CN115403740A - Biodegradable carbon dioxide-based polyurethane resin and preparation method thereof - Google Patents
Biodegradable carbon dioxide-based polyurethane resin and preparation method thereof Download PDFInfo
- Publication number
- CN115403740A CN115403740A CN202211108800.6A CN202211108800A CN115403740A CN 115403740 A CN115403740 A CN 115403740A CN 202211108800 A CN202211108800 A CN 202211108800A CN 115403740 A CN115403740 A CN 115403740A
- Authority
- CN
- China
- Prior art keywords
- carbon dioxide
- parts
- diisocyanate
- polyurethane resin
- sulfonate
- 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.)
- Withdrawn
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 83
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 83
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 241000219782 Sesbania Species 0.000 claims abstract description 57
- 229920002635 polyurethane Polymers 0.000 claims abstract description 49
- 239000004814 polyurethane Substances 0.000 claims abstract description 49
- 150000003077 polyols Chemical group 0.000 claims abstract description 40
- 229920005862 polyol Polymers 0.000 claims abstract description 34
- 239000004970 Chain extender Substances 0.000 claims abstract description 26
- 125000003158 alcohol group Chemical group 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 29
- -1 sulfonate compound Chemical class 0.000 claims description 17
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 13
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- UQOQXWZPXFPRBR-UHFFFAOYSA-K bismuth dodecanoate Chemical compound [Bi+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O UQOQXWZPXFPRBR-UHFFFAOYSA-K 0.000 claims description 4
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 4
- 229940093476 ethylene glycol Drugs 0.000 claims description 4
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- VRRABDXZDGRGPC-UHFFFAOYSA-M sodium;2-(2-aminoethylamino)ethanesulfonate Chemical compound [Na+].NCCNCCS([O-])(=O)=O VRRABDXZDGRGPC-UHFFFAOYSA-M 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 3
- VIJMMQUAJQEELS-UHFFFAOYSA-N n,n-bis(ethenyl)ethenamine Chemical compound C=CN(C=C)C=C VIJMMQUAJQEELS-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 3
- 229960004063 propylene glycol Drugs 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- BVIXTPMSXQAQBG-UHFFFAOYSA-N 2-(2-hydroxyethylamino)ethanesulfonic acid Chemical compound OCCNCCS(O)(=O)=O BVIXTPMSXQAQBG-UHFFFAOYSA-N 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- KICVIQZBYBXLQD-UHFFFAOYSA-M sodium;2,5-dihydroxybenzenesulfonate Chemical compound [Na+].OC1=CC=C(O)C(S([O-])(=O)=O)=C1 KICVIQZBYBXLQD-UHFFFAOYSA-M 0.000 claims description 2
- LQHZUHYCGBWCKC-UHFFFAOYSA-M sodium;1,4-dihydroxybutane-2-sulfonate Chemical compound [Na+].OCCC(CO)S([O-])(=O)=O LQHZUHYCGBWCKC-UHFFFAOYSA-M 0.000 claims 2
- KJIKTXVDOGQVIJ-UHFFFAOYSA-M sodium;4,6-dihydroxynaphthalene-2-sulfonate Chemical compound [Na+].C1=C(S([O-])(=O)=O)C=C(O)C2=CC(O)=CC=C21 KJIKTXVDOGQVIJ-UHFFFAOYSA-M 0.000 claims 1
- JFXDYPLHFRYDJD-UHFFFAOYSA-M sodium;6,7-dihydroxynaphthalene-2-sulfonate Chemical compound [Na+].C1=C(S([O-])(=O)=O)C=C2C=C(O)C(O)=CC2=C1 JFXDYPLHFRYDJD-UHFFFAOYSA-M 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000006065 biodegradation reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920003225 polyurethane elastomer Polymers 0.000 description 4
- 239000001273 butane Substances 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JFXDYPLHFRYDJD-UHFFFAOYSA-N sodium;6,7-dihydroxynaphthalene-2-sulfonic acid Chemical compound [Na+].C1=C(S(O)(=O)=O)C=C2C=C(O)C(O)=CC2=C1 JFXDYPLHFRYDJD-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-SVZMEOIVSA-N (+)-Galactose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-SVZMEOIVSA-N 0.000 description 2
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 2
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 2
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 2
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000005034 decoration Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229930182830 galactose Natural products 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- XPSMVRPVDSKYNJ-UHFFFAOYSA-M sodium;2-(2-hydroxyethylamino)ethanesulfonate Chemical compound [Na+].OCCNCCS([O-])(=O)=O XPSMVRPVDSKYNJ-UHFFFAOYSA-M 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108090000371 Esterases Proteins 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- SSQNAPWMQSPZRM-UHFFFAOYSA-N benzene-1,4-diol;sodium Chemical compound [Na].OC1=CC=C(O)C=C1 SSQNAPWMQSPZRM-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012707 chemical precursor Substances 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 125000000311 mannosyl group Chemical group C1([C@@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- MBAUOPQYSQVYJV-UHFFFAOYSA-N octyl 3-[4-hydroxy-3,5-di(propan-2-yl)phenyl]propanoate Chemical compound OC1=C(C=C(C=C1C(C)C)CCC(=O)OCCCCCCCC)C(C)C MBAUOPQYSQVYJV-UHFFFAOYSA-N 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000002699 waste material Substances 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
- C08G18/40—High-molecular-weight compounds
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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
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
The invention provides a biodegradable carbon dioxide-based polyurethane resin, wherein a main chain structure of the polyurethane comprises a carbon dioxide-based polyol chain segment and a sesbania gum chain segment; the biodegradable carbon dioxide-based polyurethane resin comprises the following preparation raw materials in parts by weight: sesbania gum: 3.5-6.5 parts of carbon dioxide-based polyol: 70-220 parts of aromatic diisocyanate: 8-12 parts of aliphatic diisocyanate: 20-45 parts of antioxidant: 0.28-0.95 part, 0.05-0.11 part of catalyst, alcohol chain extender: 0.6-2.3 parts of sulfonate chain extender: 0.7 to 1.6 portions. The invention uses carbon dioxide-based dihydric alcohol as a soft segment, introduces sesbania gum component into the main chain structure, and improves the biodegradability of polyurethane. The invention also provides a preparation method of the biodegradable carbon dioxide-based polyurethane resin.
