CN114940743A - Bio-based polyurethane resin dyeable by acid dye - Google Patents
Bio-based polyurethane resin dyeable by acid dye Download PDFInfo
- Publication number
- CN114940743A CN114940743A CN202210399345.3A CN202210399345A CN114940743A CN 114940743 A CN114940743 A CN 114940743A CN 202210399345 A CN202210399345 A CN 202210399345A CN 114940743 A CN114940743 A CN 114940743A
- Authority
- CN
- China
- Prior art keywords
- structural unit
- polyurethane resin
- bio
- chain extender
- chain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 195
- 239000000980 acid dye Substances 0.000 title claims abstract description 27
- 239000004970 Chain extender Substances 0.000 claims abstract description 126
- 239000012948 isocyanate Substances 0.000 claims abstract description 88
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 86
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 70
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229920001410 Microfiber Polymers 0.000 claims abstract description 31
- 239000003658 microfiber Substances 0.000 claims abstract description 31
- 239000004744 fabric Substances 0.000 claims abstract description 30
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002981 blocking agent Substances 0.000 claims abstract description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 15
- 229920000570 polyether Polymers 0.000 claims abstract description 15
- 229920000728 polyester Polymers 0.000 claims abstract description 11
- 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
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000003208 petroleum Substances 0.000 claims abstract description 6
- 150000002009 diols Chemical class 0.000 claims description 76
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 23
- 230000007062 hydrolysis Effects 0.000 claims description 20
- 238000006460 hydrolysis reaction Methods 0.000 claims description 20
- 239000000975 dye Substances 0.000 claims description 17
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 16
- HZAXFHJVJLSVMW-UHFFFAOYSA-N monoethanolamine hydrochloride Natural products NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 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 11
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid 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 33
- 230000007547 defect Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 73
- 239000002994 raw material Substances 0.000 description 55
- 229920002635 polyurethane Polymers 0.000 description 37
- 239000004814 polyurethane Substances 0.000 description 37
- 239000003795 chemical substances by application Substances 0.000 description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- 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
- 239000000203 mixture Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- -1 polytetramethylene Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 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
- 238000003756 stirring 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
- 229920000642 polymer Polymers 0.000 description 5
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical group C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 229940035437 1,3-propanediol Drugs 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
- 229920005862 polyol Polymers 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 229920000166 polytrimethylene carbonate Polymers 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
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000007788 liquid Substances 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
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000001044 red dye Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- 239000001043 yellow dye Substances 0.000 description 3
- 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000003247 decreasing effect 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
- 239000000835 fiber 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
- 230000000149 penetrating effect Effects 0.000 description 2
- 239000011846 petroleum-based material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 230000002194 synthesizing 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
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 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
- 230000032683 aging Effects 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical group CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 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
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 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
- 239000004753 textile Substances 0.000 description 1
- 230000009466 transformation Effects 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
-
- 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
-
- 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
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Abstract
The invention relates to a bio-based polyurethane resin dyeable by acid dyes, 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 units A (derived from bio-based polyester glycol), structural units B (derived from bio-based polyether glycol) and structural units C (derived from petroleum-based polypropylene oxide ethylene oxide randomly copolymerized copolyether glycol); the structural unit A, the structural unit B and the structural unit C are connected into a molecular chain of the polyurethane resin through urethane groups; the molar ratio of the structural unit B to the structural unit C is not more than 19; the bio-based polyurethane resin has a bio-based content of 60 wt% or more; 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 disclosed by the invention has the characteristics of high bio-based content and excellent dyeing, and makes up for the defects of the prior art.
Description
Technical Field
The invention belongs to the technical field of synthetic resin, and relates to a bio-based polyurethane resin dyeable by an acid dye.
Background
Polyurethane resin is an important raw material for preparing superfine fiber synthetic leather, and most of superfine fiber suede leather in the market is prepared by using polyurethane resin raw materials based on a petroleum industry chain, can generate larger pollution, and is obviously inconsistent with the requirements of low carbon and sustainable development at the present stage. The chemical raw materials for synthesizing the polyurethane resin can be divided into petroleum-based raw materials and bio-based raw materials according to different sources, and with the deep implementation of the sustainable development policy, the replacement of the traditional polyurethane synthesis path for the polyurethane resin prepared based on the bio-based raw materials becomes the most important part of the technical transformation in the future.
In general, in order to obtain a polyurethane resin prepared based on bio-based raw materials, one studies the structure of polyurethane and divides the structure of polyurethane into a soft segment composed of polymer polyol and a hard segment composed of isocyanate and a small molecule chain extender. Among the polymer polyols constituting the soft segment, a common bio-based polymer polyol is poly (1, 3-propylene glycol adipate); among the isocyanates constituting the hard segment, the usual biobased isocyanates are biobased diphenylmethane diisocyanates; among the small molecular chain extenders constituting the hard segment, a common bio-based small molecular chain extender is 1, 3-propanediol. The selectable polymer polyol from a bio-based source can be used for synthesizing full bio-based polyurethane with excellent mechanical properties, but has defects in dyeing capability, and the dyeing property is very important for polyurethane resin for microfiber suede leather, and the dyeing uniformity and depth play a critical role in the product quality of finished suede leather.
