CN116874728A - Solvent-free polyurethane resin prepared from bio-based polyol and preparation method thereof - Google Patents
Solvent-free polyurethane resin prepared from bio-based polyol and preparation method thereof Download PDFInfo
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- CN116874728A CN116874728A CN202310931392.2A CN202310931392A CN116874728A CN 116874728 A CN116874728 A CN 116874728A CN 202310931392 A CN202310931392 A CN 202310931392A CN 116874728 A CN116874728 A CN 116874728A
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- China
- Prior art keywords
- molecular weight
- polyol
- bio
- solvent
- polyurethane resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920005862 polyol Polymers 0.000 title claims abstract description 144
- 150000003077 polyols Chemical class 0.000 title claims abstract description 144
- 238000002360 preparation method Methods 0.000 title claims abstract description 81
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 70
- 238000004917 polyol method Methods 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 143
- -1 aliphatic isocyanate Chemical class 0.000 claims abstract description 66
- 239000012948 isocyanate Substances 0.000 claims abstract description 42
- 239000004970 Chain extender Substances 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 106
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 100
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 77
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 72
- 239000003921 oil Substances 0.000 claims description 66
- 235000019198 oils Nutrition 0.000 claims description 66
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 56
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 50
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 49
- 229940035437 1,3-propanediol Drugs 0.000 claims description 46
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 46
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 44
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 44
- OXSQDJLFMPMKNO-UHFFFAOYSA-N butanedioic acid;propane-1,3-diol Chemical compound OCCCO.OC(=O)CCC(O)=O OXSQDJLFMPMKNO-UHFFFAOYSA-N 0.000 claims description 41
- 239000004359 castor oil Substances 0.000 claims description 40
- 235000019438 castor oil Nutrition 0.000 claims description 40
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 40
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 33
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 claims description 28
- KUQWZSZYIQGTHT-UHFFFAOYSA-N hexa-1,5-diene-3,4-diol Chemical compound C=CC(O)C(O)C=C KUQWZSZYIQGTHT-UHFFFAOYSA-N 0.000 claims description 28
- 239000001384 succinic acid Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000010985 leather Substances 0.000 claims description 24
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 21
- 150000002513 isocyanates Chemical class 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 18
- 239000004744 fabric Substances 0.000 claims description 17
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 17
- 239000008158 vegetable oil Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 13
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 235000019482 Palm oil Nutrition 0.000 claims description 12
- 239000002540 palm oil Substances 0.000 claims description 12
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000005809 transesterification reaction Methods 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 claims description 6
- MBVGJZDLUQNERS-UHFFFAOYSA-N 2-(trifluoromethyl)-1h-imidazole-4,5-dicarbonitrile Chemical compound FC(F)(F)C1=NC(C#N)=C(C#N)N1 MBVGJZDLUQNERS-UHFFFAOYSA-N 0.000 claims description 6
- WJIOHMVWGVGWJW-UHFFFAOYSA-N 3-methyl-n-[4-[(3-methylpyrazole-1-carbonyl)amino]butyl]pyrazole-1-carboxamide Chemical compound N1=C(C)C=CN1C(=O)NCCCCNC(=O)N1N=C(C)C=C1 WJIOHMVWGVGWJW-UHFFFAOYSA-N 0.000 claims description 6
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 235000021388 linseed oil Nutrition 0.000 claims description 6
- 239000000944 linseed oil Substances 0.000 claims description 6
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- QAAXRTPGRLVPFH-UHFFFAOYSA-N [Bi].[Cu] Chemical compound [Bi].[Cu] QAAXRTPGRLVPFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002318 adhesion promoter Substances 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000012767 functional filler Substances 0.000 claims description 3
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 3
- 238000007790 scraping Methods 0.000 claims description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002562 thickening agent Substances 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 abstract description 17
- 230000007613 environmental effect Effects 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 11
- 229920002635 polyurethane Polymers 0.000 abstract description 9
- 238000004383 yellowing Methods 0.000 abstract description 9
- 238000011161 development Methods 0.000 abstract description 8
- 229910052797 bismuth Inorganic materials 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 28
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 27
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 27
- 238000012360 testing method Methods 0.000 description 24
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 15
- 150000002009 diols Chemical class 0.000 description 11
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 239000002649 leather substitute Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920005906 polyester polyol Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000007719 peel strength test Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- YTJGCGBAGAZNLA-UHFFFAOYSA-N 2-methyl-3,4-dihydro-2h-pyran Chemical compound CC1CCC=CO1 YTJGCGBAGAZNLA-UHFFFAOYSA-N 0.000 description 2
- XMICBFRKICBBKD-UHFFFAOYSA-N 3,4-dihydro-2h-pyran-2-ylmethanol Chemical compound OCC1CCC=CO1 XMICBFRKICBBKD-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005586 poly(adipic acid) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 238000004804 winding 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
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G18/30—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
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3804—Polyhydroxy compounds
- C08G18/3812—Polyhydroxy compounds having fluorine atoms
-
- 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
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- 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
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- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
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Abstract
The application relates to the technical field of solvent-free polyurethane, in particular to solvent-free polyurethane resin prepared from bio-based polyol and a preparation method thereof. The solvent-free polyurethane resin prepared from the bio-based polyol comprises a material A and a material B, wherein the material A mainly comprises the bio-based polyol, a chain extender, an auxiliary agent and a catalyst; the material B mainly comprises aliphatic isocyanate and bio-based polyol; the total molar quantity of the-NCO contained in the material B is 1.05-1.20 times of the total molar quantity of the active groups contained in the material A and the material B. The solvent-free polyurethane resin is made of a biological base material, has excellent environmental protection performance, can reduce the dependence on fossil raw materials, accords with a sustainable development concept, and has high wear resistance, high heat resistance, high yellowing resistance, good flexibility and good market prospect when being used as a bonding layer.
Description
Technical Field
The application relates to the technical field of solvent-free polyurethane, in particular to solvent-free polyurethane resin prepared from bio-based polyol and a preparation method thereof.
Background
Polyurethane synthetic leather, which is one of polyurethane elastomers, has a soft luster and a strong dermal feel, and is the most ideal substitute for natural leather. The polyurethane synthetic leather comprises solvent-type synthetic leather, water-based synthetic leather and solvent-free synthetic leather, and the solvent-free synthetic leather does not need to be added with solvent in the production and processing process, is environment-friendly and meets the development requirement of green chemical industry.
At present, aromatic diisocyanate and/or aromatic polyester polyol are generally adopted as main raw materials in solvent-free synthetic leather polyurethane synthetic leather, and benzene rings are introduced into the molecular structure, so that the polyurethane type automobile leather, luggage leather and shoe leather are prepared with good thermal stability, simple processing and low cost. The aliphatic diisocyanate and the aliphatic polyester polyol are adopted to replace the aromatic diisocyanate and the aromatic polyester polyol, and the prepared solvent-free polyurethane resin forms leather with relatively weak strength and low heat resistance grade, so that the leather cannot meet the market requirements. The leather material formed by the solvent-free polyurethane resin synthesized by taking the aromatic diisocyanate and/or the aromatic polyester polyol as the main raw materials is difficult to degrade after the leather material is used due to the benzene ring structure, is difficult to meet the requirements of green environment-friendly materials, and is gradually eliminated by the market. In order to solve the problems, the application provides a solvent-free polyurethane resin prepared from bio-based polyol and a preparation method thereof.
Disclosure of Invention
In order to solve the technical problems, the application provides a solvent-free polyurethane resin prepared from bio-based polyol and a preparation method thereof.
