.5g then successively, the 4-butyleneglycol continues reaction 2 hours as under the condition of chainextender between keeping 80 ℃~90 ℃, adds the 2.8g Diacetylmonoxime then and continues reaction 2 hours.Can add a spot of dimethyl formamide in this reaction process.Then reduce the temperature to 50 ℃ of reactant, add the carboxyl in the diethanolamine neutralization reactant of 2.6g.High-speed stirring (1000rpm) at agitator adds 100 milliliters of deionized waters down at last, and obtaining solid content is the water-based shape memory polyurethane of 40% (weight).In the present embodiment, vulcabond: hydroxyl oligopolymer: chainextender: neutralizing agent: end-capping reagent: the mol ratio=80:24:40:26:32 of linking agent.The thin film shape memory transition temperature that makes through present embodiment is 10 ℃.Shape-memory properties test: the film that obtains with this polyurethane preparation stretches one times through 20 ℃, is cooled to 0 ℃ of typing then, returns to original shape in 10 ℃ water-bath fully.
The preparation of shape-memory-fabric finishing liquid
Embodiment 1 resulting water-based shape memory polyurethane is diluted with deionized water, and interpolation softening agent and permeate agent, to be mixed with solid content 6%, softening agent (SG-6, Hai'an, Jiangsu petroleum chemical plant) 2%, the shape-memory-fabric finishing liquid of permeate agent (JFC, Hai'an, Jiangsu petroleum chemical plant) 2%.
The preparation of shape memory fabrics
Embodiment 3
To treat finish fabric (42/43 "; 30s * 30s, 68 * 68,100% cotton; bleach) be immersed in the water-based shape memory polyurethane dressing liquid of above-mentioned preparation that (solid content 6%; softening agent 2%, permeate agent 2%, two soaks two and rolls; the mangle expression weight ratio is 100%; preliminary drying 3 minutes in 85 ℃ of baking ovens then, bakes and banks up with earth 2 minutes at 150 ℃ again, is cooled to room temperature and promptly gets shape memory fabrics.
Embodiment 4
With pretreating fabrics (42/43 "; 30s * 30s; 68 * 68; 100% cotton; bleach) with blade coating; roller coating or impregnation method are coated the water-based shape memory polyurethane coating-forming agent (solid content 40 weight %) as embodiment 2 preparation equably, when coating is not dried, immerse the cohesion fill the Tai-Ace S 150 flocculation agent aqueous solution and carry out wet method film forming (coagulation liquid concentration 2% in bathing 40 ℃, 2 minutes), to be coated on 80 ℃ of oven dry then, in 0~60 ℃ water, soaked 5~30 minutes then, go up residual flocculation agent and other solvend to remove coating, promptly get film thickness and be 0.5 millimeter shape memory fabrics finished product.
The test of shape memory fabrics (sample adopts the product of the foregoing description 3,4 preparations)
Table 1 shape memory fabrics is at the crease resistance of room temperature
Embodiment 3 | Embodiment 4 | |
Rate of body weight gain (%) | 6.2 | 5.8 |
Dry creasing angle (warp-wise and broadwise) | 280 degree | 270 degree |
Ultimate strength retention rate (%) | 96 | 95 |
The DP grade | 4.3 | 4.2 |
Annotate: the dry creasing angle of untreated fabric is 210 degree, adopts the crease recovery instrument of AATCC 66-1996 standard and DAIEI KAGAKU SEIKI LTD. to measure wrinkle recovery angle, adopts Instron 4411 apparatus measures strength retentions.
As can be seen from Table 1, shape memory fabrics has good crease resistance and powerful retention property in room temperature.
The crease resistance of table 2 shape memory fabrics in high temperature
Original | Embodiment 3 | Embodiment 4 | |
Rate of body weight gain (%) | -- | 6.2 | 5.8 |
Folding line keeps grade (50 ℃ of hot water) | 1.3 | 3.9 | 3.8 |
Fabric spreading (50 ℃ of hot water) | 2.5 | 4.2 | 4 |
Folding line keeps grade (70 ℃ of warm airs) | 1.2 | 3.9 | 3.8 |
Fabric spreading (70 ℃ of warm airs) | 2.3 | 4.1 | 4 |
Ultimate strength retention rate (%) | 100 | 102 | 98 |
Annotate: folding line keeps grade and fabric spreading utilization U.S. AATCC-88C and AATCC-124 judgement criteria, and the fabric folding line is in advance prior to pressing folding line three minutes with flatiron in 140 ℃ of high temperature.
As can be seen from Table 2, the folding line of shape memory fabrics when high temperature well kept.
Protection scope of the present invention is not limited to the foregoing description, and should be as the criterion with the content that limits in the claim.Those skilled in the art can do various changes with enforcement the present invention to specific embodiments of the invention or parameter etc., and needn't pay performing creative labour according to of the present invention open.Therefore, protection scope of the present invention should be understood to comprise the variation and the change of these routines.