However, limited by the limited availability of bio-based materials, we still need some petroleum-based materials for modification, and the prior art still uses all petroleum-based or petroleum-based materials for synthesis when preparing polyurethane resins with excellent dyeing properties, such as easily dyeable polyurethane resin described in chinese patent application CN 105542108A. However, the scheme contains a large amount of adipic acid, polytetramethylene ether and other structures, and no bio-based sources exist, and the dyeing depth L value of the easily-dyed 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 the 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 an acid dye.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a molecular chain of the bio-based polyurethane resin dyeable by acid dyes comprises a soft segment formed by long-chain dihydric alcohol and a hard segment formed by isocyanate, a chain extender and a blocking agent, wherein the structural units corresponding to the long-chain dihydric alcohol comprise:
structural unit a:
x is 10-18, y is 2-3, and is derived from bio-based polyester diol with the number average molecular weight of 1000-3000;
structural unit B:
derived from bio-based polyether glycol having a number average molecular weight of 1000-3000;
structural unit C:
nx/(nx + ny) ═ 0.5-0.8, from petroleum-based polypropylene oxide ethylene oxide randomly copolymerized copolyether glycol having a number average molecular weight of 500-;
the structural unit A, the structural unit B and the structural unit C are connected into a molecular chain of the polyurethane resin through a carbamate group (-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 more than 19, the occupation ratio of the structural unit C is smaller, and the effect of introducing the structural unit C is not shown;
the polyurethane is a two-phase structure consisting of a soft segment and a hard segment, and the hard segment is distributed in a matrix formed by the soft segment in an aggregation state; in the dyeing process of polyurethane, dye dispersed in water enters a soft section of the polyurethane to realize the dyeing of the polyurethane, experiments show that introduction of a polyether structural unit B with relatively better hydrophilicity cannot obviously help to improve the dyeing property, and the structural unit A and the structural unit B simultaneously form the soft section of the polyurethane to obtain the bio-based polyurethane with excellent comprehensive performance, but the dyeing property is poor; based on the above, the inventors have conducted intensive studies on the dyeing modification, and the present invention has surprisingly found that the introduction of the structural unit C consisting of a structural unit containing a pendant propyl ether group CH can effectively improve the dyeing property of the original bio-based polyurethane 3 CH 2 CHO (from ring opening of propylene oxide) and Ether group C 2 H 4 O (from the ring opening of ethylene oxide) is linked to one another and has a better dyeing effect (evaluated in terms of dyeing depth) when it is present together in one structural unit, and therefore the structural unit C is selected for this purpose, and C of the structural units C 2 H 4 The dyeing effect is best when the proportion of the O unit is 0.5-0.8;
from the analysis of structural difference, no matter the structural unit A or the structural unit B is a crystalline unit, the polyether structural unit C containing the side group is a random copolymerization chain segment containing the side group, and the structural regularity is destroyed to form an amorphous state. Therefore, it is presumed that the occurrence of dyeing modification is simultaneously related to the aggregation form of the polymer chains and the density of ether bonds in such aggregation form when CH 3 CH 2 When CHO is too little, an amorphous region cannot be obtained effectively, and when CH is present 3 CH 2 When the amount of CHO is too large, too few ether bonds are formed in the amorphous region, 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:
according to the acid-dye-dyeable bio-based polyurethane resin, the molar ratio of the structural unit B to the structural unit C is not lower than 9, otherwise, the structural unit C occupies a larger proportion, so that the crystallization of polyurethane is seriously damaged, the mechanical property of a product is seriously reduced, and the polyurethane resin can show better dyeing depth and physical property balance only when the molar ratio of the structural unit B to the structural unit C is 9-19.
An acid-dyeable biobased polyurethane resin as described above, n A :(n B +n C ) 1-2:1, wherein n 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; 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 defines the proportion of polyester and polyether in the soft segment structure; the polyether polyurethane has excellent hydrolysis resistance and good rebound resilience, but the polyether polyurethane has the problems of low strength, low hardness and poor thermal oxidation performance; the polyester polyurethane has excellent thermal oxidation resistance, high strength and hardness, but relatively poor rebound resilience and hydrolysis resistance; in order to complement the advantages and disadvantages of polyether and polyester, polyether and polyester can be jointly used for preparing polyurethane and forming polyether polyester polyurethane; the ratio of polyester to polyether structural units in the polyurethane is variable according to the purpose of use of the polyurethane; the invention considers the kind of polyether polyester and the kind of chain extender, 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 number of polyester units in the polyurethane is too large, and the hydrolysis resistance of the product cannot meet the requirements of certain specific applications, such as the test requirement of the furniture industry at 70 ℃ for 840h under 95% humidity; 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 unit in the polyurethane is too much, and the light and heat resistance of the product cannot pass the requirements of certain specific applications, such as the test requirement of 105 ℃ for 500h in the automobile industry; when the mole number and structure of the structural unit AWhen the ratio of the total mole number of the unit B and the structural unit C is 1-2, both of them are achieved.
In the acid-dye-dyeable bio-based polyurethane resin, the structural unit D corresponding to the chain extender comprises:
structural unit D1:
derived from a tertiary amine dihydroxy chain extender;
structural unit D2: -R 4 -，R 4 The nitrogen-free polyurethane resin contains no nitrogen, and is derived from the combination of diamine chain extender and dihydroxy chain extender, or derived from the combination of hydroxylamine chain extender and dihydroxy chain extender;
the structural unit D1 is grafted into the molecular chain of the polyurethane resin through a urethane group; the structural unit D2 is partially connected into the molecular chain of the polyurethane resin through a ureido group and partially connected into the molecular chain of the polyurethane resin through a carbamate group;
the ratio of the number of moles of urethane groups used for linking structural unit D1 to the total number of moles of urethane groups and urea groups used for linking 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 hard polyurethane segment, so that the acid group on the acid dye can react with the basic tertiary amine group to form the quaternary ammonium salt, and the chemical reaction fixes dye molecules and makes the dye molecules not easy to migrate, thereby improving the dyeing depth and greatly improving the color fastness; however, the prior art does not adopt such techniques to improve the color fastness, because the introduction of a small amount of tertiary amine groups results in severe deterioration of the properties of the polyurethane resin; 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, the ratio of the tertiary amine dihydroxy chain extender in the total chain extender is limited, and when the ratio is less than 0.05, the effect of introducing the tertiary amine dihydroxy chain extender cannot be shown; when the proportion 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 leading the polyurethane to lose the use value; at a ratio of more than 0.15, the above-mentioned drawbacks are not sufficiently compensated even by the introduction of urea groups.
