CN114940743B - Acid dye-dyeable bio-based polyurethane resin - Google Patents
Acid dye-dyeable bio-based polyurethane resin Download PDFInfo
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- CN114940743B CN114940743B CN202210399345.3A CN202210399345A CN114940743B CN 114940743 B CN114940743 B CN 114940743B CN 202210399345 A CN202210399345 A CN 202210399345A CN 114940743 B CN114940743 B CN 114940743B
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- polyurethane resin
- bio
- chain
- chain extender
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 198
- 239000002253 acid Substances 0.000 title claims abstract description 39
- 239000004970 Chain extender Substances 0.000 claims abstract description 126
- 239000012948 isocyanate Substances 0.000 claims abstract description 89
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 87
- 150000002009 diols Chemical class 0.000 claims abstract description 74
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 57
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920001410 Microfiber Polymers 0.000 claims abstract description 31
- 239000004744 fabric Substances 0.000 claims abstract description 31
- 239000003658 microfiber Substances 0.000 claims abstract description 31
- 239000002981 blocking agent Substances 0.000 claims abstract description 15
- 229920000570 polyether Polymers 0.000 claims abstract description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 12
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000728 polyester Polymers 0.000 claims abstract description 10
- 239000003208 petroleum Substances 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 57
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 43
- 229920002635 polyurethane Polymers 0.000 claims description 38
- 239000004814 polyurethane Substances 0.000 claims description 38
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 23
- 230000007062 hydrolysis Effects 0.000 claims description 20
- 238000006460 hydrolysis reaction Methods 0.000 claims description 20
- HZAXFHJVJLSVMW-UHFFFAOYSA-N monoethanolamine hydrochloride Natural products NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 14
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 150000003512 tertiary amines Chemical class 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000980 acid dye Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 125000004427 diamine group Chemical group 0.000 claims description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N hydroxylamine group Chemical group NO AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 abstract description 32
- 230000007547 defect Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 description 73
- 239000002994 raw material Substances 0.000 description 55
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 29
- 239000000975 dye Substances 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- -1 polytetramethylene Polymers 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 239000002649 leather substitute Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 3
- 239000001044 red dye Substances 0.000 description 3
- 150000003384 small molecules Chemical group 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 239000001043 yellow dye Substances 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical group C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 239000011846 petroleum-based material Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- JUVSRZCUMWZBFK-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)-4-methylanilino]ethanol Chemical compound CC1=CC=C(N(CCO)CCO)C=C1 JUVSRZCUMWZBFK-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical group CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- FYSJYVHOKOFOAP-UHFFFAOYSA-N hexanedioic acid;propane-1,3-diol Chemical compound OCCCO.OC(=O)CCCCC(O)=O FYSJYVHOKOFOAP-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
- C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/39—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using acid dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/241—Polyamides; Polyurethanes using acid dyes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- Chemical & Material Sciences (AREA)
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Abstract
The invention relates to an acid dye-dyeable bio-based polyurethane resin, wherein a molecular chain comprises a soft segment formed by long-chain dihydric alcohol and a hard segment formed by isocyanate, a chain extender and a blocking agent, and a structural unit corresponding to the long-chain dihydric alcohol comprises: structural unit a (derived from bio-based polyester diol), structural unit B (derived from bio-based polyether diol) and structural unit C (derived from copolyether diol of random copolymerization of petroleum-based polypropylene oxide and ethylene oxide); the structural unit A, the structural unit B and the structural unit C are connected into the molecular chain of the polyurethane resin through carbamate groups; the molar ratio of the structural unit B to the structural unit C is not more than 19; the biobased content of the biobased polyurethane resin is more than 60 weight percent; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is less than or equal to 31. The bio-based polyurethane resin has the characteristics of high bio-based content and excellent dyeing, and overcomes the defects of the prior art.
Description
Technical Field
The invention belongs to the technical field of synthetic resin, and relates to acid dye-dyeable bio-based polyurethane resin.
Background
Polyurethane resin is an important raw material for preparing superfine fiber synthetic leather, most superfine fiber suede leather in the market is prepared by using polyurethane resin raw materials based on petroleum industry chains, and the polyurethane resin can generate larger pollution, and is obviously different from the low-carbon and sustainable development requirements at the present stage. Chemical raw materials for synthesizing polyurethane resin can be divided into petroleum-based raw materials and biological-based raw materials according to different sources, and with the deep implementation of sustainable development policies, substitution of the traditional polyurethane synthesis path for polyurethane resin prepared based on the biological-based raw materials is becoming a great weight in the future.
In general, in order to obtain polyurethane resins prepared based on bio-based raw materials, one studies the structure of polyurethane and divides the structure of polyurethane into soft segments composed of polymer polyol and hard segments composed of isocyanate and small molecule chain extender. Among the polymer polyols constituting the soft segment, a common bio-based polymer polyol is poly (1, 3-propanediol adipate) glycol; among the isocyanates constituting the hard segment, a common biobased isocyanate is biobased diphenylmethane diisocyanate; among the small molecule chain extenders constituting the hard segment, a common bio-based small molecule chain extender is 1, 3-propanediol. The polymer polyol with the optional biological source can be used for synthesizing the full biological polyurethane with excellent mechanical property, but has defects in dyeing capability, the dyeing property is very important for the polyurethane resin for the microfiber suede leather, and the dyeing uniformity and the dyeing depth play a key role in the product quality of the finished suede leather.
However, limited by the limitations of bio-based materials, some petroleum-based materials are still needed for modification, and currently, the prior art still synthesizes full petroleum-based or petroleum-based materials for preparing superior dyeing polyurethane resins, such as the easy-to-dye polyurethane resins described in chinese patent application CN 105542108A. However, the scheme contains a large amount of adipic acid, polytetramethylene ether and other structures which are not of bio-based sources, and the dyeing depth L value of the easy-to-dye polyurethane resin is difficult to be less than or equal to 31.
The invention is expected to obtain the polyurethane resin which has high biobased content and excellent dyeing and is suitable for microfiber suede leather through synthesis innovation.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a bio-based polyurethane resin dyeable by acid dye.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an acid dye-dyeable bio-based polyurethane resin, wherein a molecular chain comprises a soft segment formed by long-chain dihydric alcohol and a hard segment formed by isocyanate, a chain extender and a blocking agent, and a structural unit corresponding to the long-chain dihydric alcohol comprises:
structural unit a: x=10-18, y=2-3, derived from bio-based polyester diol having a number average molecular weight of 1000-3000;
structural unit B:from bio-based polyether diols having a number average molecular weight of 1000 to 3000;
structural unit C:nx/(nx+ny) =0.5 to 0.8, derived from a copolyether glycol of random copolymerization of petroleum-based polypropylene oxide ethylene oxide having a number average molecular weight of 500 to 3000;
the structural unit A, the structural unit B and the structural unit C are connected into the molecular chain of the polyurethane resin through carbamate groups (-NH-COO-);
the molar ratio of the structural unit B to the structural unit C is not more than 19; when the molar ratio of the structural unit B to the structural unit C is larger than 19, the structural unit C occupies smaller space, and the effect of introducing the structural unit C is not reflected;
the polyurethane is a two-phase structure composed of soft segments and hard segments, and the hard segments are distributed in an aggregation state in a matrix formed by the soft segments; in the dyeing process of polyurethane, dye dispersed in water enters a soft segment of the polyurethane to realize the dyeing of the polyurethane, and experiments show that the introduction of a polyether structural unit B with relatively better hydrophilicity can not obviously help to improve the dyeing property, and the structural unit A and the structural unit B simultaneously form the soft segment of the polyurethane to obtain the bio-based polyurethane with excellent comprehensive performance, but the dyeing property is poor; based on this, the inventors have conducted intensive studies on the dyeing modification thereof, and have unexpectedly found that the introduction of the structural unit C consisting of a side group containing Propyl ether group CH 3 CH 2 CHO (from the ring opening of propylene oxide) and diethyl ether group C 2 H 4 O (from the ring opening of ethylene oxide) is linked to each other and together in one structural unit has a good dyeing effect (evaluated in terms of dyeing depth), so structural unit C is selected to achieve this, and C in structural unit C 2 H 4 The dyeing effect is optimal when the O unit accounts for 0.5-0.8;
from the structural distinction analysis, whether the structural unit A or the structural unit B is a crystalline unit, the polyether structural unit C containing the lateral group is a random copolymerization chain segment containing the lateral group, and the structural regularity is destroyed to be in an amorphous state. Thus, it is speculated that the dye modification is produced while being related to the aggregated form of the polymer chains and the density of ether linkages in such aggregated form, when CH 3 CH 2 If CHO is too small, amorphous regions are not obtained efficiently, and CH 3 CH 2 If CHO is too much, the number of ether bonds in the amorphous region formed is too small, and the dyeability of the dye is also reduced;
the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is less than or equal to 31.