Description
Technical Field
The invention belongs to the technical field of polyurethane resin, and particularly relates to biodegradable carbon dioxide-based polyurethane resin and a preparation method thereof.
Background
The polyurethane resin is a macromolecular polymer formed by prepolymerizing aromatic or aliphatic isocyanate and polyester or polyether polyol and then extending chains, is known as 'fifth plastic' as a novel organic macromolecular material, is one of the fastest-developing varieties in the modern plastic industry, and has been widely applied to various fields of national economy due to excellent performance. However, polyurethane is not degradable in nature and is difficult to recycle, so the vigorous development of polyurethane also brings the problem that the waste thereof pollutes the environment, and therefore, the development of a biodegradable polyurethane material is considered to be one of the ideal ways to solve the problem.
The biodegradable polyurethane resin is mainly designed in two schemes, wherein the first scheme is that the soft segment structure of the polyurethane is a biodegradable component, and the second scheme is that the surface of the polyurethane is subjected to hydrophilic modification. The first scheme is representative of the preparation of biodegradable polyurethanes using polyalkylene carbonate having good biodegradability as a soft segment. CN102002142 prepares a biodegradable polyurethane with polyalkylene carbonate-polylactic acid block copolymer diol as soft segment, and its relative biodegradation rate exceeds 90% in three months under composting condition. CN1865311 prepares polyethylene carbonate polyurethane elastomer by using polyethylene carbonate diol as soft segment, schingyi et al (journal of biomedical engineering, 1999, 16, 121-122) synthesizes a category of polycarbonate polyurethane elastomer with biological properties by using polyhexamethylene glycol carbonate diol as raw material, penhan et al (chemical world, 1995, 8. The second scheme is hydrophilic modification of the surface of polyurethane, the principle of the scheme is a biodegradation process, and the biodegradation process is an enzymolysis process of polyurethane by microorganisms, and the microorganisms are required to be well attached to the surface of the polyurethane, so that the secreted esterase degrades high polymer chains of the polyurethane material to generate a low molecular weight compound, and finally the biodegradation process is finished, so that the polyurethane is required to have certain hydrophilicity, and the microorganisms are ensured to be well attached to the surface of the polyurethane to finish the degradation process. Polyethylene glycol (PEG) has been studied extensively as an important hydrophilic polymer for improving the biodegradability of polyurethane. Tian et al [ chemical precursors and Polymeric Materials,2013, 11 (3): 85-88] prepared biodegradable polyurethanes using PEG as initiator. CN1191289 reports a biodegradable polyurethane elastomer with PEG and polycaprolactone as soft segments. Lixing et al (science and engineering of high molecular materials, 2017, 33 (8): 17-26) PEG as an initiator, ring-opening polymerization is carried out on L-lactide, and the prepared polylactide-polyethylene glycol-polylactide triblock prepolymer reacts with 2, 6-hexamethylene diisocyanate to prepare biodegradable polyurethane. Although some progress has been made in biodegradable polyurethanes, the biodegradability of the polyurethanes still needs to be improved.
Disclosure of Invention
The invention aims to provide a biodegradable carbon dioxide-based polyurethane resin and a preparation method thereof.