Claims (49)
1. urethane, its weight-average molecular weight is characterized in that between 10000 to 100000, and this urethane is that the prepolymer with following component reaction preparation continues to react resulting polymkeric substance in water:
1) vulcabond;
2) hydroxyl oligopolymer, wherein said hydroxyl oligopolymer is selected from polyester polyol, polyether glycol, polycarbonate and composition thereof;
3) contain active hydrogen group chainextender and carboxylic chainextender;
4) contain the neutralizing agent of basic group;
5) end-capping reagent;
6) linking agent, and
7) Ren Xuan catalyzer,
It is characterized in that described urethane is with the isocyano of the different molal quantity ratios of NCO/OH=0.8~1.6 and hydroxy-end capped, wherein, and described component molar ratio is, vulcabond: hydroxyl oligopolymer: chainextender: neutralizing agent: end-capping reagent: linking agent: catalyzer=0.8~1.6:0.2~0.8:0.4~1:0.2~0.6:0~1.2:0~0.4:0~0.02, described urethane has the transfer of shapes temperature in-30~100 ℃ of scopes, when being higher than described shape memory transition temperature, this urethane can change shape, and finalize the design when being lower than this temperature being cooled to, when being heated to above this temperature, can recover original-shape then.
2. urethane as claimed in claim 1 is characterized in that, the molar ratio of described vulcabond and hydroxyl oligopolymer is 1.1-2.5.
3. urethane as claimed in claim 1 is characterized in that described vulcabond is selected from aliphatic diisocyanate, aromatic diisocyanate and composition thereof.
4. urethane as claimed in claim 3 is characterized in that, described aliphatic diisocyanate be selected from isophorone diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate and 1, the 6-hexamethylene diisocyanate.
5. urethane as claimed in claim 3 is characterized in that described aromatic diisocyanate is selected from 4,4 '-diphenylmethanediisocyanate, tolylene diisocyanate, xylylene diisocyanate.
6. urethane as claimed in claim 1 is characterized in that, the described chainextender that contains active hydrogen group is selected from 1,4-butyleneglycol, 1, ammediol, hexahydroaniline, ethylene glycol and dihydroxyphenyl propane.
7. urethane as claimed in claim 1 is characterized in that, described carboxylic chainextender is selected from dimethylol propionic acid.
8. urethane as claimed in claim 1 is characterized in that described neutralizing agent is selected from water miscible tertiary amine, alkali metal hydroxide and composition thereof, and in described neutralizing agent and the urethane ratio of contained carboxyl at 1:0.5 between the 1:1.2.
9. urethane as claimed in claim 1 is characterized in that, described linking agent is selected from water miscible small molecules polyvalent alcohol and polyhydric alcohol amine.
10. urethane as claimed in claim 9 is characterized in that described linking agent is selected from glycerol, diethanolamine, trolamine, TriMethylolPropane(TMP), quadrol and hexanediamine.
11. urethane as claimed in claim 1 is characterized in that, described end-capping reagent is selected from Diacetylmonoxime, sodium bisulfite, Potassium hydrogen sulfite, phenylcarbinol, salicylic acid and methyl aceto acetate.
12. a polyurethane composition, it comprises among the claim 1-11 each urethane and water, and the solid content of described composition is 5 weight %-50 weight %.
13. polyurethane composition as claimed in claim 12 is characterized in that, do not contain surpass 30 weight % can be miscible with water organic solvent.
14. polyurethane composition as claimed in claim 12 is characterized in that, does not contain any organic solvent.
15. the preparation method as each described urethane among the claim 1-11 comprises the steps:
A) the hydroxyl oligopolymer is mixed with excessive vulcabond and the mixture of gained is heated, wherein said hydroxyl oligopolymer is selected from polyester polyol, polyether glycol, polycarbonate and composition thereof;
B) in reaction process, add chainextender and the carboxylic chainextender that contains active hydrogen group;
C) add end-capping reagent;
D) add alkaline neutraliser and linking agent, make reacting liquid pH value between 6-7; And
E) gained prepolymer in the step d) is scattered in the water, makes it to continue reaction.
16. preparation method as claimed in claim 15 is characterized in that, the ratio of described vulcabond and hydroxyl oligopolymer is 1.1-2.5.
17. preparation method as claimed in claim 15 is characterized in that, described vulcabond is selected from aliphatic isocyanates, aromatic isocyanate and composition thereof.
18. preparation method as claimed in claim 17 is characterized in that, described aliphatic diisocyanate be selected from isophorone diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate and 1, the 6-hexamethylene diisocyanate.
19. preparation method as claimed in claim 17 is characterized in that, described aromatic diisocyanate is selected from 4,4 '-diphenylmethanediisocyanate, tolylene diisocyanate, xylylene diisocyanate.