As a preferable technical scheme:
the ratio of the mol ratio of the structural unit B to the mol ratio of the structural unit C of the acid dye-dyeable bio-based polyurethane resin is not less than 9, otherwise, the structural unit C occupies a large proportion, so that the crystallization of polyurethane is seriously damaged, the mechanical property of the product is seriously reduced, and the polyurethane resin can only show better dyeing depth and physical property balance when the mol ratio of the structural unit B to the structural unit C is 9-19.
An acid dye-dyeable bio-based polyurethane resin as described above, n A :(n B +n C ) =1-2:1, where n A Is the number of moles of structural unit A, n B Is the number of moles of structural unit B, n C The number of moles of structural unit C; the ratio of the number of moles of structural unit a to the total number of moles of structural unit B to structural unit C specifies the ratio of polyester to polyether in the soft segment structure; the polyether polyurethane has excellent hydrolysis resistanceThe isocyanate and rebound resilience are good, but the polyether polyurethane has the problems of low strength, low hardness and poor thermal oxidation performance; polyester polyurethane has excellent thermal oxidation resistance, high strength and hardness, but relatively poor rebound resilience and hydrolysis resistance; to complement the advantages and disadvantages of polyethers and polyesters, polyethers and polyesters can be used together to prepare polyurethanes and form polyether-polyester polyurethanes; the proportion of polyester to polyether structural units in polyurethane is variable according to the purpose of use of the polyurethane; the invention considers the polyether polyester type and the chain extender type, and limits the ratio of the mole number of the structural unit A to the total mole number of the structural unit B and the structural unit C to 1-2; when the ratio of the mole number of the structural unit A to the total mole number of the structural unit B and the structural unit C is more than 2, the hydrolysis resistance of the product cannot meet the requirements of certain specific applications, such as the test requirement of 70 ℃ for 840h under 95% humidity in the furniture industry; when the ratio of the mole number of the structural unit A to the total mole number of the structural unit B and the structural unit C is less than 1, the polyether units in the polyurethane are more, so that the heat resistance of the product cannot pass the requirements of certain specific applications, such as the test requirements of 105 ℃ for 500h in the automobile industry; when the ratio of the number of moles of the structural unit A to the total number of moles of the structural unit B and the structural unit C is 1 to 2, both are achieved.
An acid dye-dyeable bio-based polyurethane resin as described above, the chain extender corresponding structural unit D comprising:
structural unit D1:derived from tertiary amine dihydroxy chain extenders;
structural unit D2: -R 4 -，R 4 The nitrogen is not contained in the polyurethane, and is derived from a combination of a diamine chain extender and a dihydroxy chain extender, or from a combination of a hydroxylamine chain extender and a dihydroxy chain extender;
the structural unit D1 is connected into the molecular chain of the polyurethane resin through a carbamate group; the structural unit D2 is partially connected into the molecular chain of the polyurethane resin through a ureido group, and is partially connected into the molecular chain of the polyurethane resin through a carbamate group;
the ratio of the number of moles of the urethane groups for linking the structural unit D1 to the total number of moles of the urethane groups and ureido groups for linking the structural unit D is 0.05 to 0.15;
when the polyurethane is dyed, dye molecules are firstly dissociated in the polyurethane, and if the dye molecules are not anchored, the color fastness related test of the product is poor, such as dry and wet wiping, alcohol wiping and the like; according to the invention, the tertiary amine group is introduced into the polyurethane hard segment, so that the acidic group on the acidic dye can react with the tertiary amine group with basicity to form the quaternary ammonium salt, and the chemical reaction fixes dye molecules and ensures that the dye molecules are not easy to migrate, thereby improving the dyeing depth and greatly improving the color fastness; however, the prior art does not use such techniques to improve the color fastness, because the introduction of a small amount of tertiary amine groups causes serious degradation of the properties of the polyurethane resin; the invention defines that the ratio of the mole number of the carbamate groups used for connecting the structural unit D1 to the total mole number of the carbamate groups and the ureido groups used for connecting the structural unit D is 0.05-0.15, and aims to define the ratio of the tertiary amine dihydroxy chain extender in the total chain extender, and the effect of introducing the tertiary amine dihydroxy chain extender is not reflected when the ratio is smaller than 0.05; when the ratio is more than 0.15, the chain extender containing the side group can reduce the number of hydrogen bonds of the hard segment of the polyurethane, thereby greatly damaging the strength of the polyurethane and even losing the use value of the polyurethane; at a ratio of more than 0.15, it is not sufficient to compensate for the above-mentioned defects even by introducing urea groups.
An acid dye-dyeable bio-based polyurethane resin as described above, wherein the molar ratio of the urethane groups for linking the structural unit D to the ureido groups for linking the structural unit D is 3 to 9; as described above, the tertiary amine dihydroxy chain extender can obviously destroy the hydrogen bond action of polyurethane, the invention improves the hydrogen bond quantity of polyurethane by introducing ureido groups, thereby compensating the strength loss brought by tertiary amine dihydroxy chain extender, limiting the molar ratio of the carbamate group used for connecting the structural unit D to the ureido group used for connecting the structural unit D to be 3-9, and when the ratio is more than 9, the content of ureido is too small to embody the action of introducing ureido; when the ratio is less than 3, too much urea group content can cause the polyurethane to be whitened seriously under the action of stress, and the elongation is too low, so that the polyurethane is easy to break and whiten in actual use, and the product loses application value.
The structural unit E corresponding to the end capping agent is positioned at the end part of the molecular chain of the polyurethane resin, and is derived from methanol, ethanol or di-n-butylamine, and is connected into the molecular chain of the polyurethane resin through a carbamate group or a ureido group.
An acid dye-dyeable bio-based polyurethane resin as described above, wherein in the molecular chain of the polyurethane resin, the total mole number of urethane groups and urea groups=2n A +2n B +2n C +2n D +n E Wherein n is A Is the number of moles of structural unit A, n B Is the number of moles of structural unit B, n C Is the number of moles of structural unit C, n D Is the number of moles of structural unit D, n E The number of moles of the structural unit E; the carbamic acid ester group is derived from the reaction of the terminal hydroxyl groups of the polymer glycol, the chain extender and the end capping agent and the isocyanate NCO terminal group, and the carbamic acid group is derived from the reaction of the terminal amine groups of the chain extender and the end capping agent and the isocyanate NCO terminal group;
n D :(n A +n B +n C )＝2-5:1；
n E weight of polyurethane resin/molar mass of polyurethane resin, the weight of polyurethane resin is in grams, the molar mass of polyurethane resin is 50000-150000 grams/mole, n is calculated for convenience E The weight of the polyurethane resin is regarded as the sum of the weights of the diol, the chain extender and the diisocyanate.