The invention provides a biodegradable carbon dioxide-based polyurethane resin, wherein a main chain structure of the polyurethane comprises a carbon dioxide-based polyol chain segment and a sesbania gum chain segment;
the biodegradable carbon dioxide-based polyurethane resin comprises the following preparation raw materials in parts by weight:
sesbania gum: 3.5-6.5 parts of carbon dioxide-based polyol: 70-220 parts of aromatic diisocyanate: 8-12 parts of aliphatic diisocyanate: 20-45 parts of antioxidant: 0.28-0.95 parts, 0.05-0.11 parts of catalyst, alcohol chain extender: 0.6-2.3 parts of sulfonate chain extender: 0.7 to 1.6 portions.
Preferably, the molecular weight of the carbon dioxide-based polyol is 1000-5000 g/mol, and the content of the carbonic ester is 30-80 wt%.
Preferably, the aliphatic diisocyanate is one or more of hexamethylene diisocyanate, 1, 4-butane diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate;
the aromatic diisocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate and naphthalene diisocyanate.
Preferably, the catalyst is one or more of stannous octoate, stannous chloride, bismuth neodecanoate, bismuth laurate, dibutyltin dilaurate, triethyleneamine, triethanolamine and triethylamine.
Preferably, the alcohol chain extender is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 4-cyclohexanediol, trimethylolpropane, glycerol, diethylene glycol, triethylene glycol, neopentyl glycol and sorbitol;
the sulfonate chain extender is a dihydroxy sulfonate compound and/or an amino sulfonate compound.
Preferably, the dihydroxy sulfonate compound is one or more of N, N- (2-hydroxyethyl) -2-aminoethyl sulfonate, 2, 5-dihydroxy benzene sodium sulfonate, 2, 3-dihydroxy naphthalene-6-sodium sulfonate, 1, 4-dihydroxy-2-butane sodium sulfonate, 2, 8-dihydroxy naphthalene-6-sodium sulfonate, 2-dihydroxy-3-propane sodium sulfonate and 1, 4-dihydroxy butane-2-sodium sulfonate;
the sulfamate compound is one or more of sodium ethylene diamino sulfonate (AAS) and N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt.
The present invention provides a method for preparing biodegradable carbon dioxide-based polyurethane resin as described above, comprising the steps of:
a) Mixing sesbania gum, aromatic diisocyanate, an antioxidant and a catalyst, and reacting for 1-3 hours at 100-140 ℃ to obtain a polyurethane prepolymer containing a sesbania gum structure;
b) Mixing carbon dioxide-based polyol and alcohol chain extender with polyurethane prepolymer containing sesbania gum structure, and then adding aliphatic diisocyanate for reaction to obtain an intermediate;
c) And mixing the intermediate with a sulfonate chain extender, carrying out chain extension reaction, and then curing to obtain the biodegradable carbon dioxide-based polyurethane resin.
Preferably, the reaction temperature in the step B) is 80-95 ℃; the reaction time in the step B) is 1 to 2 hours.
Preferably, the temperature of the chain extension reaction is 160-180 ℃, and the time of the chain extension reaction is 15-30 min.
Preferably, the curing temperature is 80-90 ℃, and the curing time is 4-6 hours.
The invention provides a biodegradable carbon dioxide-based polyurethane resin, which is characterized in that a polyurethane main chain structure comprises a carbon dioxide-based polyol chain segment and a sesbania gum chain segment; the biodegradable carbon dioxide-based polyurethane resin comprises the following preparation raw materials in parts by weight: sesbania gum: 3.5-6.5 parts of carbon dioxide-based polyol: 70-220 parts of aromatic diisocyanate: 8-12 parts of aliphatic diisocyanate: 20-45 parts of antioxidant: 0.28-0.95 parts, 0.05-0.11 parts of catalyst, alcohol chain extender: 0.6-2.3 parts of sulfonate chain extender: 0.7 to 1.6 portions. The invention uses carbon dioxide-based dihydric alcohol as a soft segment, introduces a sesbania gum component into the main chain structure, and uses the sesbania gum with multiple functionality as a polyol to be matched with the carbon dioxide-based dihydric alcohol, thereby further improving the biodegradation performance of the polyurethane.
Furthermore, the polyurethane prepolymer with the sesbania gum structure is synthesized firstly, and then the carbon dioxide-based polyol component is introduced into the main chain structure, so that the regularity of the polyurethane structure can be effectively ensured.
Detailed Description
The invention provides a biodegradable carbon dioxide-based polyurethane resin which is characterized in that a polyurethane main chain structure comprises a carbon dioxide-based polyol chain segment and a sesbania gum chain segment;
the biodegradable carbon dioxide-based polyurethane resin comprises the following preparation raw materials in parts by weight:
sesbania gum: 3.5-6.5 parts of carbon dioxide-based polyol: 70-220 parts of aromatic diisocyanate: 8-12 parts of aliphatic diisocyanate: 20-45 parts of antioxidant: 0.28-0.95 part, 0.05-0.11 part of catalyst, alcohol chain extender: 0.6-2.3 parts of sulfonate chain extender: 0.7 to 1.6 portions.
