CN114507330A - Polyurethane composition - Google Patents
Polyurethane composition Download PDFInfo
- Publication number
- CN114507330A CN114507330A CN202210013383.0A CN202210013383A CN114507330A CN 114507330 A CN114507330 A CN 114507330A CN 202210013383 A CN202210013383 A CN 202210013383A CN 114507330 A CN114507330 A CN 114507330A
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- CN
- China
- Prior art keywords
- acrylate
- meth
- parts
- polyurethane composition
- polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 39
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 88
- 239000000463 material Substances 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 125000003003 spiro group Chemical group 0.000 claims abstract description 10
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 9
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 9
- 241000396922 Pontia daplidice Species 0.000 claims abstract description 4
- 229920005862 polyol Polymers 0.000 claims description 32
- 150000003077 polyols Chemical class 0.000 claims description 32
- -1 2-ethylhexyl Chemical group 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- 239000004970 Chain extender Substances 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 10
- 238000010526 radical polymerization reaction Methods 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 7
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 5
- 229920005749 polyurethane resin Polymers 0.000 abstract description 5
- 238000009755 vacuum infusion Methods 0.000 abstract description 5
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 6
- 239000011151 fibre-reinforced plastic Substances 0.000 description 6
- 238000005266 casting Methods 0.000 description 4
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical group CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- 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 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 101710186384 Tropomyosin-2 Proteins 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical group OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- CWLNAJYDRSIKJS-UHFFFAOYSA-N triethoxymethoxyethane Chemical compound CCOC(OCC)(OCC)OCC CWLNAJYDRSIKJS-UHFFFAOYSA-N 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical group CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- VNTDZUDTQCZFKN-UHFFFAOYSA-L zinc 2,2-dimethyloctanoate Chemical compound [Zn++].CCCCCCC(C)(C)C([O-])=O.CCCCCCC(C)(C)C([O-])=O VNTDZUDTQCZFKN-UHFFFAOYSA-L 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
- C08G18/3218—Polyhydroxy compounds containing cyclic groups having at least one oxygen atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a polyurethane composition, and belongs to the technical field of polyurethane composite materials. The invention aims to provide a polyurethane composition with small curing shrinkage and good mechanical property. The polyurethane composition comprises the following components: a. black material components: comprises polyisocyanate and initiator; b. white material components: comprises polyhydric alcohol and acrylate monomers; the polyhydric alcohol comprises spiro alcohol with a structure shown as a formula I. The invention adopts the spiro alcohol to overcome the volume shrinkage of the polyurethane resin during curingAnd the curing mechanical strength of the resin is improved, and the problems that the curing shrinkage of the existing resin system is large, a product is easy to deform and accelerate to age, the defects are large, and the mechanical property is insufficient are solved. The polyurethane obtained by curing the polyurethane composition has the advantages of low volume shrinkage rate of 0 and good mechanical property, can be used for forming in a vacuum infusion process or a pultrusion process, and has better appearance and better mechanical property.
Description
Technical Field
The invention relates to a polyurethane composition, and belongs to the technical field of polyurethane composite materials.
Background
Polyurethane (PU), a full name of polyurethane, is a high molecular compound, and a resin having a repeating-HNCOO-group in a main chain is generally obtained by stepwise addition polymerization of polyisocyanate, polyol polymer, aromatic diamine, and the like. The polyurethane molecule may contain, in addition to urethane, a group such as ether, ester, urea, biuret, allophanate, or the like. By changing the types and compositions of the raw materials, the shapes and the performances of the polyurethane resin products can be greatly changed, and the final products from soft to hard can be obtained. The polyurethane resin has the outstanding advantages of low cost, excellent mechanical property, good weather resistance and the like, and the research of polyurethane-based composite materials is more and more emphasized in recent years.
The scientific companies disclose a series of methods and patents for preparing composite materials from polyurethane, such as patents CN111748073A, CN105778005A, CN104974502A, CN105199075A, etc. In the patent technologies, an unsaturated double bond-based reactive diluent is used as a reactant (such as methyl (meth) acrylate, hydroxy (meth) acrylate and the like), and a casting body and a composite material product prepared from the unsaturated double bond-based reactive diluent have the defects of large curing shrinkage, poor mechanical property and the like undoubtedly, so that the application of the unsaturated double bond-based reactive diluent in the fields of wind power blades, yacht main bodies and automobile engine covers is influenced.