An acid dye-dyeable biobased polyurethane resin as described above, wherein the isocyanate is biobased diphenylmethane diisocyanate (MDI), the use of MDI provides superior strength and solvent resistance to the biobased dyed polyurethane compared to other diisocyanates, and the effective biobased content of the biobased diphenylmethane diisocyanate is 62%.
The acid dye-dyeable bio-based polyurethane resin has a tensile load of more than or equal to 62MPa and hydrolysis resistance of more than 78%; the light fastness grade number of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 4-5, and the rubbing color fastness grade number is 4-5; the bio-based content of the bio-based polyurethane resin is more than 60 weight percent.
Advantageous effects
Compared with the prior art, the bio-based content of the polyurethane resin can reach more than 60 weight percent, and meanwhile, the dyeing performance (dyeing depth and dyeing fastness) is superior to the prior art, and other performances are higher than or approximate to the prior art.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The test methods for each performance index in each of the following examples and comparative examples are as follows:
(1) Tensile load: preparing the prepared bio-based polyurethane resin into a sample film according to a method specified by QB/T4197-2011 polyurethane resin for synthetic leather standard, testing the tensile load performance of the sample film, and adopting a cmT6104 type tension machine of Shenzhen Sansi company;
(2) Hydrolysis resistance: preparing a sample film from the prepared bio-based polyurethane resin according to a method specified by QB/T4197-2011 polyurethane resin for synthetic leather, deliquescing the sample film to be tested for 840 hours under the condition that the temperature is 70 ℃ and the relative humidity is 95%, testing the tensile load performance of the sample film according to QB/T4197-2011 polyurethane resin for synthetic leather, and multiplying the ratio of the deliquesced tensile load to the deliquesced tensile load by 100% to obtain the hydrolysis resistance index of the bio-based polyurethane resin;
(3) Number of light fastness stages: determining the light fastness level of bio-based microfiber base fabrics prepared from different bio-based polyurethane resins according to GB/T16991-2008 textile color fastness test high temperature artificial light fastness and ageing resistance xenon arc;
(4) L value: the L value of the bio-based microfiber base cloth prepared from different bio-based polyurethane resins is tested by using a CM-700D type spectrocolorimeter of KONIC MINOLTA company, wherein the L value is a deep and shallow value, and the smaller the value is, the deeper the L value is;
(5) Number of crocking fastness classes: the method comprises the steps that a friction color fastness experiment is carried out on bio-based microfiber base cloth prepared from different bio-based polyurethane resins according to a method in GB/T3920-2008 "friction color fastness of textile color fastness experiment", and a staining grade is carried out according to GB/T251-2008 "grey sample card for staining evaluation of textile color fastness experiment";
The sample preparation method of the bio-based microfiber base cloth of (3) - (5) comprises the following steps:
firstly, non-woven fabrics (non-woven fabrics C8SW0560-GG145 of Shanghai Huafeng microfiber science and technology Co., ltd.) are put into polyurethane impregnating solution for impregnation, so as to obtain non-woven fabrics with the liquid carrying rate of 120%, and the non-woven fabrics are subjected to solidification, water washing and toluene decrement to obtain wet base fabrics; then drying the wet base cloth on a crawler-type drying line at 140 ℃ for 30 minutes; finally, dyeing the dried bio-based microfiber base cloth to obtain a bio-based microfiber base cloth sample;
the polyurethane impregnating solution consists of 100 parts by weight of bio-based polyurethane resin, 50 parts by weight of N, N-dimethylformamide and 0.8 part by weight of release agent (polyether modified silicone oil type release agent ADDITIVE No.10 of Shanghai daily high polymer materials Co., ltd.);
the dyeing steps are as follows:
1) Preparing a dyeing base solution;
adding a leveling agent (PL Conc of Shanghai elegance) and a penetrating agent (RT-806 of Qu Ruitai chemical industry Co., ltd.) into water for dissolution to prepare a dyeing base solution, wherein the concentration of the leveling agent is 2wt% and the concentration of the penetrating agent is 0.1wt%;
2) Preparing a bio-based microfiber base fabric, yellow dye (HD-3R of Shanghai Xingkang chemical Co., ltd.), red dye (ASP-G of Hangzhou tower Western Co., ltd.), black dye (D-PA of Yuzhen chemical Co., ltd.) and dyeing base solution;
The mass ratio of the bio-based microfiber base cloth to the yellow dye to the red dye to the black dye to the dyeing base liquid is 100:2.15:0.83:2.7:600;
3) Dispersing yellow dye, red dye and black dye in the dyeing base solution to obtain a dye solution;
4) Immersing the bio-based microfiber base cloth in a dye solution, heating from normal temperature, heating to 70 ℃ at a speed of 0.7 ℃/min, and preserving heat for 10min; then heating to 98 ℃ at a speed of 1 ℃/min, and preserving heat for 60min; then cooling to 60 ℃ according to the cooling speed of cooling 1.5 ℃/min; and then the dye liquor is changed into water, and the base cloth is cleaned and dried at the temperature of 60 ℃ to finish dyeing.
Example 1
A preparation method of acid dye-dyeable bio-based polyurethane resin comprises the following steps:
(1) Preparing raw materials;
diol a: polyethylene glycol tetradecanoate glycol of molecular weight 2000;
diol B: polytrimethylene ether glycol of molecular weight 2000;
diol C: polypropylene oxide ethylene oxide random copolyether glycol of molecular weight 2000, wherein C 2 H 4 The molar ratio of O structural units is 0.5 (i.e. C incorporated into the copolyethers 2 H 4 O structural unit occupies C 2 H 4 O and CH 3 CH 2 CHO building block sum ratio);
chain extender D1: n-methyldiethanolamine;
chain extender D2: a mixture of ethylene glycol and ethanolamine in a molar ratio of 1:1;
End capping agent: methanol;
isocyanate: bio-based diphenylmethane diisocyanate, a company of kesichua (china);
solvent: dimethylformamide;
the mole number of the diol A is 22.5mol; the mole number of the diol B is 14mol; the mole number of the diol C is 1 mole; the mole number of the chain extender D1 is 6.5625mol; the mole number of the chain extender D2 is 124.6875mol; the molar number of isocyanate is 168.75mol; the mole number of the end-capping agent is 1.26mol; the weight of the solvent was 376913.4g;
(2) Dividing the chain extender D1 into two parts by weight, and marking the two parts as a first part of chain extender D1 and a second part of chain extender D1; dividing the solvent into three parts by weight, namely a first part of solvent, a second part of solvent and a third part of solvent, wherein the weight ratio of the first part of solvent to the second part of solvent to the third part of solvent is 2:3:5; dividing isocyanate into two parts by weight, namely first isocyanate and second isocyanate, wherein the ratio of the mole number of the first isocyanate to the total mole number of the dihydric alcohol A, the dihydric alcohol B, the dihydric alcohol C and the first chain extender D1 is 0.75:1, and the rest isocyanate is the second isocyanate;
(3) Uniformly mixing the dihydric alcohol A, the dihydric alcohol B, the dihydric alcohol C, the first part of chain extender D1 and the first part of solvent at the temperature of 50 ℃;
(4) Adding a first part of isocyanate into the system in the step (3), heating to 69 ℃, and prepolymerizing for 1.4 hours;
(5) Adding a second part of solvent, a second part of chain extender D1 and a chain extender D2 into the system in the step (4), and stirring for 26 minutes;
(6) Adding a second part of isocyanate into the system in the step (5), reacting for 6 hours at the temperature of 65 ℃, and adding a third part of solvent and a blocking agent to prepare the bio-based polyurethane resin.