An acid-dyeable biobased polyurethane resin as described above, wherein the molar ratio of the urethane group for linking the structural unit D to the urea group for linking the structural unit D is 3 to 9; as described above, the tertiary amine dihydroxy chain extender can remarkably destroy the hydrogen bond effect of polyurethane, the invention improves the number of the hydrogen bond of the polyurethane by introducing ureido groups, thereby making up the strength loss caused by the tertiary amine dihydroxy chain extender, and limiting the molar ratio of the urethane groups used for connecting the structural unit D to the ureido groups used for connecting the structural unit D to be 3-9, when the ratio is more than 9, the content of the ureido groups is too small, and the effect of introducing the ureido groups cannot be embodied; when the ratio is less than 3, too much urea group content causes severe whitening of the polyurethane under stress, and too low elongation, so that the polyurethane is easily broken and whitened in practical use to cause loss of application value of the product.
In the acid-dye-dyeable bio-based polyurethane resin, the structural unit E corresponding to the blocking agent is located at the end of the molecular chain of the polyurethane resin, is derived from methanol, ethanol or di-n-butylamine, and is grafted into the molecular chain of the polyurethane resin through a urethane group or a urea group.
As described above, the acid-dyeable biobased polyurethane resin has a molecular chain in which the total molar number of urethane groups and urea groups is 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 Is the number of moles of structural unit E; said urethane groupThe terminal hydroxyl derived from the polymer glycol, the chain extender and the end capping agent is reacted with an isocyanate NCO end group, and the ureido group is derived from the reaction of the terminal amino of the chain extender and the end capping agent and the isocyanate NCO end group;
n D :(n A +n B +n C )＝2-5:1；
n E the unit of the weight of the polyurethane resin is in grams per molar mass of the polyurethane resin, the molar mass of the polyurethane resin is 50000-150000 grams per mole, and n is calculated for convenience E In the present invention, the weight of the polyurethane resin is defined as the sum of the weights of the diol, the chain extender and the diisocyanate.
An acid-dyeable biobased polyurethane resin as described above, the isocyanate being biobased diphenylmethane diisocyanate (MDI), the use of MDI providing superior strength and solvent resistance to the biobased dyed polyurethane compared to other diisocyanates, the biobased diphenylmethane diisocyanate having an effective biobased content of 62%.
The tensile load of the biobased polyurethane resin dyeable by the acid dye is more than or equal to 62MPa, and the hydrolysis resistance is more than 78%; the light fastness grade of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 4-5, and the rubbing color fastness grade is 4-5; the bio-based polyurethane resin has a bio-based content of 60 wt% or more.
Advantageous effects
Compared with the prior art, the bio-based content of the polyurethane resin can reach more than 60 wt%, meanwhile, the dyeing performance (dyeing depth and dyeing fastness) is superior to that of the prior art, and other performances are higher than or close to that of the prior art.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
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 model cmT6104 tensile machine of Shenzhen New Mash corporation;
(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 standard, deliquescing the sample film to be tested for 840 hours under the conditions that the temperature is 70 ℃ and the relative humidity is 95%, testing the tensile load performance of the sample film according to the QB/T4197-2011 polyurethane resin for synthetic leather standard, and multiplying the ratio of the tensile load after deliquescence to the tensile load before deliquescence by 100% to obtain the hydrolysis resistance index of the bio-based polyurethane resin;
(3) color fastness to light progression: measuring the light fastness grade of the bio-based microfiber base cloth prepared from different bio-based polyurethane resins according to GB/T169991-2008 xenon arc of high-temperature artificial light fastness and ageing resistance of textile color fastness test;
(4) l value: testing the L values of the bio-based microfiber base fabrics prepared from different bio-based polyurethane resins by using a CM-700D type spectrocolorimeter of KONIC MINOLTA company, wherein the L values are light and dark values, and the smaller the value is, the deeper the value is;
(5) the grade of the friction color fastness is as follows: carrying out rubbing color fastness test on the bio-based microfiber base cloth prepared from different bio-based polyurethane resins according to the method in GB/T3920-;
the sample preparation method of the bio-based microfiber base cloth in the steps (3) to (5) comprises the following steps:
firstly, putting a non-woven fabric (a non-woven fabric C8SW0560-GG145 of Shanghai Huafeng microfiber science and technology Co., Ltd.) into a polyurethane impregnation solution for impregnation to obtain the non-woven fabric with the liquid carrying rate of 120%, and carrying out solidification, washing and toluene reduction to obtain wet base fabric; then, drying the wet base fabric on a crawler-type drying line at the temperature of 140 ℃ for 30 minutes; finally, dyeing the dried bio-based microfiber base cloth to obtain a bio-based microfiber base cloth sample;
the polyurethane impregnation liquid consists of 100 parts of bio-based polyurethane resin, 50 parts of N, N-dimethylformamide and 0.8 part of a release agent (polyether modified silicone oil type release agent ADDITIVE No.10 of Shanghai Riduo polymer materials, Co., Ltd.);
the dyeing steps are as follows:
1) preparing a dyeing base solution;
adding a leveling agent (PL Conc of Shanghai Yayun company) and a penetrating agent (RT-806 of Ruita chemical Co., Ltd. of Quzhou city) into water for dissolving to prepare a dyeing base solution, wherein the concentration of the leveling agent is 2 wt%, and the concentration of the penetrating agent is 0.1 wt%;
2) preparing a bio-based microfiber base cloth, a yellow dye (HD-3R, Shanghai Xingkang chemical Co., Ltd.), a red dye (ASP-G, Hangzhou Taxishi chemical Co., Ltd.), a black dye (D-PA, Yuzhen chemical Co., Ltd.) and a 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 a dyeing base solution to obtain a dye solution;
4) soaking the bio-based microfiber substrate in a dye solution, heating from normal temperature to 70 ℃ at the speed of 0.7 ℃/min, and then preserving heat for 10 min; then heating to 98 ℃ at the speed of 1 ℃/min, and preserving the heat for 60 min; then the temperature is reduced to 60 ℃ at the cooling speed of 1.5 ℃/min; then changing the dye liquor into water, and cleaning and drying the base cloth at the temperature of 60 ℃ to finish dyeing.