In the present invention, the source of the carbon dioxide-based polyol is not particularly limited, and specifically, the carbon dioxide-based polyol used in the embodiment of the present invention may be prepared with reference to chinese patent CN107868239, and the molecular weight of the carbon dioxide-based polyol is preferably 1000 to 5000g/mol, more preferably 2000 to 4000g/mol, such as 1000g/mol,1500g/mol,2000g/mol,2500g/mol,3000g/mol,3500g/mol,4000g/mol,4500g/mol,5000g/mol, and preferably a range value with any of the above values as an upper limit or a lower limit; the carbonate content of the carbon dioxide based polyol is preferably 40 to 80wt%, more preferably 50 to 70wt%, such as 40wt%,50wt%,60wt%,70wt%,80wt%, preferably a value in the range with any of the above values as upper or lower limits. In a specific embodiment of the invention, the carbon dioxide based polyol used may be a polyol having a molecular weight of 1000g/mol and a carbonate content of 30wt%; or a molecular weight of 5000g/mol and a carbonate content of 80wt%; or a molecular weight of 2000g/mol and a carbonate content of 40 wt.%; or a molecular weight of 3000g/mol, a carbonate content of 50wt%; or a molecular weight of 3500g/mol and a carbonate content of 60 wt.%.
The carbon dioxide-based polyol is preferably 70 to 220 parts by weight, more preferably 100 to 200 parts by weight, such as 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, 160 parts, 170 parts, 180 parts, 190 parts, 200 parts, 210 parts, 220 parts by weight, and preferably has any of the above values as an upper limit or a lower limit.
In the invention, the sesbania gum is a linear natural high molecular compound, contains a large number of hydroxyl groups, has good solubility, can be degraded by various microorganisms in a natural environment, the main chain of the sesbania gum is mannose connected with beta-1, 4 glycosidic bonds, the side chain of the sesbania gum is galactose connected with alpha-1, 6 glycosidic bonds, the proportion of the mannose to the galactose is 2. The sesbania gum is preferably 3.5 to 6.5 parts by weight, more preferably 4 to 6 parts by weight, such as 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, and preferably ranges with any of the above numerical values as upper or lower limits.
In the invention, the aromatic diisocyanate is preferably one or more of hexamethylene diisocyanate, 1, 4-butane diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate; the weight portion of the aromatic diisocyanate is preferably 8 to 12 parts, more preferably 9 to 11 parts, such as 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, and preferably any of the above values is used as an upper limit or a lower limit.
In the present invention, the aliphatic diisocyanate is preferably one or more of 4,4 '-diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate and naphthylene diisocyanate; the weight portion of the aliphatic diisocyanate is preferably 20 to 45 parts, more preferably 25 to 40 parts, such as 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, and preferably any of the above values is an upper limit or a lower limit.
In the present invention, the antioxidant is preferably one or more of IRGANOX1010, IRGANOX1076, IRGANOX1035, IRGANOX245, IRGANOX1098, IRGANOX1135, and IRGANOX 1520; the antioxidant is preferably 0.28 to 0.95 part by weight, more preferably 0.3 to 0.8 part by weight, such as 0.28 part, 0.3 part, 0.35 part, 0.4 part, 0.45 part, 0.5 part, 0.55 part, 0.6 part, 0.65 part, 0.7 part, 0.75 part, 0.8 part, 0.85 part, 0.9 part, 0.95 part, 0.98 part, preferably within a range having any of the above values as upper or lower limits.
In the invention, the catalyst is preferably one or more of stannous octoate, stannous chloride, bismuth neodecanoate, bismuth laurate, dibutyltin dilaurate, triethyleneamine, triethanolamine and triethylamine; the weight portion of the catalyst is preferably 0.05 to 0.11 part, more preferably 0.06 to 0.1 part, such as 0.05 part, 0.06 part, 0.07 part, 0.08 part, 0.09 part, 0.1 part, 0.11 part, and preferably a range value with any of the above values as the upper limit or the lower limit.
In the present invention, the alcohol chain extender is preferably one or more of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 4-cyclohexanediol, trimethylolpropane, glycerol, diethylene glycol, triethylene glycol, neopentyl glycol and sorbitol; the weight portion of the alcohol chain extender is preferably 0.6 to 2.3 parts, more preferably 1 to 2 parts, such as 0.6 part, 0.8 part, 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.8 parts, 2 parts, 2.2 parts, 2.3 parts, and preferably a range value with any of the above values as an upper limit or a lower limit.