The molecular chain of the finally prepared acid dye-dyeable bio-based polyurethane resin comprises a soft segment formed by long-chain dihydric alcohol and a hard segment formed by isocyanate, a chain extender and a blocking agent;
the structural units corresponding to the long-chain diol comprise a structural unit A (derived from diol A in raw materials), a structural unit B (derived from diol B in raw materials) and a structural unit C (derived from diol C in raw materials); the structural unit A, the structural unit B and the structural unit C are connected into the molecular chain of the polyurethane resin through carbamate groups; the molar ratio of the structural unit B to the structural unit C is 14;
the structural unit corresponding to the isocyanate is derived from the isocyanate in the raw material;
the corresponding structural unit D of the chain extender comprises a structural unit D1 (derived from the chain extender D1 in the raw material) and a structural unit D2 (derived from the chain extender D2 in the raw material); the structural unit D1 is connected into the molecular chain of the polyurethane resin through a carbamate group; the structural unit D2 is partially connected into the molecular chain of the polyurethane resin through a ureido group, and is partially connected into the molecular chain of the polyurethane resin through a carbamate group; the ratio of the number of moles of urethane groups for linking structural unit D1 to the total number of moles of urethane groups and ureido groups for linking structural unit D was 0.05; the molar ratio of urethane groups for the attachment of structural unit D to ureido groups for the attachment of structural unit D was 3.21;
The structural unit E (derived from the end capping agent in the raw material) corresponding to the end capping agent is positioned at the end of the molecular chain of the polyurethane resin and is connected into the molecular chain of the polyurethane resin through a carbamate group or an ureido group;
total mole number of urethane groups and ureido groups in molecular chain of polyurethane resin=2n A +2n B +2n C +2n D +n E Wherein n is A Is the number of moles of structural unit A, n B Is the number of moles of structural unit B, n C Is the number of moles of structural unit C, n D Is the number of moles of structural unit D, n E The number of moles of the structural unit E; n is n D :(n A +n B +n C )＝3.5:1；n E Weight of polyurethane resin per molar mass of polyurethane resin, the weight of polyurethane resin being in grams, molar mass of polyurethane resin being 100000 grams per mole; n is n A :(n B +n C )＝1.5:1。
The finally prepared acid dye-dyeable bio-based polyurethane resin has a bio-based content of 78.9wt%, a tensile load of 70MPa and hydrolysis resistance of 85%; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 29.6, the number of light fastness classes is 4.5, and the number of rubbing color fastness classes is 4.5.
Comparative example 1
A process for preparing a polyurethane resin, which is substantially the same as in example 1, except that diol C is a mixture of a polypropylene oxide ether diol of molecular weight 2000 and a polyethylene oxide ether diol of molecular weight 2000 in a molar ratio of 1:1, the total molar amount of the mixture being the same as diol C in example 1.
The biobased content of the finally prepared polyurethane resin is 78.9wt%, the tensile load is 70MPa, and the hydrolysis resistance is 85%; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 34, the light fastness grade number is 4.5, and the rubbing color fastness grade number is 4.5.
As can be seen by comparing example 1 with comparative example 1, the L value of comparative example 1 is higher than that of example 1, since comparative example 1 does not form C 2 H 4 O and CH 3 CH 2 The random copolymerization structure formed by CHO unit structure has the advantages that the structural regularity of polyethylene oxide ether glycol is not destroyed, the polyethylene oxide ether glycol which is easy to crystallize is difficult to color, but the amorphous area formed by simply introducing the polypropylene oxide ether glycol and the ether bond density are insufficient, so that the reduction of dyeing depth is caused, namely the L value is improved.
Comparative example 2
A process for preparing a polyurethane resin, substantially as described in example 1, except that C in diol C 2 H 4 The molar ratio of the O structural unit is 0.3.
The biobased content of the finally prepared polyurethane resin is 78.9wt%, the tensile load is 68MPa, and the hydrolysis resistance is 85%; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 35, the light fastness grade number is 4.5, and the rubbing color fastness grade number is 4.5.
As can be seen by comparing example 1 with comparative example 2, comparative example 2 has a higher L value than example 1 due to C in diol C in comparative example 2 2 H 4 Too few O structures, CH 3 CH 2 CHO is too much, resulting in too few ether linkages in the amorphous region, and the intermolecular forces of the amorphous region molecular segments and dye are reduced, resulting in a reduction in the dyeing depth.
Comparative example 3
PolyurethaneThe process for producing an ester resin was substantially the same as in example 1, except that C in diol C was only 2 H 4 The molar ratio of the O structural unit is 0.9.
The biobased content of the finally prepared polyurethane resin is 78.9wt%, the tensile load is 72MPa, and the hydrolysis resistance is 83%; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 36, the light fastness grade is 4.5, and the rubbing color fastness grade is 4.
As can be seen from comparing example 1 with comparative example 3, comparative example 3 has a higher L value than example 1 due to C in diol C in comparative example 3 2 H 4 Too much O structure, and thus an effective amorphous region cannot be obtained, there is still a problem in that it is difficult for the dye to enter the crystalline region, thereby causing a decrease in dyeing depth.
Example 2
A process for producing a polyurethane resin was substantially the same as in example 1, except that the number of moles of the chain extender D1 was 2.625mol and the number of moles of the chain extender D2 was 128.625mol.
The biobased content of the finally prepared polyurethane resin is 78.9wt%, the tensile load is 71MPa, and the hydrolysis resistance is 85%; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 31, the light fastness grade number is 4.5, and the rubbing color fastness grade number is 3.5.
As can be seen by comparing example 1 with example 2, example 2 has a higher L value than example 1 and a lower number of crocking fastness levels than example 1, since example 2 has too few D1 units to react with the dye, and thus too few groups do not act as D1.
Example 3
A process for producing a polyurethane resin was substantially the same as in example 1, except that the number of moles of the chain extender D1 was 26.25mol and the number of moles of the chain extender D2 was 105mol.
The biobased content of the finally prepared polyurethane resin is 78.9wt%, the tensile load is 56MPa, and the hydrolysis resistance is 88%; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 30.4, the light fastness grade is 4.5, and the rubbing color fastness grade is 4.
As can be seen by comparing example 1 with example 3, example 3 has a significantly lower tensile load than example 1, because of the much more D1 units in example 3, the strength drops too much.
Example 4
A process for preparing a polyurethane resin is substantially the same as in example 1, except that the chain extender D1 is ethanolamine.
The biobased content of the finally prepared polyurethane resin is 78.9wt%, the tensile load is 82MPa, and the hydrolysis resistance is 83%; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 31, the light fastness grade number is 4.5, and the rubbing color fastness grade number is 3.5.
As can be seen from a comparison of example 1 with example 4, both the L value and the crocking fastness of example 4 are poor, since example 4 does not have the anchoring group tertiary amine group of the dye, and thus does not damage the strength of the resin, the mechanical properties are improved, and the crocking fastness is lowered.
Example 5
A polyurethane resin was prepared in substantially the same manner as in example 1 except that the chain extender D2 was ethanolamine, and example 5 was equivalent to using an equimolar amount of ethanolamine instead of the mixture of ethylene glycol and ethanolamine in a molar ratio of 1:1 in example 1.
The biobased content of the finally prepared polyurethane resin is 78.9wt%, the tensile load is 65MPa, the polyurethane resin is brittle fracture, and stress whitening exists; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 29.4, the number of light fastness levels is 4.5, and the number of rubbing color fastness levels is 4.5.