Example 1
A preparation method of bio-based polyurethane resin dyeable by acid dyes comprises the following steps:
(1) preparing raw materials;
diol A: polyethylene glycol tetradecanoate diol having a molecular weight of 2000;
diol B: polytrimethylene ether glycol having a molecular weight of 2000;
a diol C: a polypropylene oxide ethylene oxide random copolyether glycol of molecular weight 2000, wherein C 2 H 4 Molar ratio of O structural units 0.5 (i.e. C incorporated in the copolyether) 2 H 4 O structural unit occupation C 2 H 4 O and CH 3 CH 2 The ratio of the sum of CHO structural units);
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: biobased diphenylmethane diisocyanate, scientific institute (china) ltd;
solvent: dimethylformamide;
the mole number of the diol A is 22.5 mol; the mole number of the diol B is 14 mol; the mole number of the diol C is 1 mol; the mole number of the chain extender D1 is 6.5625 mol; the mole number of the chain extender D2 is 124.6875 mol; the mole number of the isocyanate is 168.75 mol; the mol number of the end-capping agent is 1.26 mol; weight of solvent 376913.4 g;
(2) equally dividing the chain extender D1 into two parts by weight, and marking 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, and recording the two parts as a first part of isocyanate and a second part of isocyanate, wherein the ratio of the mole number of the first part of isocyanate to the total mole number of diol A, diol B, diol C and first part of chain extender D1 is 0.75:1, and the rest isocyanate is the second part of isocyanate;
(3) uniformly mixing dihydric alcohol A, dihydric alcohol B, dihydric alcohol C, a first part of chain extender D1 and a 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 then carrying out prepolymerization for 1.4 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 obtained in the step (4), and stirring for 26 minutes;
(6) and (3) 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 bio-based polyurethane resin dyeable by the acid dye 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 dihydric alcohol comprise a structural unit A (derived from the diol A in the raw material), a structural unit B (derived from the diol B in the raw material) and a structural unit C (derived from the diol C in the raw material); the structural unit A, the structural unit B and the structural unit C are connected into a molecular chain of the polyurethane resin through a carbamate group; the molar ratio of the structural unit B to the structural unit C is 14;
structural units corresponding to the isocyanate are derived from the isocyanate in the raw materials;
the structural unit D corresponding to 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 grafted into the molecular chain of the polyurethane resin through a urethane group; the structural unit D2 is partially connected into the molecular chain of the polyurethane resin through a ureido group and partially connected into the molecular chain of the polyurethane resin through a carbamate group; the ratio of the number of moles of urethane groups used for linking structural unit D1 to the total number of moles of urethane groups and urea groups used for linking structural unit D was 0.05; the molar ratio of urethane groups for linking structural unit D to ureido groups for linking 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 urethane group or a ureido group;
the total mole number of urethane groups and urea groups in the molecular chain of the polyurethane resin is 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 Is the number of moles of structural unit E; n is D :(n A +n B +n C )＝3.5:1；n E The unit of weight of the polyurethane resin is gram per molar mass of the polyurethane resin, and the molar mass of the polyurethane resin is 100000 grams per mole; n is A :(n B +n C )＝1.5:1。
The bio-based polyurethane resin dyeable by the finally prepared acid dye has the bio-based content of 78.9 wt%, the tensile load of 70MPa and the 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 light fastness level is 4.5, and the rubbing color fastness level is 4.5.
Comparative example 1
A polyurethane resin was prepared essentially as in example 1 except that diol C was a mixture of a polypropylene oxide ether glycol of molecular weight 2000 and a polyethylene oxide ether glycol of molecular weight 2000 in a 1:1 molar ratio, the total molar amount of the mixture being the same as that of diol C in example 1.
The bio-based content of the finally prepared polyurethane resin is 78.9 wt%, 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 level is 4.5, and the rubbing color fastness level 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 because comparative example 1 does not form C 2 H 4 O and CH 3 CH 2 The random copolymerization structure formed by the CHO unit structure has the advantages that the structural regularity of the polyethylene oxide ether glycol is not damaged, the polyethylene oxide ether glycol easy to crystallize also has the problem of difficult coloring, and an amorphous area formed by simply introducing the polypropylene oxide ether glycol and the density of ether bonds are insufficient, so that the dyeing depth is reduced, namely the L value is improved.
Comparative example 2
A process for the preparation of a polyurethane resin, substantially as described in example 1, except that C is the diol C 2 H 4 The molar ratio of the O structural unit is 0.3.
The bio-based content of the finally prepared polyurethane resin is 78.9 wt%, 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 level is 4.5, and the rubbing color fastness level is 4.5.
As can be seen by comparing example 1 with comparative example 2, the value of L of comparative example 2 is higher than that of example 1, since C in diol C in comparative example 2 2 H 4 Too few O structures, CH 3 CH 2 CHO is too much, causing too few ether bonds in the amorphous region, and intermolecular forces between the molecular chain segments of the amorphous region and the dye are reduced, causing a reduction in the depth of dyeing.
Comparative example 3
A process for the preparation of a polyurethane resin, substantially as described in example 1, except that C is the diol C 2 H 4 The molar ratio of the O structural unit was 0.9.
The bio-based content of the finally prepared polyurethane resin is 78.9 wt%, 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 level is 4.5, and the rubbing color fastness level is 4.