In a first aspect, the application provides a solvent-free polyurethane resin prepared from bio-based polyol, which is realized by the following technical scheme:
the solvent-free polyurethane resin prepared from the bio-based polyol comprises a material A and a material B, wherein the material A mainly comprises the bio-based polyol, a chain extender, an auxiliary agent and a catalyst; the material B mainly comprises aliphatic isocyanate and bio-based polyol;
the total molar quantity of the-NCO contained in the material B is 1.05-1.20 times of the total molar quantity of the active groups contained in the material A and the material B;
the mass of the catalyst is equal to 10ppm-500ppm of the total mass of the aliphatic isocyanate, the bio-based polyol and the chain extender;
the catalyst is prepared by mixing at least one of an organobismuth catalyst, an organotin catalyst, a copper bismuth catalyst and DBU salt with an initiator;
the initiator comprises at least one of azodiisobutyronitrile, azodiisoheptonitrile, dibenzoyl peroxide, ditert-butyl peroxide, dicumyl peroxide, diisopropyl peroxydicarbonate and tert-butyl peroxybenzoate;
The aliphatic isocyanate comprises at least one of isophorone diisocyanate IPDI, hexamethylene diisocyanate HDI, 4' -diisocyanate HMDI, methylcyclohexane diisocyanate HTDI and trimethylhexamethylene diisocyanate TMDI;
the bio-based polyol in the material A comprises at least one of poly (1, 3-propanediol succinate) glycol with the molecular weight of 400-5000, poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate glycol and vegetable oil-based natural oil polyol with the molecular weight of 1000-5000;
the bio-based polyol in the material B is at least one of poly 1,3 propylene glycol ether with the molecular weight of 400-5000 and vegetable oil-based natural oil polyol with the molecular weight of 1000-5000;
the vegetable oil-based natural oil polyol comprises at least one of palm oil-based natural oil polyol, castor oil-based natural oil polyol, linseed oil-based natural oil polyol and linseed oil-based natural oil polyol;
the preparation method of the vegetable oil-based natural oil polyol comprises the following steps:
firstly, feeding, namely uniformly mixing vegetable oil, dihydric alcohol and tetraisopropyl titanate;
the dihydric alcohol in the first step comprises at least one of 1,3 propylene glycol and 1,4 butanediol;
Step two, heating to 130-140 ℃ and reacting to obtain effluent;
step three, heating to 220-230 ℃ and carrying out transesterification for 2-2.5h;
step four, detecting that the acid value is lower than 25mgKOH/g, starting vacuumizing, lasting for 0.1-3.0h, detecting the OH-value, and controlling the OH-value to be 35.4-115 to obtain the finished castor oil-based natural oil polyol
The chain extender is at least one of small molecular alcohol with unsaturated groups, small molecular amine with unsaturated groups, small molecular alcohol with saturated groups and small molecular amine with saturated groups;
the molar ratio of the polyol to the chain extender is controlled at 1: (0.01-0.3);
the auxiliary agent comprises at least one of a leveling agent, a slipping agent, a wetting dispersant, an adhesion promoter, a coupling agent, a defoaming agent, a thickening agent, an antioxidant, an anti-ultraviolet agent, color paste and a functional filler.
The solvent-free polyurethane resin is made of a biological base material, has excellent environmental protection performance, can reduce the dependence on fossil raw materials, accords with a sustainable development concept, and has high wear resistance, high heat resistance, high yellowing resistance, good flexibility and good market prospect when being used as a bonding layer.
Preferably, the bio-based polyol mainly comprises 1, 3-propanediol succinate glycol with a molecular weight of 3000, 1, 3-propanediol succinate/1, 4-butanediol succinate glycol with a molecular weight of 3000 and poly 1, 3-propanediol ether with a molecular weight of 2000 in a molar ratio of (0.5-2): (0.5-2): (0.5-2).
The yellowing resistance, flexibility and wear resistance of the application can be improved by adopting the bio-based polyol.
Preferably, the bio-based polyol mainly comprises 1, 3-propanediol succinate glycol with a molecular weight of 3000, 1, 3-propanediol succinate/1, 4-butanediol succinate glycol with a molecular weight of 3000, 1, 3-propanediol ether with a molecular weight of 2000 and castor oil-based natural oil polyol with a molecular weight of 3000 in a molar ratio of (0.5-2) to (0.8-3.2).
The yellowing resistance, flexibility and wear resistance of the application can be improved by adopting the bio-based polyol, and the variety of bio-based raw materials is enriched by adopting the castor oil-based natural oil polyol, so that the dependence of petroleum raw materials is further eliminated, and the overall environmental protection performance is improved.
Preferably, the bio-based polyol mainly comprises 1, 3-propanediol succinate glycol with a molecular weight of 3000, 1, 3-propanediol succinate/1, 4-butanediol succinate glycol with a molecular weight of 3000, 1, 3-propanediol ether with a molecular weight of 2000, castor oil-based natural oil polyol with a molecular weight of 3000 and modified hydroxysiloxane in a molar ratio of 1:1:1 (1.8-3.2) to (0.2-0.4); the molecular weight of the modified hydroxyl siloxane is 5000-10000, and unsaturated bonds are arranged at two ends of the modified hydroxyl siloxane.
The yellowing resistance, flexibility, wear resistance and heat resistance of the application can be further improved by adopting the bio-based polyol, but the price of the modified hydroxysiloxane is relatively high, and the modified hydroxysiloxane is suitable for the market of high-end products.
Preferably, the chain extender comprises at least one of 1, 5-hexadiene-3, 4-diol with 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 6-hexamethylenediamine, 4-trifluoro-3- (trifluoromethyl) -1, 3-butanediol, (E) -4, 4-trifluoro-but-2-en-1-ol.
Preferably, the chain extender mainly comprises 1, 5-hexadiene-3, 4-diol, 3-methyl-1, 5-pentanediol and 1, 6-hexanediol in a molar ratio of (10-20): (40-45): (40-45).
Preferably, the chain extender consists of 1, 5-hexadiene-3, 4-diol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 4-trifluoro-3- (trifluoromethyl) -1, 3-butanediol in a molar ratio of 1:2:2 (0.2-0.4).
Preferably, the chain extender mainly comprises 1, 5-hexadiene-3, 4-diol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol and (E) -4, 4-trifluoro-but-2-en-1-ol in a molar ratio of (10-25): (30-40): 40 (5-10).
The PU leather prepared by adopting the chain extender has relatively better heat resistance, weather resistance and wear resistance.
Preferably, the aliphatic isocyanate is aliphatic isocyanate with unsaturated groups and aliphatic isocyanate ADI with saturated groups; the aliphatic isocyanate ADI with saturated groups is at least one of isophorone diisocyanate IPDI, hexamethylene diisocyanate HDI, 4' -diisocyanate HMDI, methylcyclohexane diisocyanate HTDI and trimethylhexamethylene diisocyanate TMDI.
The PU leather prepared from the aliphatic isocyanate has relatively better heat resistance and wear resistance.
In a second aspect, the application provides a preparation method of solvent-free polyurethane resin from bio-based polyol, which is realized by the following technical scheme:
a preparation method of solvent-free polyurethane resin prepared from bio-based polyol comprises the steps of preparing material A and material B;
the preparation of the material A is as follows: the biological polyol, the chain extender, the catalyst and the auxiliary agent in the material A are all mixed together and stirred uniformly;
the preparation of the material B is as follows: firstly, putting aliphatic isocyanate MDI into a reaction kettle, heating to 70+/-2.0 ℃, putting all the polyalcohol of the material B into the reaction kettle, maintaining a vacuumizing state, and reacting for 2.0-2.5 hours to obtain the material B;
And uniformly mixing A, B materials according to a proportion, scraping and coating the mixture on a base fabric, heating the base fabric by an oven, and rolling the base fabric into leather.
The preparation method of the solvent-free polyurethane resin prepared from the bio-based polyol is relatively simple, the adopted equipment is conventional equipment, the operation difficulty is relatively low, and the industrial production and manufacturing are convenient to realize.
In summary, the application has the following advantages:
1. the solvent-free polyurethane resin is made of a biological base material, has excellent environmental protection performance, can reduce the dependence on fossil raw materials, accords with a sustainable development concept, and has higher wear resistance, high heat resistance, high yellowing resistance, good flexibility and good market prospect when being used as a bonding layer.
2. The preparation method of the solvent-free polyurethane resin prepared from the bio-based polyol is relatively simple, the adopted equipment is conventional equipment, the operation difficulty is relatively low, and the industrial production and manufacturing are convenient to realize.
Description of the embodiments
The present application will be described in further detail with reference to comparative examples and examples.
Preparation example 1
The preparation method of the isocyanate with unsaturated groups comprises the following steps:
s1: preparation of dihydropyran methyl methacrylate 50.0g of 2-hydroxymethyl-3, 4-dihydropyran is dissolved in 500mL of toluene, 0.50g of p-toluenesulfonic acid, 57.6g of methacrylic acid and 0.20g of hydroquinone are added, the mixture is dehydrated for 2.0h under reflux, then cooled, water and ammonia water are added for neutralization, then an organic phase is collected, toluene is removed, and brown dihydropyran methyl methacrylate liquid is obtained.
S2:100g of toluene, 54.1g of methyl dihydropyran methacrylate, 42.1g of hexamethylene diisocyanate HDI, 1.26g of p-toluenesulfonic acid and 0.2g of hydroquinone are uniformly mixed, the mixture is added into a 500mL stainless steel reaction kettle, after sealing, nitrogen is replaced, the catalyst is p-toluenesulfonic acid, the addition mass is 1.26g, the molar ratio of NCO/methyl dihydropyran methacrylate is=3.3:1, the mixture is heated to 100 ℃, after 7.0h of reaction, the temperature is reduced, reduced pressure distillation is carried out, and the fraction with unsaturated groups at 100-105 ℃ under the condition of 2mmHg column is collected to obtain the isocyanate.
Preparation example 2
The preparation method of the isocyanate with unsaturated groups comprises the following steps:
s1: preparation of dihydropyran methyl methacrylate 50.0g of 2-hydroxymethyl-3, 4-dihydropyran is dissolved in 500mL of toluene, 0.50g of p-toluenesulfonic acid, 57.6g of methacrylic acid and 0.20g of hydroquinone are added, the mixture is dehydrated for 2.0h under reflux, then cooled, water and ammonia water are added for neutralization, then an organic phase is collected, toluene is removed, and brown dihydropyran methyl methacrylate liquid is obtained.