In the invention, the sulfonate chain extender is preferably a dihydroxy sulfonate compound and/or an aminosulfonate compound, wherein the dihydroxy sulfonate compound is one or more of N, N- (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt, 2, 5-dihydroxybenzenesulfonic acid sodium salt, 2, 3-dihydroxy naphthalene-6-sodium sulfonate, 1, 4-dihydroxy-2-butane sodium sulfonate, 2, 8-dihydroxy naphthalene-6-sodium sulfonate, 2-dihydroxy-3-monopropanesulfonate and 1, 4-dihydroxy butane-2-sodium sulfonate; the sulfamate compound is one or more of sodium ethylene diamino sulfonate (AAS) and N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt; the weight portion of the sulfonate chain extender is preferably 0.7 to 1.6 parts, more preferably 1 to 1.5 parts, such as 0.7 part, 0.8 part, 0.9 part, 1 part, 1.1 part, 1.2 parts, 1.3 parts, 4 parts, 1.5 parts, 1.6 parts, and preferably a range value with any of the above numerical values as an upper limit or a lower limit.
The invention also provides a preparation method of the biodegradable carbon dioxide-based polyurethane resin, which comprises the following steps:
a) Mixing sesbania gum, aromatic diisocyanate, an antioxidant and a catalyst, and reacting for 1-3 hours at 100-140 ℃ to obtain a polyurethane prepolymer containing a sesbania gum structure;
b) Mixing carbon dioxide-based polyol and alcohol chain extender with polyurethane prepolymer containing sesbania gum structure, and then adding aliphatic diisocyanate for reaction to obtain an intermediate;
c) And mixing the intermediate with a sulfonate chain extender, carrying out chain extension reaction, and then curing to obtain the biodegradable carbon dioxide-based polyurethane resin.
In the preparation method of the present invention, the kinds of the raw materials used are the same as those and sources of the raw materials derived from the raw materials described above, and the present invention will not be described in detail herein.
The research of the invention finds that the random copolymerization of the main chain structure of the obtained polyurethane can be caused by adding the carbon dioxide-based polyol and the sesbania gum into the diisocyanate for reaction, the structure is relatively complex, and a plurality of byproducts are generated. The main reason is that the carbon dioxide-based polyol and the sesbania gum are respectively reacted with diisocyanate due to the difference of the hydroxyl activity of the carbon dioxide-based polyol and the sesbania gum.
Because the hydroxyl activity in the sesbania gum structure is lower, the sesbania gum is firstly reacted with diisocyanate, the density of NCO reaction functional groups is higher at the moment, the sesbania gum can be better connected into a polymer main chain structure, the reaction temperature is increased to 100-140 ℃ from the traditional temperature of 75-80 ℃, a polyurethane prepolymer with the sesbania gum structure is synthesized, then, a carbon dioxide-based polyol component is introduced into the main chain structure, the two components can be effectively connected into the polymer main chain structure, the regularity of the polyurethane structure is ensured, and the mechanical property and the biodegradability of the polyurethane are further improved.
In the invention, the reaction temperature of the sesbania gum and the aromatic diisocyanate is preferably 100-140 ℃, more preferably 110-130 ℃, such as 100 ℃,105 ℃,110 ℃,115 ℃,120 ℃,125 ℃,130 ℃,135 ℃,140 ℃, and is preferably a range value taking any value as an upper limit or a lower limit; the reaction time is preferably 1 to 3 hours, more preferably 2 to 2.5 hours.
In the present invention, the reaction temperature after the addition of the carbon dioxide-based polyol is preferably 80 to 95 ℃, more preferably 85 to 90 ℃, and the reaction time is preferably 1 to 2 hours.
When a sesbania gum structure is introduced, aromatic diisocyanate is used, the main components of the sesbania gum are D-galactose and D-mannose, hydroxyl in the structure is low in reaction, steric hindrance is large, the sesbania gum is difficult to react with aliphatic diisocyanate, and in order to effectively form a urethane bond with the diisocyanate, the aromatic diisocyanate with high activity is required to react with the diisocyanate; when a carbon dioxide-based structure is introduced, the steric hindrance of hydroxyl in the structure is small, the hydroxyl can be well connected into a main chain structure, and meanwhile, in consideration of the performance of the whole polyurethane, the step needs to connect carbon dioxide-based diol into the structure by using aliphatic diisocyanate.
In the present invention, the temperature of the chain extension reaction is preferably 160 to 180 ℃, more preferably 170 to 175 ℃, such as 160 ℃,165 ℃,170 ℃,175 ℃,180 ℃, preferably a range value with any of the above values as the upper limit or the lower limit; the time of the chain extension reaction is preferably 15 to 30min, and more preferably 20 to 25min.
In the present invention, the temperature of the aging is preferably 80 to 90 ℃, more preferably 85 to 88 ℃; the aging time is preferably 4 to 6 hours, and more preferably 4 to 5 hours.