As can be seen by comparing example 1 with comparative example 3, comparative example 3 has a higher L value than example 1 due to the C in diol C in comparative example 3 2 H 4 The O structure is too much to obtain an effective amorphous region, and there is still a problem that the dye is difficult to enter a crystalline region, thereby causing a decrease in dyeing depth.
Example 2
A preparation method of a polyurethane resin, which is basically the same as that of example 1, except that the molar number of the chain extender D1 is 2.625mol, and the molar number of the chain extender D2 is 128.625 mol.
The bio-based content of the finally prepared polyurethane resin is 78.9 wt%, 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 level is 4.5, and the rubbing color fastness level is 3.5.
Comparing example 1 with example 2, it can be seen that example 2 has a higher L value than example 1 and a lower number of crockfastness levels than example 1, because in example 2 there are too few D1 units, so that there are too few groups to react with the dye and do not function as D1.
Example 3
A preparation method of polyurethane resin is basically the same as that of example 1, except that the mole number of the chain extender D1 is 26.25mol, and the mole number of the chain extender D2 is 105 mol.
The bio-based content of the finally prepared polyurethane resin is 78.9 wt%, 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 level is 4.5, and the rubbing color fastness level is 4.
Comparing example 1 with example 3, it can be seen that the tensile load of example 3 is significantly lower than that of example 1, since the strength drops too much due to the more D1 cells in example 3.
Example 4
A method for preparing a polyurethane resin, which is substantially the same as in example 1, except that the chain extender D1 is ethanolamine.
The bio-based content of the finally prepared polyurethane resin is 78.9 wt%, 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 level is 4.5, and the rubbing color fastness level is 3.5.
Comparing example 1 with example 4, it can be seen that the L value and the rubbing fastness of example 4 are both deteriorated, since example 4 does not have the anchor group tertiary amine group of the dye, and thus the resin strength is not deteriorated, the mechanical properties are improved, and the rubbing fastness is decreased.
Example 5
A polyurethane resin was prepared essentially as in example 1, except that the chain extender D2 was ethanolamine and example 5 corresponded to the use of an equimolar amount of ethanolamine instead of the 1:1 molar ratio ethylene glycol to ethanolamine mixture of example 1.
The bio-based content of the finally prepared polyurethane resin is 78.9 wt%, the tensile load is 65MPa, and the polyurethane resin is brittle fracture and has stress whitening; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 29.4, the light fastness level is 4.5, and the rubbing color fastness level is 4.5.
Comparing example 1 with example 5, it can be seen that the molar ratio of the urethane groups used for linking structural unit D to the ureido groups used for linking structural unit D is decreased, and too many ureido groups result in increased brittleness of the polyurethane and easily cause stress whitening.
Example 6
A preparation method of bio-based polyurethane resin dyeable by acid dyes comprises the following steps:
(1) preparing raw materials;
diol A: 1, 3-propanediol polysebacate diol having a molecular weight of 3000;
diol B: polytrimethylene ether glycol having a molecular weight of 1000;
a diol C: a 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-bis-hydroxyisopropyl aniline;
chain extender D2: a mixture of ethylene glycol and 4, 4' -diphenylmethane diamine in a molar ratio of 4: 1;
end-capping agent: ethanol;
isocyanate: biobased diphenylmethane diisocyanate, scientific institute (china) ltd;
solvent: dimethylacetamide;
the mole number of the diol A is 18 mol; the mole number of the diol B is 9 mol; the mole number of the diol C is 1 mol; the mole number of the chain extender D1 is 5.6 mol; the mole number of the chain extender D2 is 50.4 mol; the mole number of the isocyanate is 84 mol; the mol number of the end-capping agent is 1.82 mol; weight of solvent 273510.9 g;
(2) equally dividing the chain extender D1 into two parts by weight, and marking 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, and recording the two parts as a first part of isocyanate and a second part of isocyanate, wherein the ratio of the mole number of the first part of isocyanate to the total mole number of diol A, diol B, diol C and first part of chain extender D1 is 0.75:1, and the rest isocyanate is the second part of isocyanate;
(3) uniformly mixing dihydric alcohol A, dihydric alcohol B, dihydric alcohol C, a first part of chain extender D1 and a 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 then carrying out prepolymerization 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 obtained in the step (4), and stirring for 30 minutes;
(6) and (3) 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 bio-based polyurethane resin dyeable by the acid dye 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 dihydric alcohol comprise a structural unit A (derived from the diol A in the raw material), a structural unit B (derived from the diol B in the raw material) and a structural unit C (derived from the diol C in the raw material); the structural unit A, the structural unit B and the structural unit C are connected into a molecular chain of the polyurethane resin through a carbamate group; the molar ratio of the structural unit B to the structural unit C is 9;
structural units corresponding to the isocyanate are derived from the isocyanate in the raw materials;
the structural unit D corresponding to 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 grafted into the molecular chain of the polyurethane resin through a urethane group; the structural unit D2 is partially connected into the molecular chain of the polyurethane resin through a ureido group and partially connected into the molecular chain of the polyurethane resin through a carbamate group; the ratio of the number of moles of urethane groups used for linking structural unit D1 to the total number of moles of urethane groups and urea groups used for linking structural unit D was 0.1; the molar ratio of urethane groups used for linking structural unit D to ureido groups used for linking 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 urethane group or a ureido group;
the total mole number of the urethane group and the urea group in the molecular chain of the polyurethane resin is 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 Is the number of moles of structural unit E; n is D :(n A +n B +n C )＝2:1；n E The unit of weight of the polyurethane resin is grams per molar mass of the polyurethane resin, and the molar mass of the polyurethane resin is 50000 grams per mole; n is A :(n B +n C )＝1.8:1。
The bio-based polyurethane resin dyeable by the finally prepared acid dye has the bio-based content of 82.5 wt%, the tensile load of 63MPa and the hydrolysis resistance of 81 percent; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 27.7, the light fastness level is 4.5, and the rubbing color fastness level is 4.