S2:100g of toluene, 54.1g of methyl dihydropyran methacrylate, 54.6g of isophorone diisocyanate, 1.4g of p-toluenesulfonic acid and 0.2g of hydroquinone are uniformly mixed, the mixture is added into a 500mL stainless steel reaction kettle, after sealing, nitrogen replacement is performed, the catalyst is p-toluenesulfonic acid, the addition mass is 1.4g, the molar ratio of NCO/methyl dihydropyran methacrylate is 3.3:1, after heating to 100 ℃ for reacting for 7.0h, the temperature is reduced, reduced pressure distillation is performed, and fractions with unsaturated groups at 100-105 ℃ under a 2mmHg column are collected to obtain isocyanate.
Preparation example 3
The preparation method of the palm oil-based natural oil polyol comprises the following steps:
firstly, feeding, namely feeding palm oil, 1, 4-butanediol and propylene glycol into a reaction kettle according to a molar ratio of 4:3.1:3.1, and then adding tetraisopropyl titanate with the mass of 60ppm of the palm oil, and uniformly mixing for later use;
step two, heating to 130-135.0 ℃, and maintaining the temperature between 130-135 ℃ to react until yielding water;
step three, heating to 220-225 ℃, and maintaining the temperature at 220-225 ℃ for transesterification for 2.0h;
detecting the acid value, and continuing the transesterification reaction for 15min to detect the acid value until the acid value is lower than 25mgKOH/g if the acid value is higher than 25mgKOH/g; when the acid value is lower than 25mgKOH/g, vacuumizing is started, the gauge pressure is pumped from 0.018MPa to 0.098MPa, and the OH of the material is detected after 15min - The OH value is controlled at 37.4+/-2, and the palm oil-based natural oil polyol with the molecular weight of 3000.
Preparation example 4
The preparation method of the castor oil-based natural oil polyol comprises the following steps:
firstly, feeding, namely feeding castor oil, 1, 4-butanediol and propylene glycol into a reaction kettle according to a molar ratio of 4:3.1:3.1, and then adding tetraisopropyl titanate with the mass of 60ppm of palm oil, and uniformly mixing for later use;
step two, heating to 130-135.0 ℃, and maintaining the temperature between 130-135 ℃ to react until yielding water;
Step three, heating to 220-225 ℃, and maintaining the temperature at 220-225 ℃ for transesterification for 2.0h;
detecting the acid value, and continuing the transesterification reaction for 15min to detect the acid value until the acid value is lower than 25mgKOH/g if the acid value is higher than 25mgKOH/g; when the acid value is lower than 25mgKOH/g, vacuumizing is started, the gauge pressure is pumped from 0.018MPa to 0.098MPa, and the OH of the material is detected after 15min - The OH value is controlled at 56+/-3, and the castor oil-based natural oil polyol with the molecular weight of 3000.
Preparation example 5
The preparation method of the castor oil-based natural oil polyol comprises the following steps:
firstly, feeding, namely feeding castor oil, 1, 4-butanediol and propylene glycol into a reaction kettle according to a molar ratio of 4:3.1:3.1, and then adding tetraisopropyl titanate with the mass of 60ppm of palm oil, and uniformly mixing for later use;
step two, heating to 130-135.0 ℃, and maintaining the temperature between 130-135 ℃ to react until yielding water;
step three, heating to 220-225 ℃, and maintaining the temperature at 220-225 ℃ for transesterification for 2.0h;
detecting the acid value, and continuing the transesterification reaction for 15min to detect the acid value until the acid value is lower than 25mgKOH/g if the acid value is higher than 25mgKOH/g; when the acid value is lower than 25mgKOH/g, vacuumizing is started, the gauge pressure is pumped from 0.018MPa to 0.098MPa, and the OH of the material is detected after 15min - The OH value is controlled at 37.4+/-2, and the castor oil-based natural oil polyol with the molecular weight of 3000.
Examples
A solvent-free polyurethane resin prepared from bio-based polyol is prepared from materials A and B through proportionally mixing A, B, scraping the mixture on a base fabric, heating in an oven, and winding. Wherein, the material A mainly comprises biological polyol, chain extender, auxiliary agent and catalyst, and the material B comprises aliphatic isocyanate and biological polyol. The total molar amount of-NCO contained in the material B is 1.05-1.20 times, preferably 1.06-1.12 times, the total molar amount of active groups contained in the material A and the material B.
The mass of the catalyst is equal to 10ppm-500ppm of the total mass of the aliphatic isocyanate, the bio-based polyol and the chain extender. The catalyst is mainly prepared by mixing at least one of an organic bismuth catalyst, an organic tin catalyst, a copper bismuth catalyst and DBU salt with an initiator. The initiator comprises at least one of azodiisobutyronitrile, azodiisoheptonitrile, dibenzoyl peroxide, ditert-butyl peroxide, dicumyl peroxide, diisopropyl peroxydicarbonate and tert-butyl peroxybenzoate.
The aliphatic isocyanate comprises at least one of isophorone diisocyanate IPDI, hexamethylene diisocyanate HDI, 4' -diisocyanate HMDI, methylcyclohexane diisocyanate HTDI and trimethylhexamethylene diisocyanate TMDI. Preferably, the aliphatic isocyanate is aliphatic isocyanate with unsaturated groups and aliphatic isocyanate ADI with saturated groups, wherein the aliphatic isocyanate ADI with saturated groups is at least one of isophorone diisocyanate IPDI, hexamethylene diisocyanate HDI, 4' -diisocyanate HMDI, methylcyclohexane diisocyanate HTDI and trimethylhexamethylene diisocyanate TMDI.
The bio-based polyol in the material A comprises at least one of poly (1, 3-propanediol succinate) glycol with the molecular weight of 400-5000, poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate glycol and vegetable oil-based natural oil polyol with the molecular weight of 1000-5000.
The bio-based polyol in the material B is at least one of poly 1,3 propylene glycol ether with the molecular weight of 400-5000 and vegetable oil-based natural oil polyol with the molecular weight of 1000-5000.
The vegetable oil-based natural oil polyol comprises at least one of palm oil-based natural oil polyol, castor oil-based natural oil polyol, linseed oil-based natural oil polyol, and linseed oil-based natural oil polyol.
Preferably, the bio-based polyol is mainly composed of poly (1, 3-propanediol succinate) glycol with a molecular weight of 3000, poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate glycol with a molecular weight of 3000, poly (1, 3-propanediol ether) with a molecular weight of 2000 in a molar ratio of (0.5-2): (0.5-2): (0.5-2).
Preferably, the bio-based polyol mainly comprises 1, 3-propanediol succinate glycol with a molecular weight of 3000, 1, 3-propanediol succinate/1, 4-butanediol succinate glycol with a molecular weight of 3000, poly 1, 3-propanediol ether with a molecular weight of 2000 and castor oil-based natural oil polyol with a molecular weight of 3000 in a molar ratio of (0.5-2): (0.5-2): (0.5-2): (0.8-3.2).
Preferably, the bio-based polyol mainly comprises 1, 3-propanediol succinate diol with a molecular weight of 3000, 1, 3-propanediol succinate/1, 4-butanediol succinate diol with a molecular weight of 3000, 1, 3-propanediol ether with a molecular weight of 2000, castor oil-based natural oil polyol with a molecular weight of 3000 and modified hydroxysiloxane with a molar ratio of 1:1:1 (1.8-3.2) (0.2-0.4), wherein the molecular weight of the modified hydroxysiloxane is 5000-10000 and both ends of the modified hydroxysiloxane are provided with unsaturated bonds, in particular FM-7721 and FM-7725 of JNC.
The preparation method of the vegetable oil-based natural oil polyol comprises the following steps:
firstly, feeding, namely uniformly mixing vegetable oil, dihydric alcohol and tetraisopropyl titanate;
the dihydric alcohol in the first step comprises at least one of 1,3 propylene glycol and 1,4 butanediol;
step two, heating to 130-140 ℃ and reacting to obtain effluent;
step three, heating to 220-230 ℃ and carrying out transesterification for 2-2.5h;
and fourthly, detecting that the acid value is lower than 25mgKOH/g, starting vacuumizing, continuously detecting the OH-value for 0.1-3.0h, and controlling the OH-value to be 35.4-115 to obtain the finished castor oil-based natural oil polyol.
The chain extender is at least one of small molecular alcohol with unsaturated groups, small molecular amine with unsaturated groups, small molecular alcohol with saturated groups and small molecular amine with saturated groups.
Preferably, the chain extender comprises at least one of 1, 5-hexadiene-3, 4-diol with 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 6-hexanediamine, 4-trifluoro-3- (trifluoromethyl) -1, 3-butanediol, (E) -4, 4-trifluoro-but-2-en-1-ol.