Comparing example 1 with example 5, it can be seen that the molar ratio of urethane groups used to attach structural unit D to urea groups used to attach structural unit D decreases, and that too many urea groups result in increased brittleness of the polyurethane, which is prone to stress whitening.
Example 6
A preparation method of acid dye-dyeable bio-based polyurethane resin comprises the following steps:
(1) Preparing raw materials;
diol a: polysebacic acid 1, 3-propylene glycol ester diol with molecular weight of 3000;
diol B: polytrimethylene ether glycol of molecular weight 1000;
diol C: polypropylene oxide ethylene oxide random copolyether glycol of molecular weight 1500, wherein C 2 H 4 The molar ratio of the O structural unit is 0.8;
chain extender D1: n, N-dihydroxyisopropyl aniline;
chain extender D2: a mixture of ethylene glycol and 4,4' -diphenyl methane diamine in a molar ratio of 4:1;
end capping agent: ethanol;
isocyanate: bio-based diphenylmethane diisocyanate, a company of kesichua (china);
solvent: dimethylacetamide;
the mole number of the diol A is 18mol; the mole number of the diol B is 9mol; the mole number of the diol C is 1 mole; the mole number of the chain extender D1 is 5.6mol; the mole number of the chain extender D2 is 50.4mol; the molar number of isocyanate is 84mol; the mole number of the end-capping agent is 1.82mol; the weight of the solvent was 273510.9g;
(2) Dividing the chain extender D1 into two parts by weight, and marking the two parts as a first part of chain extender D1 and a second part of chain extender D1; dividing the solvent into three parts by weight, namely a first part of solvent, a second part of solvent and a third part of solvent, wherein the weight ratio of the first part of solvent to the second part of solvent to the third part of solvent is 2:3:5; dividing isocyanate into two parts by weight, namely first isocyanate and second isocyanate, wherein the ratio of the mole number of the first isocyanate to the total mole number of the dihydric alcohol A, the dihydric alcohol B, the dihydric alcohol C and the first chain extender D1 is 0.75:1, and the rest isocyanate is the second isocyanate;
(3) Uniformly mixing the dihydric alcohol A, the dihydric alcohol B, the dihydric alcohol C, the first part of chain extender D1 and the first part of solvent at the temperature of 52 ℃;
(4) Adding a first part of isocyanate into the system in the step (3), heating to 66 ℃, and prepolymerizing for 1.3 hours;
(5) Adding a second part of solvent, a second part of chain extender D1 and a second part of chain extender D2 into the system in the step (4), and stirring for 30 minutes;
(6) Adding a second part of isocyanate into the system in the step (5), reacting for 5.5 hours at the temperature of 70 ℃, and adding a third part of solvent and a blocking agent to prepare the bio-based polyurethane resin.
The molecular chain of the finally prepared acid dye-dyeable bio-based polyurethane resin comprises a soft segment formed by long-chain dihydric alcohol and a hard segment formed by isocyanate, a chain extender and a blocking agent;
the structural units corresponding to the long-chain diol comprise a structural unit A (derived from diol A in raw materials), a structural unit B (derived from diol B in raw materials) and a structural unit C (derived from diol C in raw materials); the structural unit A, the structural unit B and the structural unit C are connected into the molecular chain of the polyurethane resin through carbamate groups; the molar ratio of the structural unit B to the structural unit C is 9;
the structural unit corresponding to the isocyanate is derived from the isocyanate in the raw material;
the corresponding structural unit D of the chain extender comprises a structural unit D1 (derived from the chain extender D1 in the raw material) and a structural unit D2 (derived from the chain extender D2 in the raw material); the structural unit D1 is connected into the molecular chain of the polyurethane resin through a carbamate group; the structural unit D2 is partially connected into the molecular chain of the polyurethane resin through a ureido group, and is partially connected into the molecular chain of the polyurethane resin through a carbamate group; the ratio of the number of moles of urethane groups for linking structural unit D1 to the total number of moles of urethane groups and ureido groups for linking structural unit D was 0.1; the molar ratio of urethane groups for the attachment of structural unit D to ureido groups for the attachment of structural unit D was 4.56;
The structural unit E (derived from the end capping agent in the raw material) corresponding to the end capping agent is positioned at the end of the molecular chain of the polyurethane resin and is connected into the molecular chain of the polyurethane resin through a carbamate group or an ureido group;
total mole number of urethane groups and ureido groups in molecular chain of polyurethane resin=2n A +2n B +2n C +2n D +n E Wherein n is A Is the number of moles of structural unit A, n B Is the number of moles of structural unit B, n C Is the number of moles of structural unit C, n D Is the number of moles of structural unit D, n E The number of moles of the structural unit E; n is n D :(n A +n B +n C )＝2:1；n E Weight of polyurethane resin per molar mass of polyurethane resin, the weight of polyurethane resin being in grams, molar mass of polyurethane resin being 50000 grams per mole; n is n A :(n B +n C )＝1.8:1。
The finally prepared acid dye-dyeable bio-based polyurethane resin has a bio-based content of 82.5wt%, a tensile load of 63MPa and a hydrolysis resistance of 81%; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 27.7, the light fastness grade number is 4.5, and the rubbing color fastness grade number is 4.
Example 7
A preparation method of acid dye-dyeable bio-based polyurethane resin comprises the following steps:
(1) Preparing raw materials;
diol a: a polyethylene glycol dioctadecyl dibasic acid glycol with molecular weight of 1000;
Diol B: polytrimethylene ether glycol of molecular weight 3000;
diol C: polypropylene oxide ethylene oxide random copolyether glycol of molecular weight 1000, wherein C 2 H 4 The molar ratio of the O structural unit is 0.6;
chain extender D1: n, N-dihydroxyisopropyl p-toluidine;
chain extender D2: a mixture of butanediol and 4,4' -diphenyl methane diamine in a molar ratio of 7:1;
end capping agent: di-n-butylamine;
isocyanate: bio-based diphenylmethane diisocyanate, a company of kesichua (china);
solvent: dimethylformamide;
the mole number of the diol A is 20mol; the mole number of the diol B is 19mol; the mole number of the diol C is 1 mole; the mole number of the chain extender D1 is 18mol; the mole number of the chain extender D2 is 102mol; the mole number of the isocyanate is 160mol; the mole number of the end-capping agent is 1.89mol; the weight of the solvent was 397729.8g;
(2) Dividing the chain extender D1 into two parts by weight, and marking the two parts as a first part of chain extender D1 and a second part of chain extender D1; dividing the solvent into three parts by weight, namely a first part of solvent, a second part of solvent and a third part of solvent, wherein the weight ratio of the first part of solvent to the second part of solvent to the third part of solvent is 2:3:5; dividing isocyanate into two parts by weight, namely first isocyanate and second isocyanate, wherein the ratio of the mole number of the first isocyanate to the total mole number of the dihydric alcohol A, the dihydric alcohol B, the dihydric alcohol C and the first chain extender D1 is 0.75:1, and the rest isocyanate is the second isocyanate;
(3) Uniformly mixing the dihydric alcohol A, the dihydric alcohol B, the dihydric alcohol C, the first part of chain extender D1 and the first part of solvent at the temperature of 60 ℃;
(4) Adding a first part of isocyanate into the system in the step (3), heating to 70 ℃, and prepolymerizing for 1.2 hours;
(5) Adding a second part of solvent, a second part of chain extender D1 and a second part of chain extender D2 into the system in the step (4), and stirring for 25 minutes;
(6) Adding a second part of isocyanate into the system in the step (5), reacting for 5 hours at the temperature of 75 ℃, and adding a third part of solvent and a blocking agent to prepare the bio-based polyurethane resin.