20. preparation method as claimed in claim 15 is characterized in that, the described chainextender that contains active hydrogen group is selected from 1,4-butyleneglycol, 1, ammediol, hexahydroaniline, ethylene glycol and dihydroxyphenyl propane.
21. preparation method as claimed in claim 15 is characterized in that, the described chainextender that contains carboxyl is a dimethylol propionic acid.
22. preparation method as claimed in claim 15 is characterized in that, described neutralizing agent is selected from water miscible tertiary amine, alkali metal hydroxide and composition thereof, and in described neutralizing agent and the urethane ratio of contained carboxyl at 1:0.5 between the 1:1.2.
23. preparation method as claimed in claim 15 is characterized in that, the water that uses in the step e) is deionized water, and the temperature of this deionized water is at 5-80 ℃.
24. preparation method as claimed in claim 15 is characterized in that, described linking agent is selected from water miscible small molecules polyvalent alcohol and polyhydric alcohol amine.
25. preparation method as claimed in claim 24 is characterized in that, described linking agent is selected from glycerol, diethanolamine, trolamine, TriMethylolPropane(TMP), quadrol and hexanediamine.
26. preparation method as claimed in claim 15 is characterized in that, described end-capping reagent is selected from Diacetylmonoxime, sodium bisulfite, Potassium hydrogen sulfite, phenylcarbinol, salicylic acid and methyl aceto acetate.
27. the preparation method of a shape memory fabrics comprises using to comprise as the finishing composition of each urethane among the claim 1-11 substrate fabric is put in order.
28. preparation method as claimed in claim 27 is characterized in that, described adjustment method comprises the steps: a) to pad substrate fabric with finishing composition; B) oven dry; And c) bakes and banks up with earth.
29. preparation method as claimed in claim 27 is characterized in that, described adjustment method comprises the steps: a) to pad substrate fabric with finishing composition, and two soak two rolls mangle expression 100%~150%; B) 80~90 ℃ of oven dry 1~3 minute; And c) baked and banked up with earth 1~3 minute at 140~170 ℃.
30., it is characterized in that described finishing composition comprises following composition: the urethane of 4-10% weight part as each described preparation method among the claim 27-29; The softening agent of 1-3% weight part; Permeate agent with the 1-3% weight part.
31. as each described preparation method among the claim 27-29, described substrate fabric is textile fibres or non-woven fibre.
32., it is characterized in that described fiber is the mixed fibre of natural fiber, regenerated fiber, synthon or these fibers as each described preparation method among the claim 27-29.
33. the preparation method of a shape memory fabrics comprises and uses the coating-forming agent that contains as each described urethane among the claim 1-11 that substrate fabric is applied.
34. preparation method as claimed in claim 33 wherein also comprises with flocculation agent and handles the substrate fabric that has applied.
35. preparation method as claimed in claim 33 wherein carries out coated with blade coating, roller coating or impregnation method.
36. preparation method as claimed in claim 33, wherein solid content is 10-60 weight % in the used coating agent.
37. preparation method as claimed in claim 33, wherein solid content is 20-50 weight % in the used coating agent.
38. preparation method as claimed in claim 33 is wherein to cause on the fabric coating amount to count 10-200g/m to do weightening finish
2The agent of amount applying coating.
39. preparation method as claimed in claim 33 is wherein to cause on the fabric coating amount to count 20-100g/m to do weightening finish
2The agent of amount applying coating.
40. preparation method as claimed in claim 34, wherein used flocculation agent is the metal-salt that is selected from aluminium salt, molysite, calcium salt, magnesium salts, zinc salt, pink salt, sodium salt, sylvite, perhaps be selected from the organic or inorganic acid of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetate, perhaps be selected from the mixture that described material constitutes.
41. preparation method as claimed in claim 34, the concentration of wherein said flocculation agent are 0.5-40% by weight.
42. preparation method as claimed in claim 34, the concentration of wherein said flocculation agent are 1-20% by weight.
43. preparation method as claimed in claim 34, the substrate fabric that has wherein applied treatment time in flocculation agent is 10 seconds to 10 minutes.
44. preparation method as claimed in claim 34, the substrate fabric that has wherein applied treatment time in flocculation agent is 1 to 5 minute.
45. preparation method as claimed in claim 33 is characterized in that, described substrate fabric is textile fibres or non-woven fibre.
46. preparation method as claimed in claim 33 is characterized in that, described fiber is the mixed fibre of natural fiber, regenerated fiber, synthon or these fibers.
47. a shape memory fabrics is characterized in that, it comprises among substrate fabric and the claim 1-11 each urethane, on the wherein said substrate fabric through arrangement or apply and contain described urethane.
48. the described fabric of claim 47 is characterized in that, described substrate fabric is textile fibres or non-woven fibre.
49. fabric as claimed in claim 47 is characterized in that, described fiber is the mixed fibre of natural fiber, regenerated fiber, synthon or these fibers.
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