Preferably, the chain extender mainly comprises 1, 5-hexadiene-3, 4-diol, 3-methyl-1, 5-pentanediol and 1, 6-hexanediol in a molar ratio of (10-20): (40-45): (40-45).
Preferably, the chain extender is composed of 1, 5-hexadiene-3, 4-diol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 4-trifluoro-3- (trifluoromethyl) -1, 3-butanediol in a molar ratio of 1:2:2 (0.2-0.4).
Preferably, the chain extender consists essentially of 1, 5-hexadiene-3, 4-diol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, (E) -4, 4-trifluoro-but-2-en-1-ol in a molar ratio of (10-25): (30-40): 40 (5-10).
The molar ratio of polyol to chain extender is controlled at 1: (0.01-0.3).
The auxiliary agent comprises at least one of a leveling agent, a slipping agent, a wetting dispersant, an adhesion promoter, a coupling agent, a defoaming agent, a thickening agent, an antioxidant, an anti-ultraviolet agent, color paste and a functional filler.
The preparation method of the solvent-free polyurethane resin prepared from the bio-based polyol comprises the preparation of a material A and the preparation of a material B, wherein the preparation of the material A is as follows: the biological polyol, the chain extender, the catalyst and the auxiliary agent in the material A are all mixed together and stirred uniformly; the preparation of the material B is as follows: firstly, putting aliphatic isocyanate MDI into a reaction kettle, heating to 70+/-2.0 ℃, putting all the polyalcohol of the material B into the reaction kettle, maintaining a vacuumizing state, and reacting for 2.0-2.5 hours to obtain the material B; when in use, A, B materials are uniformly mixed according to a proportion, the mixture is scraped on a base fabric, and the base fabric is heated by an oven and then rolled into PU leather.
Example 1: the solvent-free polyurethane resin prepared from the bio-based polyol consists of a material A and a material B.
The material A consists of 100g of poly (1, 3-propanediol succinate) glycol with the molecular weight of 3000, 100g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol with the molecular weight of 3000, 10g of 1, 4-butanediol, 0.12g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168 and 1g of UV-326.
The material B consists of 36g of hexamethylene diisocyanate HDI and 50g of poly (1, 3) propylene glycol ether with molecular weight of 2000.
The preparation method of the solvent-free polyurethane resin prepared from the bio-based polyol comprises the following steps:
the preparation of the material A is as follows: placing 1, 3-propanediol succinate diol with molecular weight of 3000, 100g of 1, 3-propanediol succinate diol with molecular weight of 3000, 10g of 1, 4-butanediol, 0.12g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168 and 1g of UV-326 into a reaction kettle, replacing nitrogen, and uniformly mixing at 300rpm to obtain a material A;
the preparation of the material B is as follows: putting 36g of hexamethylene diisocyanate HDI into a reaction kettle, heating to 70+/-2.0 ℃, putting 50g of poly (1, 3) propylene glycol ether with molecular weight of 2000 into the reaction kettle, maintaining a vacuumizing state, and reacting for 2.0h to obtain a material B;
When in use, the A, B materials prepared above are uniformly mixed, scraped and coated on a base fabric, and rolled into PU leather after being heated by an oven.
Example 2 differs from example 1 in that: the material A consists of 100g of poly (1, 3-propanediol succinate) glycol with the molecular weight of 3000, 100g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol with the molecular weight of 3000, 10g of 1, 4-butanediol, 0.13g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168 and 1g of UV-326.
The material B consists of 36.8g of hexamethylene diisocyanate HDI, 30g of poly (1, 3) propylene glycol ether having a molecular weight of 2000, 30g of a palm oil-based natural oil polyol having a molecular weight of 3000 as in preparation example 1.
Example 3 differs from example 1 in that: the material B consists of 36.8g of hexamethylene diisocyanate HDI, 20g of poly (1, 3-propylene glycol) ether with a molecular weight of 2000 and 20g of castor oil-based natural oil polyol with a molecular weight of 2000 in preparation example 4.
Example 4 differs from example 1 in that: the material A consists of 100g of poly (1, 3-propanediol succinate) glycol with the molecular weight of 3000, 100g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol with the molecular weight of 3000, 10g of 1, 4-butanediol, 0.14g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168 and 1g of UV-326. The material B consists of 36.8g of hexamethylene diisocyanate HDI, 20g of poly (1, 3) propylene glycol ether having a molecular weight of 2000, 30g of castor oil-based natural oil polyol having a molecular weight of 3000 in preparation example 5.
Example 5 differs from example 4 in that: the material B consists of 38.5g of hexamethylene diisocyanate HDI, 20g of poly (1, 3) propylene glycol ether with a molecular weight of 2000 and 30g of castor oil-based natural oil polyol with a molecular weight of 3000 in preparation example 5.
Example 6 differs from example 4 in that: the material B consists of 40.8g of hexamethylene diisocyanate HDI, 20g of poly (1, 3) propylene glycol ether with a molecular weight of 2000 and 30g of castor oil-based natural oil polyol with a molecular weight of 3000 in preparation example 5.
Example 7 differs from example 1 in that: the material A consists of 50g of poly (1, 3-propanediol succinate) glycol with the molecular weight of 3000, 50g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate glycol with the molecular weight of 3000, 100g of castor oil-based natural oil polyol with the molecular weight of 3000 in preparation example 5, 10g of 1, 4-butanediol, 0.14g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168 and 1g of UV-326. The material B consists of 39.0g of hexamethylene diisocyanate HDI and 50g of poly (1, 3-propanediol ether) with molecular weight of 2000.
Example 8 differs from example 1 in that: the material A consists of 50g of poly (1, 3-propanediol succinate) glycol with the molecular weight of 3000, 50g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate glycol with the molecular weight of 3000, 100g of palm oil-based natural oil polyol with the molecular weight of 3000 in preparation example 3, 10g of 1, 4-butanediol, 0.14g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168 and 1g of UV-326. The material B consists of 39.0g of hexamethylene diisocyanate HDI and 50g of poly (1, 3-propanediol ether) with molecular weight of 2000.
Example 9 differs from example 1 in that: the material A consists of 80g of poly (1, 3-propanediol succinate) glycol with the molecular weight of 3000, 60g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate glycol with the molecular weight of 3000, 60g of castor oil-based natural oil polyol with the molecular weight of 3000 in preparation example 5, 10g of 1, 4-butanediol, 0.14g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168 and 1g of UV-326. The material B consists of 38.8g of hexamethylene diisocyanate HDI, 30g of a palm oil-based natural oil polyol having a molecular weight of 3000 in preparation 3, 30g of a poly 1, 3-propylene glycol ether having a molecular weight of 2000.
Example 10 differs from example 1 in that: the material A consists of 50g of poly (1, 3-propanediol succinate) glycol with the molecular weight of 3000, 50g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate glycol with the molecular weight of 3000, 100g of castor oil-based natural oil polyol with the molecular weight of 3000 in preparation example 5, 10g of 1, 4-butanediol, 0.14g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168 and 1g of UV-326. The material B consists of 39.0g of hexamethylene diisocyanate HDI, 18g of modified hydroxysiloxane-JBC-FM 7721 with molecular weight of 5000 and 43g of poly (1, 3) propylene glycol ether with molecular weight of 2000.
Example 11 differs from example 1 in that: the material A consists of 60g of poly (1, 3-propanediol succinate) glycol with the molecular weight of 3000, 60g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate glycol with the molecular weight of 3000, 120g of castor oil-based natural oil polyol with the molecular weight of 3000 in preparation example 5, 10g of 1, 4-butanediol, 0.14g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168 and 1g of UV-326. The material B consists of 42.0g of hexamethylene diisocyanate HDI, 20g of modified hydroxysiloxane-JBC-FM 7721 with molecular weight of 5000 and 40g of poly (1, 3) propylene glycol ether with molecular weight of 2000.
Example 12 differs from example 11 in that: the material B consists of 42.5g of hexamethylene diisocyanate HDI, 40g of modified hydroxysiloxane-JNC-FM 7721 with molecular weight of 5000 and 40g of poly (1, 3) propylene glycol ether with molecular weight of 2000.
Example 13 differs from example 11 in that: the material B consists of 42.2g of hexamethylene diisocyanate HDI, 40g of modified hydroxysiloxane-JNC-FM 7725 with molecular weight 10000 and 40g of poly 1,3 propylene glycol ether with molecular weight 2000.
Example 14 differs from example 11 in that: the material B consists of 41.8g of hexamethylene diisocyanate HDI, 10g of modified hydroxysiloxane-JNC-FM 7721 with molecular weight of 5000 and 40g of poly (1, 3) propylene glycol ether with molecular weight of 2000.