Disclosure of Invention
Aiming at the defect of large curing shrinkage of polyurethane, the invention provides a polyurethane composition with small curing shrinkage and good mechanical property.
The polyurethane composition comprises the following components:
a. black material components: comprises polyisocyanate and initiator;
b. white material components: comprises polyhydric alcohol and acrylate monomers; the polyhydric alcohol comprises spirocyclic alcohol;
wherein the structure of the spironols is shown as a formula I:
the structure of the acrylate monomer is shown as a formula II:
in the formula II, R1Is hydrogen or methyl, R2Is alkyl, cycloalkyl or hydroxyalkyl.
In one embodiment of the present invention, the acrylate monomer is at least one of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
In a preferred embodiment, the acrylate monomers are methyl (meth) acrylate and hydroxypropyl (meth) acrylate.
In a more preferred embodiment, the weight ratio of methyl (meth) acrylate to hydroxypropyl (meth) acrylate is 1:8 to 15.
In one embodiment, the weight ratio of methyl (meth) acrylate to hydroxypropyl (meth) acrylate is 1: 11.
Further, the polyol also includes polyether polyol or polyester polyol.
In one embodiment of the present invention, the weight percentage of the spiroglycol to the polyol is 10 to 15%.
In a preferred embodiment, the spiro alcohol is present in an amount of 13% by weight of the polyol.
In one embodiment of the present invention, the weight ratio of the polyol to the acrylate monomer is 1:1 to 3.
In a preferred embodiment, the weight ratio of polyol to acrylate monomer is 1: 1.5.
In one embodiment of the invention, the white material component further comprises an auxiliary agent, and the auxiliary agent is at least one of a free radical polymerization inhibitor, a chain extender, a water removing agent, a surfactant, an accelerator and a gel catalyst.
In one embodiment of the invention, the weight ratio of the white material component to the black material component is 100: 40-130.
In a preferred embodiment, the weight ratio of the white material component to the black material component is 100: 85.
Preferably, the white material component comprises the following components in parts by weight: 40-60 parts of methyl methacrylate, 400-650 parts of hydroxypropyl methacrylate, 150-250 parts of 3-functional polyether polyol, 100-200 parts of 2-functional polyol, 40-60 parts of spirocyclic alcohol, 0.01-0.5 part of free radical polymerization inhibitor, 1-10 parts of chain extender, 0.1-1 part of water remover, 1-5 parts of surfactant, 0.5-2 parts of cobalt naphthenate and 0.01-0.2 part of gel catalyst.
In a preferred embodiment, the white material component consists of the following components in parts by weight: 50 parts of methyl methacrylate, 550 parts of hydroxypropyl methacrylate, 200 parts of 3-functional polyether polyol, 148 parts of 2-functional polyol, 52 parts of spiro alcohol, 0.1 part of free radical polymerization inhibitor, 5 parts of chain extender, 0.5 part of water scavenger, 2 parts of surfactant, 1 part of cobalt naphthenate and 0.1 part of gel catalyst.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the spirocyclic alcohol, overcomes the volume shrinkage of polyurethane resin during curing, improves the curing mechanical strength of the resin, and solves the problems of large curing shrinkage of the existing resin system, easy deformation, accelerated aging, multiple defects and insufficient mechanical properties of products. The polyurethane obtained by curing the polyurethane composition has the advantages of low volume shrinkage rate of 0 and good mechanical property, can be used for forming in a vacuum infusion process or a pultrusion process, and has better appearance and better mechanical property.
Detailed Description
The polyurethane composition comprises the following components:
a. black material components: comprises polyisocyanate and an initiator;
b. white material components: comprises polyhydric alcohol and acrylate monomers; the polyhydric alcohol comprises spirocyclic alcohol;
wherein the structure of the spironols is shown as a formula I:
the structure of the acrylate monomer is shown as a formula II:
in the formula II, R1Is hydrogen or methyl, R2Is alkyl, cycloalkyl or hydroxyalkyl.
Generally, the polyurethane polymerization process can generate volume expansion, and the spirocyclic alcohol is adopted in the invention, so that the volume shrinkage of polyurethane resin during curing is overcome, the curing mechanical strength of the resin is improved, and the problems of large curing shrinkage, easy deformation, accelerated aging, multiple defects and insufficient mechanical property of the existing resin system are solved. The polyurethane obtained by curing the polyurethane composition has the advantages of low volume shrinkage rate of 0 and good mechanical property, can be used for forming in a vacuum infusion process or a pultrusion process, and has better appearance and better mechanical property.