The molecular chain of the finally prepared acid dye-dyeable bio-based polyurethane resin comprises a soft segment formed by long-chain dihydric alcohol and a hard segment formed by isocyanate, a chain extender and a blocking agent;
the structural units corresponding to the long-chain diol comprise a structural unit A (derived from diol A in raw materials), a structural unit B (derived from diol B in raw materials) and a structural unit C (derived from diol C in raw materials); the structural unit A, the structural unit B and the structural unit C are connected into the molecular chain of the polyurethane resin through carbamate groups; the molar ratio of the structural unit B to the structural unit C is 19;
the structural unit corresponding to the isocyanate is derived from the isocyanate in the raw material;
The corresponding structural unit D of the chain extender comprises a structural unit D1 (derived from the chain extender D1 in the raw material) and a structural unit D2 (derived from the chain extender D2 in the raw material); the structural unit D1 is connected into the molecular chain of the polyurethane resin through a carbamate group; the structural unit D2 is partially connected into the molecular chain of the polyurethane resin through a ureido group, and is partially connected into the molecular chain of the polyurethane resin through a carbamate group; the ratio of the number of moles of urethane groups for linking structural unit D1 to the total number of moles of urethane groups and ureido groups for linking structural unit D was 0.15; the molar ratio of urethane groups for the attachment of structural unit D to ureido groups for the attachment of structural unit D was 8.41;
the structural unit E (derived from the end capping agent in the raw material) corresponding to the end capping agent is positioned at the end of the molecular chain of the polyurethane resin and is connected into the molecular chain of the polyurethane resin through a carbamate group or an ureido group;
total mole number of urethane groups and ureido groups in molecular chain of polyurethane resin=2n A +2n B +2n C +2n D +n E Wherein n is A Is the number of moles of structural unit A, n B Is the number of moles of structural unit B, n C Is the number of moles of structural unit C, n D Is the number of moles of structural unit D, n E The number of moles of the structural unit E; n is n D :(n A +n B +n C )＝3:1；n E Weight of polyurethane resin per molar mass of polyurethane resin, the weight of polyurethane resin in grams, molar mass of polyurethane resin 70000 grams per mole; n is n A :(n B +n C )＝1:1。
The finally prepared acid dye-dyeable bio-based polyurethane resin has a bio-based content of 76.0wt%, a tensile load of 67MPa and hydrolysis resistance of 93%; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 27.0, the light fastness grade number is 4, and the rubbing color fastness grade number is 4.
Example 8
A preparation method of acid dye-dyeable bio-based polyurethane resin comprises the following steps:
(1) Preparing raw materials;
diol a: 1, 3-propanediol of polydodecanedioic acid with molecular weight of 1500;
diol B: polytrimethylene ether glycol of molecular weight 1500;
diol C: polypropylene oxide ethylene oxide random copolyether glycol of molecular weight 500, wherein C 2 H 4 The molar ratio of the O structural unit is 0.7;
chain extender D1: n, N-dihydroxyethyl aniline;
chain extender D2: a mixture of butanediol and ethanolamine in a molar ratio of 4:5;
end capping agent: methanol;
isocyanate: bio-based diphenylmethane diisocyanate, a company of kesichua (china);
Solvent: dimethylformamide;
the mole number of the diol A is 14.3mol; the mole number of the diol B is 12mol; the mole number of the diol C is 1 mole; the mole number of the chain extender D1 is 13.65mol; the mole number of the chain extender D2 is 122.85mol; the molar number of isocyanate is 163.8mol; the mole number of the end-capping agent is 1.16mol; the weight of the solvent was 277353.6g;
(2) Dividing the chain extender D1 into two parts by weight, and marking the two parts as a first part of chain extender D1 and a second part of chain extender D1; dividing the solvent into three parts by weight, namely a first part of solvent, a second part of solvent and a third part of solvent, wherein the weight ratio of the first part of solvent to the second part of solvent to the third part of solvent is 2:3:5; dividing isocyanate into two parts by weight, namely first isocyanate and second isocyanate, wherein the ratio of the mole number of the first isocyanate to the total mole number of the dihydric alcohol A, the dihydric alcohol B, the dihydric alcohol C and the first chain extender D1 is 0.75:1, and the rest isocyanate is the second isocyanate;
(3) Uniformly mixing the dihydric alcohol A, the dihydric alcohol B, the dihydric alcohol C, the first part of chain extender D1 and the first part of solvent at the temperature of 58 ℃;
(4) Adding a first part of isocyanate into the system in the step (3), heating to 75 ℃, and prepolymerizing for 1 hour;
(5) Adding a second part of solvent, a second part of chain extender D1 and a chain extender D2 into the system in the step (4), and stirring for 28 minutes;
(6) Adding a second part of isocyanate into the system in the step (5), reacting for 5.7 hours at the temperature of 72 ℃, and adding a third part of solvent and a blocking agent to prepare the bio-based polyurethane resin.
The molecular chain of the finally prepared acid dye-dyeable bio-based polyurethane resin comprises a soft segment formed by long-chain dihydric alcohol and a hard segment formed by isocyanate, a chain extender and a blocking agent;
the structural units corresponding to the long-chain diol comprise a structural unit A (derived from diol A in raw materials), a structural unit B (derived from diol B in raw materials) and a structural unit C (derived from diol C in raw materials); the structural unit A, the structural unit B and the structural unit C are connected into the molecular chain of the polyurethane resin through carbamate groups; the molar ratio of the structural unit B to the structural unit C is 12;
the structural unit corresponding to the isocyanate is derived from the isocyanate in the raw material;
the corresponding structural unit D of the chain extender comprises a structural unit D1 (derived from the chain extender D1 in the raw material) and a structural unit D2 (derived from the chain extender D2 in the raw material); the structural unit D1 is connected into the molecular chain of the polyurethane resin through a carbamate group; the structural unit D2 is partially connected into the molecular chain of the polyurethane resin through a ureido group, and is partially connected into the molecular chain of the polyurethane resin through a carbamate group; the ratio of the number of moles of urethane groups for linking structural unit D1 to the total number of moles of urethane groups and ureido groups for linking structural unit D was 0.1; the molar ratio of urethane groups for the attachment of structural unit D to ureido groups for the attachment of structural unit D is 3;
The structural unit E (derived from the end capping agent in the raw material) corresponding to the end capping agent is positioned at the end of the molecular chain of the polyurethane resin and is connected into the molecular chain of the polyurethane resin through a carbamate group or an ureido group;
total mole number of urethane groups and ureido groups in molecular chain of polyurethane resin=2n A +2n B +2n C +2n D +n E Wherein n is A Is the number of moles of structural unit A, n B Is the number of moles of structural unit B, n C Is the number of moles of structural unit C, n D Is the number of moles of structural unit D, n E The number of moles of the structural unit E; n is n D :(n A +n B +n C )＝5:1；n E Weight of polyurethane resin per molar mass of polyurethane resin, the weight of polyurethane resin in grams, molar mass of polyurethane resin 80000 grams per mole; n is n A :(n B +n C )＝1.1:1。
The finally prepared acid dye-dyeable bio-based polyurethane resin has the bio-based content of 70.1wt%, the tensile load of 76MPa and the hydrolysis resistance of 90%; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 28.1, the light fastness grade number is 5, and the rubbing color fastness grade number is 4.5.