The invention provides a biodegradable carbon dioxide-based polyurethane resin which is characterized in that a polyurethane main chain structure comprises a carbon dioxide-based polyol chain segment and a sesbania gum chain segment; the biodegradable carbon dioxide-based polyurethane resin comprises the following preparation raw materials in parts by weight: sesbania gum: 3.5-6.5 parts of carbon dioxide-based polyol: 70-220 parts of aromatic diisocyanate: 8-12 parts of aliphatic diisocyanate: 20-45 parts of antioxidant: 0.28-0.95 part, 0.05-0.11 part of catalyst, alcohol chain extender: 0.6-2.3 parts of sulfonate chain extender: 0.7 to 1.6 portions. The invention uses carbon dioxide-based dihydric alcohol as a soft segment, introduces a sesbania gum component into the main chain structure, and uses the sesbania gum with multiple functionality as a polyalcohol to be matched with the carbon dioxide-based dihydric alcohol, thereby further improving the biodegradation performance of polyurethane.
Furthermore, the polyurethane prepolymer with the sesbania gum structure is synthesized firstly, and then the carbon dioxide-based polyol component is introduced into the main chain structure, so that the regularity of the polyurethane structure can be effectively ensured.
In order to further illustrate the present invention, the following examples are provided to describe a biodegradable carbon dioxide-based polyurethane resin and a preparation method thereof in detail, but should not be construed as limiting the scope of the present invention.
Example 1
a) 3.5g of sesbania gum (water content less than 300 ppm) and 8g of 4,4' -diphenylmethane diisocyanate, 0.05g of stannous octoate and 0.28g of IRGANOX1010, which were previously freed of water, were charged into a three-neck reaction flask and the temperature was controlled at 100 ℃ for 3 hours.
b) Adding 70-220 g of carbon dioxide-based polyol (with the molecular weight of 1000g/mol, the content of the carbonic ester of 30wt percent and the water content of less than 300 ppm) and 0.6g of ethylene glycol which are dehydrated in advance into a product obtained in the step a), controlling the temperature at 80 ℃, adding 20g of hexamethylene diisocyanate, and reacting for 2 hours;
c) Heating the reaction product obtained in the step b) to 160 ℃, adding 0.7g of N, N- (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt, reacting for 30min, and curing at 80 ℃ for 6 hours to obtain the biodegradable carbon dioxide-based polyurethane.
Example 2
a) 6.5g of sesbania gum (water content less than 300 ppm) and 12g of 2,4' -diphenylmethane diisocyanate, 0.11g of stannous chloride and 0.95g of IRGANOX1076, which were previously dewatered, were put into a three-neck reaction flask and reacted at 140 ℃ for 1 hour.
b) Adding 220g of carbon dioxide-based polyol (with the molecular weight of 5000g/mol, the content of carbonic ester of 80wt% and the water content of less than 300 ppm) and 2.3g of 1, 3-propylene glycol which are dehydrated in advance into the product obtained in the step a), controlling the temperature at 95 ℃, adding 45g of isophorone diisocyanate, and reacting for 1 hour;
c) Heating the reaction product obtained in the step b) to 180 ℃, adding 1.6g of 2, 5-dihydroxy sodium benzenesulfonate, reacting for 15min, and curing at 90 ℃ for 4 hours to obtain the biodegradable carbon dioxide-based polyurethane.
Example 3
a) 4g of sesbania gum (water content less than 300 ppm) and 10.2g of 2,2' -diphenylmethane diisocyanate, 0.07g of bismuth neodecanoate and 0.37g of IRGANOX1035, which were previously freed of water, were charged into a three-neck reaction flask, the temperature was controlled at 110 ℃ and the reaction was carried out for 1 hour.
b) 100g of a carbon dioxide-based polyol (molecular weight 2000g/mol, carbonate content 40% by weight, water content less than 300 ppm) previously freed of water and 1.1g of 1, 4-butanediol are added to the product obtained in a), the temperature is controlled at 90 ℃ and 30g of 1, 4-butane diisocyanate are added and reacted for 1.5 hours;
c) Heating the reaction product obtained in the step b) to 170 ℃, adding 1.2g of 2, 3-dihydroxy naphthalene-6-sodium sulfonate, reacting for 20min, and then curing at 85 ℃ for 5 hours to obtain the biodegradable carbon dioxide-based polyurethane.
Example 4
a) 5g of sesbania gum (water content less than 300 ppm) and 10g of 2, 4-toluene diisocyanate, 0.08g of bismuth laurate and 0.76g of IRGANOX245, from which water had been previously removed, were charged into a three-necked reaction vessel and reacted at 120 ℃ for 1.5 hours.
b) 150g of a carbon dioxide-based polyol (molecular weight 3000g/mol, carbonate content 50% by weight, water content less than 300 ppm) previously freed of water and 1.6g of 1, 6-hexanediol are added to the product obtained in a), the temperature is controlled at 85 ℃ and 35g of dicyclohexylmethane diisocyanate are added and reacted for 2 hours;
c) Heating the reaction product obtained in the step b) to 165 ℃, adding 0.95g of 1, 4-dihydroxy-2-butane sodium sulfonate, reacting for 25min, and then curing at 85 ℃ for 4.5 hours to obtain the biodegradable carbon dioxide-based polyurethane.