Wherein the component a is a black material component and comprises polyisocyanate and an initiator.
The polyisocyanate of the present invention is a generic name of various esters containing 2 or more isocyanate groups. Polyisocyanates commonly used in the art are suitable for use in the present invention. In some embodiments of the present invention, the polyisocyanate includes, but is not limited to, Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), Lysine Diisocyanate (LDI), 1, 5-Naphthalene Diisocyanate (NDI), p-phenylene diisocyanate (PPDI), p-phenylene diisocyanate (XDI), and the like, as well as polymers of these isocyanates or combinations thereof.
The initiator mainly initiates the double bonds in the white material component to generate free radical reaction. Free radical initiators commonly used in the art are suitable for use in the present invention and include, but are not limited to, benzoyl peroxide, lauroyl peroxide, t-butyl peroxy-2-ethylhexanoate, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, and the like. The free radical initiator is used in amounts conventional in the art.
The component b is a white material component which comprises polyhydric alcohol containing spiro alcohol and acrylate monomers.
The spirocyclic alcohol is an active monomer which has a spirocyclic structure and has hydroxyl, and the spirocyclic alcohol is added into the polyurethane composition disclosed by the invention, so that the problem that the existing unsaturated resin modified polyurethane system has large curing shrinkage is solved, and the resin curing mechanical strength is further improved. The structure of the spironols is shown in a formula I:
the spiroglycol may be commercially available or may be self-prepared. In one embodiment of the invention, the spirocyclic alcohol is prepared by the following method:
the synthesis method comprises the following steps of taking trimethylolpropane as an initial raw material, taking hydrochloric acid, acetic acid, p-toluenesulfonic acid, sulfuric acid or nitric acid as a catalyst, and synthesizing with tetraethyl orthocarbonate to obtain the spirocyclic alcohol, wherein the synthesis route is as follows:
in one embodiment of the present invention, the acrylate monomer is at least one of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
The "(meth) acrylic acid … …" used herein refers to acrylic acid … … or methacrylic acid … …. For example, hydroxyethyl (meth) acrylate is hydroxyethyl acrylate or hydroxyethyl methacrylate, methyl (meth) acrylate is methyl acrylate or methyl methacrylate, and ethyl (meth) acrylate is ethyl acrylate or ethyl methacrylate.
In a preferred embodiment, the acrylate monomers are methyl (meth) acrylate and hydroxypropyl (meth) acrylate.
In a more preferred embodiment, the weight ratio of methyl (meth) acrylate to hydroxypropyl (meth) acrylate is 1:8 to 15.
In one embodiment, the weight ratio of methyl (meth) acrylate to hydroxypropyl (meth) acrylate is 1: 11.
Further, the polyol also includes polyether polyol or polyester polyol.
In one embodiment of the present invention, the weight percentage of the spiroglycol to the polyol is 10 to 15%.
In a preferred embodiment, the spiro alcohol is present in an amount of 13% by weight of the polyol.
In one embodiment of the present invention, the weight ratio of the polyol to the acrylate monomer is 1:1 to 3.
In a preferred embodiment, the weight ratio of polyol to acrylate monomer is 1: 1.5.
In one embodiment of the invention, the white material component further comprises an auxiliary agent, and the auxiliary agent is at least one of a free radical polymerization inhibitor, a chain extender, a water remover, a surfactant, an accelerator and a gel catalyst.
In one embodiment of the invention, the free radical polymerization inhibitor is methyl hydroquinone, the chain extender is dipropylene glycol, the water removal agent is triethyl orthoformate, the surfactant is silicone oil B8870, the accelerator is cobalt naphthenate, and the gel catalyst is polyurethane organic bismuth catalyst BICAT 8.
In one embodiment of the invention, the weight ratio of the white material component to the black material component is 100: 40-130.
In a preferred embodiment, the weight ratio of the white material component to the black material component is 100: 85.
Preferably, the white material component comprises the following components in parts by weight: 40-60 parts of methyl methacrylate, 400-650 parts of hydroxypropyl methacrylate, 150-250 parts of 3-functional polyether polyol, 100-200 parts of 2-functional polyol, 40-60 parts of spirocyclic alcohol, 0.01-0.5 part of free radical polymerization inhibitor, 1-10 parts of chain extender, 0.1-1 part of water remover, 1-5 parts of surfactant, 0.5-2 parts of cobalt naphthenate and 0.01-0.2 part of gel catalyst.