Example 15: a solvent-free polyurethane resin prepared from bio-based polyol consists of a material A and a material B. The material A consists of 60g of poly (1, 3-propanediol succinate) glycol with the molecular weight of 3000, 60g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate glycol with the molecular weight of 3000, 100g of castor oil-based natural oil polyol with the molecular weight of 3000 in preparation example 5, 2g of 1, 5-hexadiene-3, 4-diol, 5g of 3-methyl-1, 5-pentanediol, 5g of 1, 6-hexanediol, 0.12g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168, 1g of UV-326 and 0.5g of polymerization inhibitor-methyl hydroquinone THQ. The material B consists of 38.8g of hexamethylene diisocyanate HDI, 20g of modified hydroxysiloxane-JNC-FM 7721 with molecular weight of 5000 and 40g of poly (1, 3) propylene glycol ether with molecular weight of 2000.
The preparation method of the solvent-free polyurethane resin prepared from the bio-based polyol comprises the following steps:
the preparation of the material A is as follows: 60g of poly (1, 3-propanediol succinate) glycol with molecular weight of 3000, 60g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate glycol with molecular weight of 3000, 100g of castor oil-based natural oil polyol with molecular weight of 3000 in preparation example 5, 2g of 1, 5-hexadiene-3, 4-diol, 5g of 3-methyl-1, 5-pentanediol, 5g of 1, 6-hexanediol, 0.12g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168, 1g of UV-326 and 0.5g of polymerization inhibitor-methylhydroquinone THQ are placed in a reaction kettle, replaced with nitrogen, and uniformly mixed at 300rpm to obtain a material A;
The preparation of the material B is as follows: putting 38.8g of hexamethylene diisocyanate HDI into a reaction kettle, heating to 70+/-2.0 ℃, putting 20g of modified hydroxysiloxane-JNC-FM 7721 with molecular weight of 5000 and 40g of poly (1, 3) propylene glycol ether with molecular weight of 2000 into the reaction kettle, maintaining a vacuumizing state, and reacting for 2.0h to obtain a material B;
when in use, the A, B material prepared above and 0.2g of initiator-azodiisobutyronitrile are mixed uniformly, the mixture is scraped and coated on a base fabric, and the PU leather is rolled after being heated by an oven.
Example 16 differs from example 15 in that: the material A consists of 60g of poly (1, 3-propanediol succinate) glycol with the molecular weight of 3000, 60g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate glycol with the molecular weight of 3000, 100g of castor oil-based natural oil polyol with the molecular weight of 3000 in preparation example 5, 2.8g of 1, 5-hexadiene-3, 4-diol, 6g of 3-methyl-1, 5-pentanediol, 6g of 1, 6-hexanediol, 0.14g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168, 1g of UV-326 and 0.5g of polymerization inhibitor-methylhydroquinone THQ. The material B consists of 41.2g of hexamethylene diisocyanate HDI, 20g of modified hydroxysiloxane-JNC-FM 7721 with molecular weight of 5000 and 40g of poly (1, 3) propylene glycol ether with molecular weight of 2000.
Example 17 differs from example 15 in that: the material A consists of 60g of poly (1, 3-propanediol succinate) diol with a molecular weight of 3000, 60g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate diol with a molecular weight of 3000, 100g of castor oil-based natural oil polyol with a molecular weight of 3000 in preparation example 5, 2.4g of 1, 5-hexadiene-3, 4-diol, 5g of 3-methyl-1, 5-pentanediol, 5g of 1, 6-hexanediol, 0.9g of 4, 4-trifluoro-3- (trifluoromethyl) -1, 3-butanediol, 0.14g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168, 1g of UV-326 and 0.5g of inhibitor-methylhydroquinone THQ. The material B consists of 40.2g of hexamethylene diisocyanate HDI, 20g of modified hydroxysiloxane-JNC-FM 7721 with molecular weight of 5000 and 40g of poly (1, 3) propylene glycol ether with molecular weight of 2000.
Example 18 differs from example 15 in that: the material A consists of 60g of poly (1, 3-propanediol succinate) diol with a molecular weight of 3000, 60g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate diol with a molecular weight of 3000, 100g of castor oil-based natural oil polyol with a molecular weight of 3000 in preparation example 5, 2.3g of 1, 5-hexadiene-3, 4-diol, 4.9g of 3-methyl-1, 5-pentanediol, 4.9g of 1, 6-hexanediol, 1.7g of 4, 4-trifluoro-3- (trifluoromethyl) -1, 3-butanediol, 0.14g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168, 1g of UV-326 and 0.5g of inhibitor-methylhydroquinone THQ. The material B consists of 40.2g of hexamethylene diisocyanate HDI, 20g of modified hydroxysiloxane-JNC-FM 7721 with molecular weight of 5000 and 40g of poly (1, 3) propylene glycol ether with molecular weight of 2000.
Example 19 differs from example 15 in that: the material A consists of 60g of poly (1, 3-propanediol succinate) diol with a molecular weight of 3000, 60g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate diol with a molecular weight of 3000, 100g of castor oil-based natural oil polyol with a molecular weight of 3000 in preparation example 5, 2.5g of 1, 5-hexadiene-3, 4-diol, 5.1g of 3-methyl-1, 5-pentanediol, 5.1g of 1, 6-hexanediol, 0.5g of 4, 4-trifluoro-3- (trifluoromethyl) -1, 3-butanediol, 0.14g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168, 1g of UV-326 and 0.5g of inhibitor-methylhydroquinone THQ. The material B consists of 40.5g of hexamethylene diisocyanate HDI, 20g of modified hydroxysiloxane-JNC-FM 7721 with molecular weight of 5000 and 40g of poly (1, 3) propylene glycol ether with molecular weight of 2000.
Example 20 differs from example 15 in that: the material A consists of 60g of poly (1, 3-propanediol succinate) diol with a molecular weight of 3000, 60g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate diol with a molecular weight of 3000, 100g of castor oil-based natural oil polyol with a molecular weight of 3000 in preparation example 5, 2.3g of 1, 5-hexadiene-3, 4-diol, 4.8g of 3-methyl-1, 5-pentanediol, 4.8g of 1, 6-hexanediol, 2.1g of 4, 4-trifluoro-3- (trifluoromethyl) -1, 3-butanediol, 0.14g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168, 1g of UV-326 and 0.5g of inhibitor-methylhydroquinone THQ. The material B consists of 40.5g of hexamethylene diisocyanate HDI, 20g of modified hydroxysiloxane-JNC-FM 7721 with molecular weight of 5000 and 40g of poly (1, 3) propylene glycol ether with molecular weight of 2000.
Example 21 differs from example 15 in that: the material A consists of 60g of poly (1, 3-propanediol succinate) diol with a molecular weight of 3000, 60g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate diol with a molecular weight of 3000, 100g of castor oil-based natural oil polyol with a molecular weight of 3000 in preparation example 5, 1.4g of 1, 5-hexadiene-3, 4-diol, 4.9g of 3-methyl-1, 5-pentanediol, 4.9g of 1, 6-hexanediol, 2.1g of 4, 4-trifluoro-3- (trifluoromethyl) -1, 3-butanediol, 0.14g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168, 1g of UV-326 and 0.5g of inhibitor-methylhydroquinone THQ. The material B consisted of 36.5g of hexamethylene diisocyanate HDI, 20g of modified hydroxysiloxane-JNC-FM 7721 having a molecular weight of 5000, 40g of poly 1,3 propylene glycol ether having a molecular weight of 2000, 12g of the isocyanate having an unsaturated group in preparation example 1.
Example 22 differs from example 15 in that: the material A consists of 60g of poly (1, 3-propanediol succinate) diol with a molecular weight of 3000, 60g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate diol with a molecular weight of 3000, 100g of castor oil-based natural oil polyol with a molecular weight of 3000 in preparation example 5, 1.4g of 1, 5-hexadiene-3, 4-diol, 4.9g of 3-methyl-1, 5-pentanediol, 4.9g of 1, 6-hexanediol, 2.1g of 4, 4-trifluoro-3- (trifluoromethyl) -1, 3-butanediol, 0.14g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168, 1g of UV-326 and 0.5g of inhibitor-methylhydroquinone THQ. The material B consisted of 38g of hexamethylene diisocyanate HDI, 20g of modified hydroxysiloxane-JNC-FM 7721 having a molecular weight of 5000, 40g of poly 1,3 propylene glycol ether having a molecular weight of 2000, 8g of isocyanate having an unsaturated group in preparation example 1.
Example 23 differs from example 15 in that: the material A consists of 60g of poly (1, 3-propanediol succinate) diol with a molecular weight of 3000, 60g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate diol with a molecular weight of 3000, 100g of castor oil-based natural oil polyol with a molecular weight of 3000 in preparation example 5, 1.4g of 1, 5-hexadiene-3, 4-diol, 4.9g of 3-methyl-1, 5-pentanediol, 4.9g of 1, 6-hexanediol, 2.1g of 4, 4-trifluoro-3- (trifluoromethyl) -1, 3-butanediol, 0.14g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168, 1g of UV-326 and 0.5g of inhibitor-methylhydroquinone THQ. The material B consists of 38g of hexamethylene diisocyanate HDI, 20g of modified hydroxysiloxane-JNC-FM 7721 having a molecular weight of 5000, 40g of poly 1, 3-propanediol ether having a molecular weight of 2000 and 8g of isocyanate having an unsaturated group in preparation example 2.