Example 5
a) 5.5g of sesbania gum (water content less than 300 ppm) and 9.5g of 2, 6-tolylene diisocyanate (water content less than 300 ppm) were preliminarily removed with water, 0.09g of dibutyltin dilaurate and 0.81g of IRGANOX1098 were charged into a three-necked reaction flask, and the temperature was controlled at 115 ℃ for 2 hours.
b) Adding 180g of carbon dioxide-based polyol (with the molecular weight of 3500g/mol, the carbonate content of 60wt percent and the water content of less than 300 ppm) and 1.9g of 1, 7-heptanediol which are dehydrated in advance into the product obtained in the step a), controlling the temperature at 85 ℃, adding 38g of hexamethylene diisocyanate, and reacting for 1 hour;
c) Heating the reaction product obtained in the step b) to 170 ℃, adding 1.3g of sodium ethylene diamino sulfonate, reacting for 20min, and curing at 90 ℃ for 4.5 hours to obtain the biodegradable carbon dioxide-based polyurethane.
Example 6
a) 6g of sesbania gum (water content less than 300 ppm) and 11.5g of 4,4' -diphenylmethane diisocyanate, 0.1g of triethanolamine and 0.9g of IRGANOX1520, which were previously freed of water, were charged into a three-necked reaction vessel and reacted at 130 ℃ for 1.5 hours.
b) Adding 210g of carbon dioxide-based polyol (with the molecular weight of 5000g/mol, the content of carbonic ester of 80wt% and the water content of less than 300 ppm) and 2g of diethylene glycol which are dehydrated in advance into the product obtained in the step a), controlling the temperature at 90 ℃, adding 40g of isophorone diisocyanate, and reacting for 2 hours;
c) Heating the reaction product obtained in the step b) to 170 ℃, adding 1.4g of N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, reacting for 20min, and then curing for 5 hours at 80 ℃ to obtain the biodegradable carbon dioxide-based polyurethane.
Comparative example 1
Prepared according to the method of example 1 except that sesbania gum and 4,4' -diphenylmethane diisocyanate were removed and other conditions were unchanged.
Comparative example 2
Prepared according to the method of example 2 except that sesbania gum and 2,4' -diphenylmethane diisocyanate were removed and other conditions were unchanged.
Comparative example 3
Prepared according to the method of example 1, except that 70 to 220g of the carbon dioxide based polyol in b) was also added together with 3.5g of the sesbania gum in a), and the other reaction conditions were unchanged.
Comparative example 4
Prepared according to the method of example 1, except that the temperature in a) is controlled from 100 ℃ to 80 ℃ and the other conditions are not changed.
Testing the biodegradation performance of the polyurethane material:
in a 2L test system, the test mixture was aerated at a controlled rate with carbon dioxide free air using polyurethane elastomer as the organic carbon source. The degradation rate was determined by measuring the amount of carbon dioxide produced. 240g of culture soil was mixed with 40g of polyurethane according to the examples and comparative examples (prepared as a 10 μm polyurethane film) and 40g of microcrystalline cellulose, and 240g of culture soil was used as a blank control, and distilled water was added to adjust the humidity of the mixture to about 50%. Placing the compost container in a test environment at (58 +/-2) DEG C and using CO-free 2 The test system was aerated at a flow rate of 0.05L/min with saturated air at a temperature of (58. + -. 2) ℃ and the test was carried out. The biodegradation rate of the test material was determined as the ratio of the amount of carbon dioxide actually produced by the test material during the test to the theoretical amount of carbon dioxide released from the test material.
TABLE 1 examples and comparative biodegradation test results
From the mechanical properties and the biodegradability of the embodiments 1 to 6, the mechanical properties are 26.8 to 30.2MPa, and the elongation at break is 510 to 680%, which indicates that the polyurethane reported by the invention has excellent mechanical properties, and belongs to a strong and tough polyurethane material, and from the viewpoint of biodegradability, the biodegradation rate exceeds 70% after 30 days, and the biodegradation rate exceeds 98% after 180 days, which indicates that the polyurethane material has excellent degradability. From comparative examples 1 and 2, since sesbania gum and aromatic diisocyanate were removed, the resulting polyurethane was deteriorated in mechanical properties due to the hydrogen bonding caused by urethane bonds consisting of less rigid aromatic diisocyanate components, and also deteriorated in biodegradability due to less bio-based sesbania gum components. From the results of comparative examples 3 and 4, the regularity of the obtained polyurethane is deteriorated due to the change of the feeding sequence and the reaction temperature, and from the result of the biodegradability, although the sesbania gum component is not completely and regularly incorporated into the main chain structure of the polyurethane, the sesbania gum component has a certain biodegradability as a bio-based component, so that the biodegradability is not reduced too much in comparison example 4, the sesbania gum component is not incorporated into the main chain structure of the polyurethane due to the excessively low temperature, and the mechanical property of the polyurethane is deteriorated.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A biodegradable carbon dioxide-based polyurethane resin is characterized in that the main chain structure of the polyurethane comprises a carbon dioxide-based polyol chain segment and a sesbania gum chain segment;
the biodegradable carbon dioxide-based polyurethane resin comprises the following preparation raw materials in parts by weight:
sesbania gum: 3.5-6.5 parts of carbon dioxide-based polyol: 70-220 parts of aromatic diisocyanate: 8-12 parts of aliphatic diisocyanate: 20-45 parts of antioxidant: 0.28-0.95 parts, 0.05-0.11 parts of catalyst, alcohol chain extender: 0.6-2.3 parts of sulfonate chain extender: 0.7 to 1.6 portions.