Example 7
A preparation method of bio-based polyurethane resin dyeable by acid dyes comprises the following steps:
(1) preparing raw materials;
diol A: poly (ethylene glycol octadecanoate) glycol with a molecular weight of 1000;
diol B: polytrimethylene ether glycol having a molecular weight of 3000;
a diol C: a polypropylene oxide ethylene oxide random copolyether glycol having a molecular weight of 1000, wherein C 2 H 4 The molar ratio of the O structural unit is 0.6;
chain extender D1: n, N-bishydroxyisopropyl-p-toluidine;
chain extender D2: a mixture of butanediol and 4, 4' -diphenylmethane diamine in a molar ratio of 7: 1;
end-capping agent: di-n-butylamine;
isocyanate: biobased diphenylmethane diisocyanate, scientific institute (china) ltd;
solvent: dimethylformamide;
the mole number of the diol A is 20 mol; the mole number of the diol B is 19 mol; the mole number of the diol C is 1 mol; the mole number of the chain extender D1 is 18 mol; the mole number of the chain extender D2 is 102 mol; the mole number of the isocyanate is 160 mol; the mole number of the end capping agent is 1.89 mol; weight of solvent 397729.8 g;
(2) equally dividing the chain extender D1 into two parts by weight, and marking 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, and recording the two parts as a first part of isocyanate and a second part of isocyanate, wherein the ratio of the mole number of the first part of isocyanate to the total mole number of diol A, diol B, diol C and first part of chain extender D1 is 0.75:1, and the rest isocyanate is the second part of isocyanate;
(3) uniformly mixing dihydric alcohol A, dihydric alcohol B, dihydric alcohol C, a first part of chain extender D1 and a 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 then carrying out prepolymerization 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 obtained in the step (4), and stirring for 25 minutes;
(6) and (3) 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 bio-based polyurethane resin dyeable by the acid dye 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 dihydric alcohol comprise a structural unit A (derived from the diol A in the raw material), a structural unit B (derived from the diol B in the raw material) and a structural unit C (derived from the diol C in the raw material); the structural unit A, the structural unit B and the structural unit C are connected into a molecular chain of the polyurethane resin through a carbamate group; 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 materials;
the structural unit D corresponding to 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 grafted into the molecular chain of the polyurethane resin through a urethane group; the structural unit D2 is partially connected into the molecular chain of the polyurethane resin through a ureido group and partially connected into the molecular chain of the polyurethane resin through a carbamate group; the ratio of the number of moles of urethane groups used for linking structural unit D1 to the total number of moles of urethane groups and urea groups used for linking structural unit D was 0.15; the molar ratio of urethane groups used for linking structural unit D to ureido groups used for linking 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 urethane group or a ureido group;
the total mole number of urethane groups and urea groups in the molecular chain of the polyurethane resin is 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 Is the number of moles of structural unit E; n is D :(n A +n B +n C )＝3:1；n E The weight of the polyurethane resin per the molar mass of the polyurethane resin, the unit of the weight of the polyurethane resin is grams, and the molar mass of the polyurethane resin is 70000 grams per mole; n is A :(n B +n C )＝1:1。
The bio-based polyurethane resin dyeable by the finally prepared acid dye has the bio-based content of 76.0 wt%, the tensile load of 67MPa and the hydrolysis resistance of 93 percent; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 27.0, the light fastness level is 4, and the rubbing color fastness level is 4.
Example 8
A preparation method of bio-based polyurethane resin dyeable by acid dyes comprises the following steps:
(1) preparing raw materials;
diol A: 1, 3-propanediol docosadioate glycol having a molecular weight of 1500;
diol B: polytrimethylene ether glycol having a molecular weight of 1500;
a diol C: a 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-dihydroxyethylaniline;
chain extender D2: a mixture of butanediol and ethanolamine at a molar ratio of 4: 5;
end-capping agent: methanol;
isocyanate: biobased diphenylmethane diisocyanate, scientific institute (china) ltd;
solvent: dimethylformamide;
the mole number of the diol A is 14.3 mol; the mole number of the diol B is 12 mol; the mole number of the diol C is 1 mol; the mole number of the chain extender D1 is 13.65 mol; the mole number of the chain extender D2 is 122.85 mol; the mole number of the isocyanate is 163.8 mol; the mol number of the end capping agent is 1.16 mol; weight of solvent 277353.6 g;
(2) equally dividing the chain extender D1 into two parts by weight, and marking 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, marking as a first part of isocyanate and a second part of isocyanate, wherein the ratio of the mole number of the first part of isocyanate to the total mole number of the dihydric alcohol A, the dihydric alcohol B, the dihydric alcohol C and the first part of chain extender D1 is 0.75:1, and the rest isocyanate is the second part of isocyanate;
(3) uniformly mixing dihydric alcohol A, dihydric alcohol B, dihydric alcohol C, a first part of chain extender D1 and a 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 then carrying out prepolymerization for 1 hour;
(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 obtained in the step (4), and stirring for 28 minutes;
(6) and (3) 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 bio-based polyurethane resin dyeable by the acid dye 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 dihydric alcohol comprise a structural unit A (derived from the diol A in the raw material), a structural unit B (derived from the diol B in the raw material) and a structural unit C (derived from the diol C in the raw material); the structural unit A, the structural unit B and the structural unit C are connected into a molecular chain of the polyurethane resin through a carbamate group; the molar ratio of the structural unit B to the structural unit C is 12;
structural units corresponding to the isocyanate are derived from the isocyanate in the raw materials;
the structural unit D corresponding to 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 grafted into the molecular chain of the polyurethane resin through a urethane group; the structural unit D2 is partially connected into the molecular chain of the polyurethane resin through a ureido group and partially connected into the molecular chain of the polyurethane resin through a carbamate group; the ratio of the number of moles of urethane groups used for linking structural unit D1 to the total number of moles of urethane groups and urea groups used for linking structural unit D was 0.1; the molar ratio of urethane groups for linking structural unit D to ureido groups for linking 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 urethane group or a ureido group;
the total mole number of urethane groups and urea groups in the molecular chain of the polyurethane resin is 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 Is the number of moles of structural unit E; n is D :(n A +n B +n C )＝5:1；n E The unit of weight of the polyurethane resin is grams per molar mass of the polyurethane resin, and the molar mass of the polyurethane resin is 80000 grams per mole; n is a radical of an alkyl radical A :(n B +n C )＝1.1:1。
The bio-based polyurethane resin dyeable by the finally prepared acid dye has the bio-based content of 70.1 wt%, the tensile load of 76MPa and the hydrolysis resistance of 90 percent; the L value of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 28.1, the light fastness level is 5, and the rubbing color fastness level is 4.5.