Example 9
A preparation method of acid dye-dyeable bio-based polyurethane resin comprises the following steps:
(1) Preparing raw materials;
diol a: polyethylene hexadecyl glycol dibasic acid glycol with molecular weight 2500;
Diol B: polytrimethylene ether glycol having a molecular weight of 2500;
diol C: polypropylene oxide ethylene oxide random copolyether glycol of molecular weight 2500, wherein C 2 H 4 The molar ratio of the O structural unit is 0.55;
chain extender D1: n, N-dihydroxyethyl-p-toluidine;
chain extender D2: a mixture of ethylene glycol and 4,4' -diphenyl methane diamine in a molar ratio of 6.36:1;
end capping agent: ethanol;
isocyanate: bio-based diphenylmethane diisocyanate, a company of kesichua (china);
solvent: dimethylformamide;
the mole number of the diol A is 22.1mol; the mole number of the diol B is 16mol; the mole number of the diol C is 1 mole; the mole number of the chain extender D1 is 12.512mol; the mole number of the chain extender D2 is 143.888mol; the molar number of isocyanate is 195.5mol; the mole number of the end-capping agent is 1.34mol; the weight of the solvent was 481957.5g;
(2) Dividing the chain extender D1 into two parts by weight, and marking the two parts as a first part of chain extender D1 and a second part of chain extender D1; dividing the solvent into three parts by weight, namely a first part of solvent, a second part of solvent and a third part of solvent, wherein the weight ratio of the first part of solvent to the second part of solvent to the third part of solvent is 2:3:5; dividing isocyanate into two parts by weight, namely first isocyanate and second isocyanate, wherein the ratio of the mole number of the first isocyanate to the total mole number of the dihydric alcohol A, the dihydric alcohol B, the dihydric alcohol C and the first chain extender D1 is 0.75:1, and the rest isocyanate is the second isocyanate;
(3) Uniformly mixing the dihydric alcohol A, the dihydric alcohol B, the dihydric alcohol C, the first part of chain extender D1 and the first part of solvent at the temperature of 55 ℃;
(4) Adding a first part of isocyanate into the system in the step (3), heating to 72 ℃, and prepolymerizing for 1.1 hours;
(5) Adding a second part of solvent, a second part of chain extender D1 and a second part of chain extender D2 into the system in the step (4), and stirring for 30 minutes;
(6) Adding a second part of isocyanate into the system in the step (5), reacting for 5.6 hours at the temperature of 70 ℃, and adding a third part of solvent and a blocking agent to prepare the bio-based polyurethane resin.
The molecular chain of the finally prepared acid dye-dyeable bio-based polyurethane resin comprises a soft segment formed by long-chain dihydric alcohol and a hard segment formed by isocyanate, a chain extender and a blocking agent;
the structural units corresponding to the long-chain diol comprise a structural unit A (derived from diol A in raw materials), a structural unit B (derived from diol B in raw materials) and a structural unit C (derived from diol C in raw materials); the structural unit A, the structural unit B and the structural unit C are connected into the molecular chain of the polyurethane resin through carbamate groups; the molar ratio of the structural unit B to the structural unit C is 16;
the structural unit corresponding to the isocyanate is derived from the isocyanate in the raw material;
The corresponding structural unit D of the chain extender comprises a structural unit D1 (derived from the chain extender D1 in the raw material) and a structural unit D2 (derived from the chain extender D2 in the raw material); the structural unit D1 is connected into the molecular chain of the polyurethane resin through a carbamate group; the structural unit D2 is partially connected into the molecular chain of the polyurethane resin through a ureido group, and is partially connected into the molecular chain of the polyurethane resin through a carbamate group; the ratio of the number of moles of urethane groups for the linking structural unit D1 to the total number of moles of urethane groups and ureido groups for the linking structural unit D was 0.08; the molar ratio of urethane groups for the attachment of structural unit D to ureido groups for the attachment of structural unit D is 7;
the structural unit E (derived from the end capping agent in the raw material) corresponding to the end capping agent is positioned at the end of the molecular chain of the polyurethane resin and is connected into the molecular chain of the polyurethane resin through a carbamate group or an ureido group;
total mole number of urethane groups and ureido groups in molecular chain of polyurethane resin=2n A +2n B +2n C +2n D +n E Wherein n is A Is the number of moles of structural unit A, n B Is the number of moles of structural unit B, n C Is the number of moles of structural unit C, n D Is the number of moles of structural unit D, n E The number of moles of the structural unit E; n is n D :(n A +n B +n C )＝4:1；n E Weight of polyurethane resin per molar mass of polyurethane resin, the weight of polyurethane resin being in grams, the molar mass of polyurethane resin being 120000 grams per mole; n is n A :(n B +n C )＝1.3:1。
The finally prepared acid dye-dyeable bio-based polyurethane resin has a bio-based content of 78.2wt%, a tensile load of 68MPa and a hydrolysis resistance of 89%; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 29.5, the light fastness grade is 4.5, and the rubbing color fastness grade is 5.
Example 10
A preparation method of acid dye-dyeable bio-based polyurethane resin comprises the following steps:
(1) Preparing raw materials;
diol a: polysebacic acid 1, 3-propylene glycol ester diol with molecular weight of 2000;
diol B: polytrimethylene ether glycol having a molecular weight of 1800;
diol C: polypropylene oxide ethylene oxide random copolyether glycol with molecular weight of 3000, wherein C 2 H 4 The molar ratio of the O structural unit is 0.65;
chain extender D1: a mixture of N-methyldiethanolamine and N, N-dihydroxyethylaniline (molar ratio 1:1);
chain extender D2: a mixture of butanediol and 4,4' -diphenylmethane diamine in a molar ratio of 7.9:1;
end capping agent: di-n-butylamine;
Isocyanate: bio-based diphenylmethane diisocyanate, a company of kesichua (china);
solvent: dimethylformamide;
the mole number of the diol A is 36mol; the mole number of the diol B is 17mol; the mole number of the diol C is 1 mole; the mole number of the chain extender D1 is 26.73mol; the mole number of the chain extender D2 is 216.27mol; the molar number of isocyanate is 297mol; the mole number of the end-capping agent is 1.37mol; the weight of the solvent was 618445.5g;
(2) Dividing the chain extender D1 into two parts by weight, and marking the two parts as a first part of chain extender D1 and a second part of chain extender D1; dividing the solvent into three parts by weight, namely a first part of solvent, a second part of solvent and a third part of solvent, wherein the weight ratio of the first part of solvent to the second part of solvent to the third part of solvent is 2:3:5; dividing isocyanate into two parts by weight, namely first isocyanate and second isocyanate, wherein the ratio of the mole number of the first isocyanate to the total mole number of the dihydric alcohol A, the dihydric alcohol B, the dihydric alcohol C and the first chain extender D1 is 0.75:1, and the rest isocyanate is the second isocyanate;
(3) Uniformly mixing the dihydric alcohol A, the dihydric alcohol B, the dihydric alcohol C, the first part of chain extender D1 and the first part of solvent at the temperature of 53 ℃;
(4) Adding a first part of isocyanate into the system in the step (3), heating to 65 ℃, and prepolymerizing for 1.5 hours;
(5) Adding a second part of solvent, a second part of chain extender D1 and a second part of chain extender D2 into the system in the step (4), and stirring for 25 minutes;
(6) Adding a second part of isocyanate into the system in the step (5), reacting for 5.9 hours at the temperature of 68 ℃, and adding a third part of solvent and a blocking agent to prepare the bio-based polyurethane resin.