2. The biodegradable carbon dioxide-based polyurethane resin according to claim 1, wherein the carbon dioxide-based polyol has a molecular weight of 1000 to 5000g/mol and a carbonate content of 30 to 80wt%.
3. The biodegradable carbon dioxide-based polyurethane resin according to claim 1, wherein the aliphatic diisocyanate is one or more of hexamethylene diisocyanate, 1, 4-butane diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate;
the aromatic diisocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate and naphthalene diisocyanate.
4. The biodegradable carbon dioxide-based polyurethane resin according to claim 1, wherein the catalyst is one or more selected from stannous octoate, stannous chloride, bismuth neodecanoate, bismuth laurate, dibutyltin dilaurate, triethyleneamine, triethanolamine and triethylamine.
5. The biodegradable carbon dioxide-based polyurethane resin according to claim 1, wherein the alcohol chain extender is one or more selected from the group consisting of ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 4-cyclohexanediol, trimethylolpropane, glycerol, diethylene glycol, triethylene glycol, neopentyl glycol and sorbitol;
the sulfonate chain extender is a dihydroxy sulfonate compound and/or an amino sulfonate compound.
6. The biodegradable carbon dioxide-based polyurethane resin according to claim 5, wherein the dihydroxy sulfonate compound is one or more of sodium N, N- (2-hydroxyethyl) -2-aminoethanesulfonate, sodium 2, 5-dihydroxybenzenesulfonate, sodium 2, 3-dihydroxynaphthalene-6-sulfonate, sodium 1, 4-dihydroxy-2-butanesulfonate, sodium 2, 8-dihydroxynaphthalene-6-sulfonate, sodium 2-dihydroxy-3-monopropanesulfonate and sodium 1, 4-dihydroxybutane-2-sulfonate;
the sulfamate compound is one or more of sodium ethylene diamino sulfonate (AAS) and N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt.
7. The method for preparing a biodegradable carbon dioxide-based polyurethane resin according to claim 1, comprising the steps of:
a) Mixing sesbania gum, aromatic diisocyanate, an antioxidant and a catalyst, and reacting for 1-3 hours at 100-140 ℃ to obtain a polyurethane prepolymer containing a sesbania gum structure;
b) Mixing carbon dioxide-based polyol and alcohol chain extender with polyurethane prepolymer containing sesbania gum structure, and then adding aliphatic diisocyanate for reaction to obtain an intermediate;
c) And mixing the intermediate with a sulfonate chain extender, carrying out chain extension reaction, and then curing to obtain the biodegradable carbon dioxide-based polyurethane resin.
8. The preparation method according to claim 7, wherein the temperature of the reaction in the step B) is 80-95 ℃; the reaction time in the step B) is 1 to 2 hours.
9. The preparation method according to claim 7, characterized in that the temperature of the chain extension reaction is 160-180 ℃, and the time of the chain extension reaction is 15-30 min.
10. The method according to claim 7, wherein the temperature of the aging is 80 to 90 ℃ and the time of the aging is 4 to 6 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117757404A (en) * | 2023-12-22 | 2024-03-26 | 广州市嘉雁粘合剂有限公司 | Preparation method of PUR hot melt adhesive for binding |
| CN118459708A (en) * | 2024-04-01 | 2024-08-09 | 广州闻佳新材料科技有限公司 | Biodegradable waterborne polyurethane and preparation method and application thereof |
| CN119061511A (en) * | 2024-11-04 | 2024-12-03 | 山东联欣环保科技有限公司 | A kind of carbon dioxide based polyurethane fiber and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117757404A (en) * | 2023-12-22 | 2024-03-26 | 广州市嘉雁粘合剂有限公司 | Preparation method of PUR hot melt adhesive for binding |
| CN118459708A (en) * | 2024-04-01 | 2024-08-09 | 广州闻佳新材料科技有限公司 | Biodegradable waterborne polyurethane and preparation method and application thereof |
| CN119061511A (en) * | 2024-11-04 | 2024-12-03 | 山东联欣环保科技有限公司 | A kind of carbon dioxide based polyurethane fiber and preparation method thereof |
| CN119061511B (en) * | 2024-11-04 | 2025-01-28 | 山东联欣环保科技有限公司 | Carbon dioxide-based polyurethane fiber and preparation method thereof |
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