Example 9
A preparation method of bio-based polyurethane resin dyeable by acid dyes comprises the following steps:
(1) preparing raw materials;
diol A: polyethylene glycol hexadecanoate glycol having a molecular weight of 2500;
glycol B: polytrimethylene ether glycol having a molecular weight of 2500;
a diol C: a polypropylene oxide ethylene oxide random copolyether glycol having a molecular weight of 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' -diphenylmethane diamine in a molar ratio of 6.36: 1;
end capping agent: ethanol;
isocyanate: biobased diphenylmethane diisocyanate, scientific institute (china) ltd;
solvent: dimethylformamide;
the mole number of the diol A is 22.1 mol; the mole number of the diol B is 16 mol; the mole number of the diol C is 1 mol; the mole number of the chain extender D1 is 12.512 mol; the mole number of the chain extender D2 is 143.888 mol; the mole number of the isocyanate is 195.5 mol; the mol number of the end capping agent is 1.34 mol; weight of solvent 481957.5 g;
(2) equally dividing the chain extender D1 into two parts by weight, and marking 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, marking as a first part of isocyanate and a second part of isocyanate, wherein the ratio of the mole number of the first part of isocyanate to the total mole number of the dihydric alcohol A, the dihydric alcohol B, the dihydric alcohol C and the first part of chain extender D1 is 0.75:1, and the rest isocyanate is the second part of isocyanate;
(3) uniformly mixing dihydric alcohol A, dihydric alcohol B, dihydric alcohol C, a first part of chain extender D1 and a 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 then carrying out prepolymerization 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 obtained in the step (4), and stirring for 30 minutes;
(6) and (3) 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 bio-based polyurethane resin dyeable by the acid dye 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 dihydric alcohol comprise a structural unit A (derived from the diol A in the raw material), a structural unit B (derived from the diol B in the raw material) and a structural unit C (derived from the diol C in the raw material); the structural unit A, the structural unit B and the structural unit C are connected into a molecular chain of the polyurethane resin through a carbamate group; 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 materials;
the structural unit D corresponding to 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 grafted into the molecular chain of the polyurethane resin through a urethane group; the structural unit D2 is partially connected into the molecular chain of the polyurethane resin through a ureido group and partially connected into the molecular chain of the polyurethane resin through a carbamate group; the ratio of the number of moles of urethane groups used for linking structural unit D1 to the total number of moles of urethane groups and urea groups used for linking structural unit D was 0.08; the molar ratio of urethane groups used for linking structural unit D to ureido groups used for linking 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 urethane group or a ureido group;
the total mole number of urethane groups and urea groups in the molecular chain of the polyurethane resin is 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 Is the number of moles of structural unit E; n is D :(n A +n B +n C )＝4:1；n E The unit of weight of the polyurethane resin is grams per molar mass of the polyurethane resin, and the molar mass of the polyurethane resin is 120000 grams per mole; n is A :(n B +n C )＝1.3:1。
The bio-based polyurethane resin dyeable by the finally prepared acid dye has the bio-based content of 78.2 wt%, the tensile load of 68MPa and the 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 level is 4.5, and the rubbing color fastness level is 5.
Example 10
A preparation method of bio-based polyurethane resin dyeable by acid dyes comprises the following steps:
(1) preparing raw materials;
diol A: 1, 3-propanediol polysebacate diol having a molecular weight of 2000;
diol B: polytrimethylene ether glycol having a molecular weight of 1800;
a diol C: a polypropylene oxide ethylene oxide random copolyether glycol of molecular weight 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 of 1: 1);
chain extender D2: a mixture of butanediol and 4, 4' -diphenylmethanediamine in a molar ratio of 7.9: 1;
end-capping agent: di-n-butylamine;
isocyanate: biobased diphenylmethane diisocyanate, scientific institute (china) ltd;
solvent: dimethylformamide;
the mole number of the diol A is 36 mol; the mole number of the diol B is 17 mol; the mole number of the diol C is 1 mol; the mole number of the chain extender D1 is 26.73 mol; the mole number of the chain extender D2 is 216.27 mol; the mole number of the isocyanate is 297 mol; the mol number of the end capping agent is 1.37 mol; weight of solvent 618445.5 g;
(2) equally dividing the chain extender D1 into two parts by weight, and marking 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, and recording the two parts as a first part of isocyanate and a second part of isocyanate, wherein the ratio of the mole number of the first part of isocyanate to the total mole number of diol A, diol B, diol C and first part of chain extender D1 is 0.75:1, and the rest isocyanate is the second part of isocyanate;
(3) uniformly mixing a dihydric alcohol A, a dihydric alcohol B, a dihydric alcohol C, a first part of chain extender D1 and a 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 then carrying out prepolymerization 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 obtained in the step (4), and stirring for 25 minutes;
(6) and (3) 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 bio-based polyurethane resin dyeable by the acid dye 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 dihydric alcohol comprise a structural unit A (derived from the diol A in the raw material), a structural unit B (derived from the diol B in the raw material) and a structural unit C (derived from the diol C in the raw material); the structural unit A, the structural unit B and the structural unit C are connected into a molecular chain of the polyurethane resin through a carbamate group; the molar ratio of the structural unit B to the structural unit C is 17;
structural units corresponding to the isocyanate are derived from the isocyanate in the raw materials;
the structural unit D corresponding to 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 grafted into the molecular chain of the polyurethane resin through a urethane group; part of the structural unit D2 is connected into a molecular chain of the polyurethane resin through a carbamido group, and part of the structural unit D2 is connected into the molecular chain of the polyurethane resin through a urethane group; the ratio of the number of moles of urethane groups used for linking structural unit D1 to the total number of moles of urethane groups and urea groups used for linking structural unit D was 0.11; the molar ratio of urethane groups used for linking structural unit D to ureido groups used for linking 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 urethane group or a ureido group;
the total mole number of urethane groups and urea groups in the molecular chain of the polyurethane resin is 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 Is the number of moles of structural unit E; n is D :(n A +n B +n C )＝4.5:1；n E The unit of the weight of the polyurethane resin is gram per the molar mass of the polyurethane resin, and the molar mass of the polyurethane resin is 150000 grams per mole; n is A :(n B +n C )＝2:1。
The bio-based polyurethane resin dyeable by the finally prepared acid dye has the bio-based content of 72.1 wt%, the tensile load of 72MPa and the 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 level is 5, and the rubbing color fastness level is 4.5.