Example 24 differs from example 15 in that: the material A consists of 60g of poly (1, 3-propanediol succinate) diol with a molecular weight of 3000, 60g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate diol with a molecular weight of 3000, 100g of castor oil-based natural oil polyol with a molecular weight of 3000 in preparation example 5, 1.4g of 1, 5-hexadiene-3, 4-diol, 4.9g of 3-methyl-1, 5-pentanediol, 4.9g of 1, 6-hexanediol, 2.1g of 4, 4-trifluoro-3- (trifluoromethyl) -1, 3-butanediol, 0.14g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168, 1g of UV-326 and 0.5g of inhibitor-methylhydroquinone THQ. The material B consisted of 36g of hexamethylene diisocyanate HDI, 20g of modified hydroxysiloxane-JNC-FM 7721 having a molecular weight of 5000, 40g of poly 1,3 propylene glycol ether having a molecular weight of 2000, 12g of isocyanate having an unsaturated group in preparation example 2.
Example 25 differs from example 15 in that: the material A consists of 60g of poly (1, 3-propanediol succinate) glycol with the molecular weight of 3000, 60g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate glycol with the molecular weight of 3000, 100g of castor oil-based natural oil polyol with the molecular weight of 3000 in preparation example 5, 2.5g of 1, 5-hexadiene-3, 4-diol, 3.9g of 3 methyl-1, 5-pentanediol, 5.2g of 1, 6-hexanediol, 0.14g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168, 1g of UV-326 and 0.5g of polymerization inhibitor-methyl hydroquinone THQ. The material B consisted of 38.5g of hexamethylene diisocyanate HDI, 20g of modified hydroxysiloxane-JNC-FM 7721 having a molecular weight of 5000, 40g of poly 1, 3-propylene glycol ether having a molecular weight of 2000, 10g of isocyanate having an unsaturated group in preparation example 2, 1.4g of (E) -4, 4-trifluoro-but-2-en-1-ol, and 0.2g of polymerization inhibitor-methylhydroquinone THQ.
The preparation method of the solvent-free polyurethane resin prepared from the bio-based polyol comprises the following steps:
the preparation of the material A is as follows: 60g of poly (1, 3-propanediol succinate) glycol with molecular weight of 3000, 60g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate glycol with molecular weight of 3000, 100g of castor oil-based natural oil polyol with molecular weight of 3000 in preparation example 5, 2.5g of 1, 5-hexadiene-3, 4-diol, 3.9g of 3 methyl-1, 5-pentanediol, 5.2g of 1, 6-hexanediol, 0.14g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168, 1g of UV-326 and 0.5g of polymerization inhibitor-methylhydroquinone THQ are placed in a reaction kettle, replaced with nitrogen, and uniformly mixed at 300rpm to obtain a material A;
The preparation of the material B is as follows: putting 38.5g of hexamethylene diisocyanate HDI, 10g of isocyanate with unsaturated groups in preparation example 2 and 0.2g of polymerization inhibitor-methyl hydroquinone THQ into a reaction kettle, heating to 70+/-2.0 ℃, putting 20g of modified hydroxysiloxane-JNC-FM 7721 with molecular weight of 5000 and 40g of poly (1, 3) propylene glycol ether with molecular weight of 2000 into the reaction kettle, maintaining a vacuumizing state, and reacting for 2.0h to obtain a material B;
when in use, the A, B material prepared above and 0.24g of initiator-azodiisobutyronitrile are uniformly mixed, the mixture is scraped and coated on a base fabric, and the base fabric is heated by an oven and then rolled into PU leather.
Comparative example 1 differs from example 1 in that: the material A consists of 100g of poly (1, 3-propanediol succinate) glycol with the molecular weight of 3000, 100g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol with the molecular weight of 3000, 10g of 1, 4-butanediol, 0.12g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168 and 1g of UV-326. The material B consists of 53.6g of MDI and 50g of poly (1, 3-propanediol ether) with a molecular weight of 2000.
Comparative example 2 differs from example 1 in that: the material A consists of 200g of poly (adipic acid) diacid/1, 6-hexanediol ester diol with the molecular weight of 3000, 10g of 1,4 butanediol, 0.12g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168 and 1g of UV-326. The material B consists of 53.6g of MDI and 50g of poly-1, 6-hexanediol ether with a molecular weight of 2000.
Comparative example 3 differs from example 1 in that: the material A consists of 200g of terephthalic acid/1, 6-hexanediol ester glycol with a molecular weight of 3000, 10g of 1, 4-butanediol, 0.12g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168 and 1g of UV-326. The material B consists of 36g of hexamethylene diisocyanate HDI and 50g of poly (1, 6-hexanediol) ether with a molecular weight of 2000.
Comparative example 4 differs from example 1 in that: the material A consists of 200g of terephthalic acid/1, 6-hexanediol ester glycol with a molecular weight of 3000, 10g of 1, 4-butanediol, 0.12g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168 and 1g of UV-326. The material B consists of 53.6g of MDI and 50g of poly-1, 6-hexanediol ether with a molecular weight of 2000.
Comparative example 5 differs from example 1 in that: a bio-based polyester polyol solvent-based polyurethane resin is composed of 100g of poly (1, 3-propanediol succinate) glycol with a molecular weight of 3000, 100g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol ester glycol with a molecular weight of 3000, 10g of 1, 4-butanediol, 0.15g of bismuth octoate, 1g of antioxidant 1010, 0.2g of antioxidant 168, 1g of UV-326, 36g of hexamethylene diisocyanate HDI, 50g of poly (1, 3-propanediol ether) with a molecular weight of 2000, 500g of DMF, 200g of xylene and 1.0g of methanol.
Biological materialThe preparation method of the solvent-based polyurethane resin prepared from the polyester polyol is a solvent method, and specifically comprises the following steps: adding 100g of poly (1, 3-propanediol succinate) glycol with molecular weight of 3000, 100g of poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate glycol with molecular weight of 3000, 50g of poly (1, 3-propanediol ether) with molecular weight of 2000, 300g of dimethylformamide DMF, 6g of 1, 4-butanediol into a reactor, heating to 45 ℃, stirring for 30min, adding 36g of hexamethylene diisocyanate HDI and 0.15g of bismuth octoate, heating to 95 ℃ for reaction for 2.0h, adding 200g of dimethylformamide DMF and 200g of dimethylbenzene, cooling to 40 ℃, adding the rest of 4.0g of 1, 4-butanediol into the reactor at a dropping speed of 1.0g/10s, and when the reaction viscosity is detected to reach 1.8-2.0x10 5 And adding 1.0g of methanol to react for 30min at the temperature of mPas/25 ℃ to terminate the reaction, thus obtaining the finished resin. When the PU leather is used, in the production process of the synthetic leather, the finished resin is used as a surface layer to be coated, and the PU leather is obtained after being rolled up after being dried in a baking oven at 150 ℃ for 10 min.
1. The heat resistance testing method comprises the following steps: the polyurethane resins of examples 1 to 25 and comparative examples 1 to 5 were respectively formed into films on release papers, and two samples of 4cm long and 1cm wide (no bubbles, no cracks, no pinholes, no gaps, and smooth edges were required) were drawn on the formed films with a ruler. Binding the two ends of the sample with wires respectively, hanging a clip at one end and three clips at the other end, and separating the leather film from the release paper. And hanging the worn test sample on an oven (one clip is hung above and three clips are hung below), starting the oven, and recording the temperature when the clip at the lower end touches the bottom of the oven, namely the softening point temperature of the resin.
2. Peel strength test method: the basic cloth is superfine cloth provided by Hexin colali microfiber skin (Jiaxing) limited company, the surface layer resin is an aqueous surface layer for automobile leather made by Hexin technology, the adhesive between the basic cloth and the surface layer is solvent-free polyurethane resin prepared by biological-based polyalcohol prepared in examples 1-25 and comparative examples 1-5, test samples 1-25 and comparative samples 1-5 are prepared, a method GB/T2791-1995 is adopted for testing the peel strength of flexible materials to flexible materials by an adhesive T peel strength test method, and the test samples 1-25 and comparative samples 1-5 and the comparative example 1 automobile leather are tested for peel strength. Cutting a test piece: two 200mm by 120mm specimens were cut in the warp (weft) direction.