The molecular chain of the finally prepared acid dye-dyeable bio-based polyurethane resin comprises a soft segment formed by long-chain dihydric alcohol and a hard segment formed by isocyanate, a chain extender and a blocking agent;
the structural units corresponding to the long-chain diol comprise a structural unit A (derived from diol A in raw materials), a structural unit B (derived from diol B in raw materials) and a structural unit C (derived from diol C in raw materials); the structural unit A, the structural unit B and the structural unit C are connected into the molecular chain of the polyurethane resin through carbamate groups; the molar ratio of the structural unit B to the structural unit C is 17;
the structural unit corresponding to the isocyanate is derived from the isocyanate in the raw material;
the corresponding structural unit D of the chain extender comprises a structural unit D1 (derived from the chain extender D1 in the raw material) and a structural unit D2 (derived from the chain extender D2 in the raw material); the structural unit D1 is connected into the molecular chain of the polyurethane resin through a carbamate group; the structural unit D2 is partially connected into the molecular chain of the polyurethane resin through a ureido group, and is partially connected into the molecular chain of the polyurethane resin through a carbamate group; the ratio of the number of moles of urethane groups for linking structural unit D1 to the total number of moles of urethane groups and ureido groups for linking structural unit D was 0.11; the molar ratio of urethane groups for the attachment of structural unit D to ureido groups for the attachment of structural unit D is 9;
The structural unit E (derived from the end capping agent in the raw material) corresponding to the end capping agent is positioned at the end of the molecular chain of the polyurethane resin and is connected into the molecular chain of the polyurethane resin through a carbamate group or an ureido group;
total mole number of urethane groups and ureido groups in molecular chain of polyurethane resin=2n A +2n B +2n C +2n D +n E Wherein n is A Is the number of moles of structural unit A, n B Is the number of moles of structural unit B, n C Is the number of moles of structural unit C, n D Is the number of moles of structural unit D, n E The number of moles of the structural unit E; n is n D :(n A +n B +n C )＝4.5:1；n E Weight of polyurethane resin per molar mass of polyurethane resin, the weight of polyurethane resin being in grams, the molar mass of polyurethane resin being 150000 grams per mole; n is n A :(n B +n C )＝2:1。
The finally prepared acid dye-dyeable bio-based polyurethane resin has a bio-based content of 72.1wt%, a tensile load of 72MPa and hydrolysis resistance of 78%; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 28.3, the light fastness grade number is 5, and the rubbing color fastness grade number is 4.5.
Example 11
A polyurethane resin was prepared in substantially the same manner as in example 10, except that the chain extender D2 was butanediol, and example 11 was conducted by substituting an equimolar amount of butanediol for the mixture of butanediol and 4,4' -diphenylmethane diamine in the molar ratio of 7.9:1 in example 10.
The biobased content of the finally prepared polyurethane resin is 78.9wt%, the tensile load is 55MPa, and the hydrolysis resistance is 80%; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 27.6, the number of light fastness classes is 4.5, and the number of rubbing color fastness classes is 4.5.
As can be seen by comparing example 10 with example 11, the groups used to attach structural unit D are urethane groups, with only few urea groups present at the end groups, which results in a decrease in the number of hydrogen bonds in the hard segment of the polyurethane caused by the chain extender D1 containing pendant groups, and the broken intermolecular forces are not repaired, resulting in a significant decrease in the strength of the polyurethane.
Claims (7)
1. An acid dye-dyeable bio-based polyurethane resin, wherein a molecular chain comprises a soft segment formed by long-chain dihydric alcohol and a hard segment formed by isocyanate, a chain extender and a blocking agent, and the acid dye-dyeable bio-based polyurethane resin is characterized in that a structural unit corresponding to the long-chain dihydric alcohol comprises:
structural unit a:x=10-18, y=2-3, derived from bio-based polyester diol having a number average molecular weight of 1000-3000;
structural unit B:from bio-based polyether diols having a number average molecular weight of 1000 to 3000;
structural unit C:nx/(nx+ny) =0.5 to 0.8, derived from a copolyether glycol of random copolymerization of petroleum-based polypropylene oxide ethylene oxide having a number average molecular weight of 500 to 3000;
The structural unit A, the structural unit B and the structural unit C are connected into the molecular chain of the polyurethane resin through carbamate groups;
the molar ratio of the structural unit B to the structural unit C is not more than 19 and is not less than 9;
the structural unit D corresponding to the chain extender comprises:
structural unit D1:derived from tertiary amine dihydroxy chain extenders;
structural unit D2: -R 4 -，R 4 The nitrogen is not contained in the polyurethane, and is derived from a combination of a diamine chain extender and a dihydroxy chain extender, or from a combination of a hydroxylamine chain extender and a dihydroxy chain extender;
n D :(n A +n B +n C ) =2-5:1, where n A As the number of moles of the structural unit a,n B is the number of moles of structural unit B, n C Is the number of moles of structural unit C, n D The number of moles of structural unit D;
the isocyanate is bio-based diphenyl methane diisocyanate;
the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is less than or equal to 31.
2. An acid dye dyeable bio-based polyurethane resin according to claim 1, wherein n A :(n B +n C )＝1-2:1。
3. An acid dye dyeable bio-based polyurethane resin according to claim 1, wherein the structural unit D1 is incorporated into the molecular chain of the polyurethane resin by a urethane group; the structural unit D2 is partially connected into the molecular chain of the polyurethane resin through a ureido group, and is partially connected into the molecular chain of the polyurethane resin through a carbamate group;
The ratio of the number of moles of the urethane groups for the linking structural unit D1 to the total number of moles of the urethane groups and the ureido groups for the linking structural unit D is 0.05 to 0.15.
4. An acid dye dyeable bio-based polyurethane resin according to claim 3, wherein the molar ratio of urethane groups for linking structural unit D to ureido groups for linking structural unit D is 3-9.
5. An acid dye dyeable bio-based polyurethane resin according to claim 4, wherein the structural unit E corresponding to the end capping agent is located at the end of the molecular chain of the polyurethane resin and is derived from methanol, ethanol or di-n-butylamine, and is incorporated into the molecular chain of the polyurethane resin through a urethane group or a ureido group.
6. An acid dye-dyeable bio-based polyurethane tree according to claim 5A resin characterized in that the total mole number of urethane groups and urea groups in the molecular chain of the polyurethane resin=2n A +2n B +2n C +2n D +n E ，n E The number of moles of the structural unit E;
n E weight of polyurethane resin per molar mass of polyurethane resin, the weight of polyurethane resin is in grams, and the molar mass of polyurethane resin is 50000-150000 grams per mole.
7. The acid dye-dyeable bio-based polyurethane resin according to any one of claims 1 to 6, wherein the tensile load of the bio-based polyurethane resin is not less than 62MPa and the hydrolysis resistance is not less than 78%; the light fastness grade number of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 4-5, and the rubbing color fastness grade number is 4-5; the bio-based content of the bio-based polyurethane resin is more than 60 weight percent.
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| CN105693992A (en) * | 2016-03-21 | 2016-06-22 | 美瑞新材料股份有限公司 | Bio-based waterproof moisture-permeable thermoplastic polyurethane resin and preparation method thereof |
| KR101684872B1 (en) * | 2015-11-20 | 2016-12-12 | 주식회사 효성 | Polyurethane urea elastic fiber having an improved dyeability and heat set property, and method of manufacturing the same |
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| CN101326212A (en) * | 2005-12-06 | 2008-12-17 | 纳幕尔杜邦公司 | Thermoplastic polyurethanes comprising polytrimethylene ether soft segments |
| KR101684872B1 (en) * | 2015-11-20 | 2016-12-12 | 주식회사 효성 | Polyurethane urea elastic fiber having an improved dyeability and heat set property, and method of manufacturing the same |
| CN105693992A (en) * | 2016-03-21 | 2016-06-22 | 美瑞新材料股份有限公司 | Bio-based waterproof moisture-permeable thermoplastic polyurethane resin and preparation method thereof |
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