Example 11
A polyurethane resin was prepared essentially as in example 10 except that the chain extender D2 was butanediol and example 11 corresponded to using an equimolar amount of butanediol instead of the 7.9:1 molar ratio of butanediol to 4, 4' -diphenylmethanediamine mixture of example 10.
The bio-based content of the finally prepared polyurethane resin is 78.9 wt%, 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 light fastness level is 4.5, and the rubbing color fastness level is 4.5.
Comparing example 10 with example 11, it can be seen that the groups used for connecting structural units D are urethane groups, and only the terminal groups have a small number of urea groups, which causes the chain extender D1 containing pendant groups to cause a decrease in the number of hydrogen bonds of the hard segments of the polyurethane, and the broken intermolecular forces are not repaired, resulting in a significant decrease in the strength of the polyurethane.
Claims (9)
1. The utility model provides a biobased polyurethane resin that acid dyes can dye, the molecular chain includes the soft section that comprises long chain dihydric alcohol and the hard section that comprises isocyanate, chain extender, blocking agent, its characterized in that, the constitutional unit that long chain dihydric alcohol corresponds includes:
structural unit a:
x is 10-18, y is 2-3, and is derived from bio-based polyester diol with the number average molecular weight of 1000-3000;
structural unit B:
derived from bio-based polyether glycol having a number average molecular weight of 1000-3000;
structural unit C:
nx/(nx + ny) ═ 0.5-0.8, from petroleum-based polypropylene oxide ethylene oxide randomly copolymerized copolyether glycol having a number average molecular weight of 500-;
the structural unit A, the structural unit B and the structural unit C are connected into a molecular chain of the polyurethane resin through urethane groups;
the molar ratio of the structural unit B to the structural unit C is not more than 19;
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. The acid-dyeable biobased polyurethane resin according to claim 1, wherein the molar ratio of the structural unit B to the structural unit C is not less than 9.
3. The acid-dyeable biobased polyurethane resin of claim 1, wherein n is n A :(n B +n C ) 1-2:1, wherein n 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.
4. The acid dye-dyeable bio-based polyurethane resin according to claim 1, wherein the structural unit D corresponding to the chain extender comprises:
structural unit D1:
derived from a tertiary amine dihydroxy chain extender;
structural unit D2: -R 4 -，R 4 The nitrogen-free polyurethane resin contains no nitrogen, and is derived from the combination of diamine chain extender and dihydroxy chain extender, or derived from the combination of hydroxylamine chain extender and dihydroxy chain extender;
the structural unit D1 is connected into the molecular chain of the polyurethane resin through a urethane group; the structural unit D2 is partially connected into the molecular chain of the polyurethane resin through a ureido group and partially connected into the molecular chain of the polyurethane resin through a carbamate group;
the ratio of the number of moles of urethane groups used for linking structural unit D1 to the total number of moles of urethane groups and urea groups used for linking structural unit D is 0.05 to 0.15.
5. The acid-dyeable biobased polyurethane resin according to claim 4, wherein the molar ratio of the urethane group for bonding the structural unit D to the urea group for bonding the structural unit D is 3 to 9.
6. The acid-dyeable biobased polyurethane resin as claimed in claim 5, wherein the structural unit E corresponding to the blocking agent is located at the end of the molecular chain of the polyurethane resin, is derived from methanol, ethanol or di-n-butylamine, and is grafted into the molecular chain of the polyurethane resin through a urethane group or a urea group.
7. The acid-dyeable biobased polyurethane resin according to claim 6, wherein the total molar number of urethane groups and urea groups in the molecular chain of the polyurethane resin is 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 Is the number of moles of structural unit E;
n D :(n A +n B +n C )＝2-5:1；
n E the unit of the weight of the polyurethane resin is gram per the molar mass of the polyurethane resin, and the molar mass of the polyurethane resin is 50000-150000 g/mole.
8. The acid-dyeable biobased polyurethane resin of claim 1, wherein the isocyanate is biobased diphenylmethane diisocyanate.
9. The acid dye-dyeable biobased polyurethane resin according to any one of claims 1 to 8, wherein the tensile load of the biobased polyurethane resin is not less than 62MPa, and the hydrolysis resistance is 78% or more; the light fastness grade of the bio-based microfiber base cloth prepared from the bio-based polyurethane resin is 4-5, and the rubbing color fastness grade is 4-5; the bio-based polyurethane resin has a bio-based content of 60 wt% or more.
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