The testing method comprises the following steps: the solvent-free polyurethane resin glue prepared by using a proper amount of the bio-based polyol prepared in examples 1-25 and comparative examples 1-5 is coated on the surface of one of the samples, and is adhered to the surface of the other sample, and then the samples are pushed by a small hammer or rolled for a plurality of times, so that the samples can be well adhered. The test specimen was left at the beginning end of about 50 a mm a without glue. And placing the bonded sample in a blast constant temperature drying oven with the temperature of 120+/-5 ℃, drying for 20min, taking out the sample, and cooling to the room temperature. The test pieces were cut into three groups of 150mm×30mm, and then peel strength test was performed on the test pieces after the bonding treatment. And respectively clamping the two separated ends on a clamp of an electronic tension machine, setting the stretching speed to be 100mm/min, selecting the test state as a leather peeling test, starting the tension machine, and observing the peeling state of the sample. After the peeling force of the test specimen was stabilized, the electronic tensile machine was manually stopped to reset the test specimen, and the peeling strength (average value) of the test specimen was recorded.
The preparation method of the water-based surface layer for the automobile leather specifically comprises the following steps: 43 parts of caprolactone type polycarbonate diol with the molecular weight of 2000, 5 parts of HDI, 20 parts of H12MDI and 0.08 part of organic bismuth are sequentially added at the stirring rotation speed of 150 minutes, and the mixture is reacted for 2.0 hours at the temperature of 88.9 ℃; then adding 3 parts of 1, 5-pentanediol, 3.5 parts of DMPA and 8 parts of acetone, and reacting for 2 hours at 80 ℃, wherein the reaction kettle is required to be provided with an acetone condensation reflux device and a pressure relief device; adding the rest 12 parts of acetone into the mixture for 4 times for dilution, and controlling the viscosity to be 600 Pa.s; when the temperature is lower than 45 ℃, adding 2 parts of dimethylethanolamine for neutralization for 3 minutes; adding 60 parts of deionized water for dispersing under high-speed shearing of a shearing and dispersing machine; distilling to remove acetone to obtain the target product.
3. Hydrolysis resistance test method: and (3) placing the test samples 1-25 and the comparison samples 1-5 in deionized water at 80 ℃ for soaking for 168 hours, and observing whether the degumming problem occurs among the base cloth, the adhesive layer and the surface layer.
4. The jungle testing method comprises the following steps:
test (1): after being placed in an environment with 80 ℃ and 75% humidity for 1000 hours, the steel plate is bent for 10 ten thousand times at 25 ℃ to observe whether cracking occurs; and bending for 2 ten thousand times at the temperature of minus 20 ℃ to observe whether cracking occurs.
Test (2): the peel strength A1 of examples 1 to 22 and comparative examples 1 to 5 was measured, and then after being left under an atmosphere of 80℃and 75% humidity for 1000 hours, the peel strength A2 of examples 1 to 22 and comparative examples 1 to 5 was measured.
5. The aging resistance test method comprises the following steps: the number of samples tested per group was 3 pieces tested according to the method of Q/JLJ 160004-2015& Q/JLYJ 7110279B-2014 interior trim.
6. Light fastness test: xenon lamp testing was performed in accordance with ISO 105-B06.
Table 1 is a table of test parameters for the solvent-free polyurethane resins of examples 1-25 and comparative examples 1-5
Table 2 is a table of test parameters for the solvent-free polyurethane resins of examples 1 to 25 and comparative examples 1 to 5
As can be seen from the combination of examples 1 to 25 and comparative examples 1 to 5 and the comparison of examples 1 to 2, the polyurethane resin prepared by the solvent method has better heat resistance and bonding strength than the polyurethane resin prepared by the solvent-free method, and the polyurethane resin prepared by the solvent-free method has better environmental protection performance, and the bonding strength meets the conventional use requirement and the requirement of the masses on the environmental protection polyurethane adhesive, although the heat resistance of the polyurethane resin prepared by the solvent-free method is relatively poorer.
As can be seen from the combination of examples 1 to 25 and comparative examples 1 to 5 and the combination of tables 1 to 2, the comparison of examples 1 and comparative examples 1 to 2 shows that the polyurethane resin prepared by the solvent-free method prepared from the petroleum-based polyol has relatively better heat resistance and bonding strength than the polyurethane resin prepared by the solvent-free method prepared from the bio-based polyol, but the heat resistance and bonding strength of the polyurethane resin prepared by the solvent-free method prepared from the bio-based polyol are not greatly different, and the polyurethane resin prepared by the solvent-free method prepared from the bio-based polyol has better environmental protection performance, and the bonding strength of the polyurethane resin also meets the conventional use requirements, meets the requirements of masses on environmental protection polyurethane adhesives, reduces the dependence on fossil raw materials and accords with the sustainable development concept.
As can be seen from a combination of examples 1 to 25 and comparative examples 1 to 5 and a combination of tables 1 to 2, the solvent-free polyurethane resin prepared using the aromatic isocyanate and/or the polyol having a benzene ring structure has excellent heat resistance but relatively weak yellowing resistance and abrasion resistance as compared with the solvent-free polyurethane resin prepared using the aliphatic isocyanate of example 1, as can be seen from a comparison of examples 1 and comparative examples 1 to 4. The solvent-free polyurethane resin in the embodiment 1 has better yellowing resistance and wear resistance, and is prepared from a biological base material and combined with aliphatic isocyanate, so that the solvent-free polyurethane resin has good environmental protection performance, the bonding strength is more than or equal to 45N/3cm, the conventional use requirement is met, the requirement of the masses on environmental-friendly polyurethane adhesive is met, the dependence on fossil raw materials is reduced, and the sustainable development concept is met.
As can be seen by combining examples 1-25 and comparative examples 1-5 and combining tables 1-2, the bio-based polyol in the A material comprises at least one of poly (1, 3-propanediol ester) diol with molecular weight of 400-5000, poly (1, 3-propanediol ester) diol with molecular weight of 1000-5000, and vegetable oil-based natural oil polyol with molecular weight of 1000-5000, and the bio-based polyol in the B material is at least one of poly (1, 3-propanediol ether) with molecular weight of 400-5000 and vegetable oil-based natural oil polyol with molecular weight of 1000-5000, so that the polyurethane resin prepared by comparing the example 1 with the examples 2-10 has better environmental protection performance and similar bonding performance, enriches the sources of the bio-based polyol, can further reduce the dependence on fossil raw materials, and accords with the sustainable development concept.
As can be seen from a comparison of examples 10 with examples 11-14, the addition of the modified hydroxysiloxane improves the overall heat stability and weather resistance as well as from a comparison of examples 1-25 and comparative examples 1-5 in combination with tables 1-2.
As can be seen from the combination of examples 1-25 and comparative examples 1-5 and the combination of tables 1-2, the polyurethane resin prepared from the chain extender mainly comprising 1, 5-hexadiene-3, 4-diol, 3-methyl-1, 5-pentanediol and 1, 6-hexanediol in the molar ratio of (10-20): (40-45): (40-45) has better mechanical properties, heat resistance, weather resistance and bonding stability.
As can be seen from the combination of examples 1 to 25 and comparative examples 1 to 5 and the combination of tables 1 to 2, the polyurethane resin prepared from 1, 5-hexadiene-3, 4-diol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 4-trifluoro-3- (trifluoromethyl) -1, 3-butanediol in a molar ratio of 1:2:2 (0.2 to 0.4) has a peel strength reduced, but still is not less than 45N/3cm, meets the conventional use requirements, and has better mechanical properties, heat resistance, excellent weather resistance and bonding stability.
As can be seen from the combination of examples 1 to 25 and comparative examples 1 to 5 and the combination of tables 1 to 2, the addition of the isocyanate having an unsaturated group in preparation example 1 improves the heat-resistant stability of the whole, does not affect the mechanical properties and the adhesive properties thereof, and can expand the range of use of the whole as compared with example 20.
As can be seen from the comparison of examples 23 to 24 and example 20 in combination with examples 1 to 25 and comparative examples 1 to 5, the addition of the isocyanate having an unsaturated group in preparation example 2 improves the overall heat resistance stability without affecting the mechanical properties and adhesive properties, and can expand the overall application range.
As can be seen from the comparison of examples 1-25 and comparative examples 1-5 in combination with tables 1-2, the chain extender is mainly a solvent-free polyurethane resin prepared from 1, 5-hexadiene-3, 4-diol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, (E) -4, 4-trifluoro-but-2-en-1-ol in a molar ratio of (10-25): 30-40): 40 (5-10), although the peel strength is reduced, the peel strength is still more than or equal to 45N/3cm, the conventional use requirement is met, in addition, the heat resistance is comparable to that of an aromatic isocyanate and/or a polyol with a benzene ring structure, the polyurethane resin has good environmental protection performance, weather resistance and bonding stability (the peel strength retention rate after a jungle test is more than 85 percent), and the whole use range is expanded.
In conclusion, the solvent-free polyurethane resin disclosed by the application adopts the bio-based polyol to be combined with the aliphatic isocyanate, has excellent environmental protection performance, can reduce dependence on fossil raw materials, accords with a sustainable development concept, and has higher wear resistance, high heat resistance, high yellowing resistance, good flexibility and good market prospect when being used as a binder for preparing leather materials. In addition, the preparation method of the solvent-free polyurethane resin prepared from the bio-based polyol is relatively simple, production equipment is conventional equipment, the operation difficulty is relatively low, and the industrial production and manufacturing are convenient to realize.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. A solvent-free polyurethane resin prepared from bio-based polyol is characterized in that: the preparation method comprises a material A and a material B, wherein the material A mainly comprises bio-based polyol, a chain extender, an auxiliary agent and a catalyst; the material B mainly comprises aliphatic isocyanate and bio-based polyol;
the total molar quantity of the-NCO contained in the material B is 1.05-1.20 times of the total molar quantity of the active groups contained in the material A and the material B;
the mass of the catalyst is equal to 10ppm-500ppm of the total mass of the aliphatic isocyanate, the bio-based polyol and the chain extender;
the catalyst is prepared by mixing at least one of an organobismuth catalyst, an organotin catalyst, a copper bismuth catalyst and DBU salt with an initiator;
the initiator comprises at least one of azodiisobutyronitrile, azodiisoheptonitrile, dibenzoyl peroxide, ditert-butyl peroxide, dicumyl peroxide, diisopropyl peroxydicarbonate and tert-butyl peroxybenzoate;
The aliphatic isocyanate comprises at least one of isophorone diisocyanate IPDI, hexamethylene diisocyanate HDI, 4' -diisocyanate HMDI, methylcyclohexane diisocyanate HTDI and trimethylhexamethylene diisocyanate TMDI;
the bio-based polyol in the material A comprises at least one of poly (1, 3-propanediol succinate) glycol with the molecular weight of 400-5000, poly (succinic acid)/1, 3-propanediol/1, 4-butanediol succinate glycol and vegetable oil-based natural oil polyol with the molecular weight of 1000-5000;
the bio-based polyol in the material B is at least one of poly 1,3 propylene glycol ether with the molecular weight of 400-5000 and vegetable oil-based natural oil polyol with the molecular weight of 1000-5000;
the vegetable oil-based natural oil polyol comprises at least one of palm oil-based natural oil polyol, castor oil-based natural oil polyol, linseed oil-based natural oil polyol and linseed oil-based natural oil polyol;
the preparation method of the vegetable oil-based natural oil polyol comprises the following steps:
firstly, feeding, namely uniformly mixing vegetable oil, dihydric alcohol and tetraisopropyl titanate;
the dihydric alcohol in the first step comprises at least one of 1,3 propylene glycol and 1,4 butanediol;
Step two, heating to 130-140 ℃ and reacting to obtain effluent;
step three, heating to 220-230 ℃ and carrying out transesterification for 2-2.5h;
step four, detecting that the acid value is lower than 25mgKOH/g, starting vacuumizing, lasting for 0.1-3.0h, detecting the OH-value, and controlling the OH-value to be 35.4-115 to obtain the finished castor oil-based natural oil polyol
The chain extender is at least one of small molecular alcohol with unsaturated groups, small molecular amine with unsaturated groups, small molecular alcohol with saturated groups and small molecular amine with saturated groups;
the molar ratio of the polyol to the chain extender is controlled at 1: (0.01-0.3);
the auxiliary agent comprises at least one of a leveling agent, a slipping agent, a wetting dispersant, an adhesion promoter, a coupling agent, a defoaming agent, a thickening agent, an antioxidant, an anti-ultraviolet agent, color paste and a functional filler.
2. The solvent-free polyurethane resin made of the bio-based polyol according to claim 1, wherein the solvent-free polyurethane resin is characterized in that: the bio-based polyol mainly comprises 1, 3-propanediol succinate glycol with a molecular weight of 3000, 1, 3-propanediol succinate/1, 4-butanediol succinate glycol with a molecular weight of 3000 and poly 1, 3-propanediol ether with a molecular weight of 2000 in a molar ratio of (0.5-2) to (0.5-2).
3. The solvent-free polyurethane resin made of the bio-based polyol according to claim 1, wherein the solvent-free polyurethane resin is characterized in that: the bio-based polyol mainly comprises 1, 3-propanediol succinate glycol with the molecular weight of 3000, 1, 3-propanediol succinate/1, 4-butanediol succinate glycol with the molecular weight of 3000, poly 1, 3-propanediol ether with the molecular weight of 2000 and castor oil-based natural oil polyol with the molecular weight of 3000 in a molar ratio of (0.5-2) to (0.8-3.2).
4. The solvent-free polyurethane resin made of the bio-based polyol according to claim 1, wherein the solvent-free polyurethane resin is characterized in that: the bio-based polyol mainly comprises 1, 3-propanediol succinate diol with a molecular weight of 3000, 1, 3-propanediol succinate diol/1, 4-butanediol succinate diol with a molecular weight of 3000, 1, 3-propanediol ether with a molecular weight of 2000, castor oil-based natural oil polyol with a molecular weight of 3000 and modified hydroxysiloxane with a molar ratio of 1:1:1 (1.8-3.2) to (0.2-0.4); the molecular weight of the modified hydroxyl siloxane is 5000-10000, and unsaturated bonds are arranged at two ends of the modified hydroxyl siloxane.
5. The solvent-free polyurethane resin made of the bio-based polyol according to claim 1, wherein the solvent-free polyurethane resin is characterized in that: the chain extender comprises at least one of 1, 5-hexadiene-3, 4-diol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 6-hexamethylenediamine, 4-trifluoro-3- (trifluoromethyl) -1, 3-butanediol and (E) -4, 4-trifluoro-but-2-en-1-ol.
6. The solvent-free polyurethane resin made of the bio-based polyol according to claim 5, wherein the solvent-free polyurethane resin is characterized in that: the chain extender mainly comprises 1, 5-hexadiene-3, 4-diol, 3-methyl-1, 5-pentanediol and 1, 6-hexanediol according to the molar ratio of (10-20): (40-45): (40-45).
7. The solvent-free polyurethane resin made of the bio-based polyol according to claim 5, wherein the solvent-free polyurethane resin is characterized in that: the chain extender consists of 1, 5-hexadiene-3, 4-diol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol and 4, 4-trifluoro-3- (trifluoromethyl) -1, 3-butanediol with the molar ratio of 1:2:2 (0.2-0.4).
8. The solvent-free polyurethane resin made of the bio-based polyol according to claim 5, wherein the solvent-free polyurethane resin is characterized in that: the chain extender mainly comprises 1, 5-hexadiene-3, 4-diol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol and (E) -4, 4-trifluoro-but-2-en-1-ol according to the molar ratio of (10-25): (30-40): 40 (5-10).
9. The solvent-free polyurethane resin made of the bio-based polyol according to claim 1, wherein the solvent-free polyurethane resin is characterized in that: the aliphatic isocyanate is aliphatic isocyanate ADI with unsaturated groups and saturated groups; the aliphatic isocyanate ADI with saturated groups is at least one of isophorone diisocyanate IPDI, hexamethylene diisocyanate HDI, 4' -diisocyanate HMDI, methylcyclohexane diisocyanate HTDI and trimethylhexamethylene diisocyanate TMDI.
10. A method for preparing a solvent-free polyurethane resin from a bio-based polyol according to any one of claims 1 to 9, wherein: comprises the preparation of material A and the preparation of material B;
the preparation of the material A is as follows: the biological polyol, the chain extender, the catalyst and the auxiliary agent in the material A are all mixed together and stirred uniformly;
the preparation of the material B is as follows: firstly, putting aliphatic isocyanate into a reaction kettle, heating to 70+/-2.0 ℃, putting all the polyalcohol of the material B into the reaction kettle, maintaining a vacuumizing state, and reacting for 2.0-2.5 hours to obtain the material B;
and uniformly mixing A, B materials according to a proportion, scraping and coating the mixture on a base fabric, heating the base fabric by an oven, and rolling the base fabric into leather.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117821000A (en) * | 2023-12-25 | 2024-04-05 | 昆山红苹果塑胶新材料有限公司 | TPU adhesive, production process thereof and TPU product using TPU adhesive |
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| CN115044009A (en) * | 2022-05-30 | 2022-09-13 | 西安交通大学 | Preparation method of bio-based degradable waterborne polyurethane resin |
| CN116042160A (en) * | 2023-01-04 | 2023-05-02 | 万华化学（北京）有限公司 | Solvent-free polyurethane-based adhesive and preparation method thereof |
| CN116063975A (en) * | 2021-11-02 | 2023-05-05 | 浙江华峰合成树脂有限公司 | Polyurethane adhesive and preparation and application thereof |
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| JP2011226047A (en) * | 2010-04-02 | 2011-11-10 | Honda Motor Co Ltd | Synthetic imitation leather made by using bio-polyurethane resin |
| CN103642449A (en) * | 2013-12-09 | 2014-03-19 | 山东一诺威聚氨酯股份有限公司 | Solvent-free non-yellowing type polyurethane adhesive for sport field |
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