In a preferred embodiment, the white material component consists of the following components in parts by weight: 50 parts of methyl methacrylate, 550 parts of hydroxypropyl methacrylate, 200 parts of 3-functional polyether polyol, 148 parts of 2-functional polyol, 52 parts of spiro alcohol, 0.1 part of free radical polymerization inhibitor, 5 parts of chain extender, 0.5 part of water scavenger, 2 parts of surfactant, 1 part of cobalt naphthenate and 0.1 part of gel catalyst.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Examples
The polyurethane compositions of the present invention are formulated as shown in Table 1.
TABLE 1
Wherein PM200 is polymeric MDI, functionality of 2.7, NCO content of 30.75%, available from Vanhua chemical polyurethane.
HPMA is hydroxypropyl methacrylate.
DMT450 is a trimethylolpropane-initiator amount of a 3-functional polyether polyol, molecular weight 450, available from Federal chemical industries, Zibode, Shandong.
DL400 is a propylene glycol initiated 2 functional polyether polyol having a molecular weight of 400, available from Shandong Lanxingdao Co., Ltd.
MMA is methyl methacrylate.
Spirocyclic alcohol was made by house according to CN 112812124A example 3.
And (3) performance testing:
1. mechanical properties of the cast body
Preparing a casting body by mixing 100 parts of white material and 85 parts of black material according to the weight ratio of the black material to the white material, wherein the preparation condition of the casting body is room temperature, the temperature is 20-25 ℃, the humidity is 50-65%, and the curing condition is as follows: and mixing and defoaming the two components, introducing the components into a glass interlayer, standing for 24 hours, heating to 70 ℃, and curing for 4 hours. Taking out, cutting and polishing into sample strips with standard sizes, and measuring the mechanical properties. The results are shown in Table 2.
TABLE 2
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Tensile strength/MPa | 91.5 | 93.5 | 93.8 | 75.2 | 74.5 |
| Tensile modulus/Gpa | 3.62 | 3.71 | 3.82 | 3.09 | 3.25 |
| Elongation at break/% | 7.28 | 8.52 | 6.43 | 5.63 | 5.12 |
| Flexural Strength/MPa | 142 | 148 | 140 | 118 | 108 |
| Flexural modulus/Gpa | 3.88 | 3.85 | 3.77 | 3.28 | 3.06 |
| Volume shrinkage percentage% | 0 | 0.24 | 0.13 | 11.5 | -3.2 |
Therefore, the casting body prepared by the invention completely overcomes the shrinkage defect after curing, and has higher mechanical strength and better comprehensive performance.
2. FRP (fiber reinforced Plastic) by vacuum infusion process
The two components are mixed evenly according to the proportion of white materials to black materials of 100:85, defoamed, the glass fiber type is Zhejiang Hengshi UD1200, 4 layers are laid, vacuum defoamed and mixed evenly, FRP is poured, and the performance is measured, and the result is shown in Table 3.
TABLE 3
3. FRP (fiber reinforced Plastic) by pultrusion process
By adopting a pultrusion process, the glass fiber raw yarn is TMII type of Chongqing International composite material Co., Ltd, the number of the yarns is 406, the temperature of the three area is 100 ℃ in the first area, 160 ℃ in the second area, 185 ℃ in the third area, the pultrusion speed is 1m/min, FRP is prepared, and then the performance is measured, and the result is shown in Table 4.
TABLE 4
Therefore, no matter vacuum infusion or pultrusion molding is carried out, under the condition that the glass fiber content is the same, the product has better product appearance and better mechanical property.
Claims (10)
1. A polyurethane composition characterized by comprising the following components:
a. black material components: comprises polyisocyanate and initiator;
b. white material components: comprises polyhydric alcohol and acrylate monomers; the polyhydric alcohol comprises spirocyclic alcohol;
wherein the structure of the spironols is shown as a formula I:
the structure of the acrylate monomer is shown as a formula II:
in the formula II, R1Is hydrogen or methyl, R2Is alkyl, cycloalkyl or hydroxyalkyl.
2. The polyurethane composition of claim 1, wherein: the acrylate monomer is at least one of methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate.
3. The polyurethane composition of claim 2, wherein: the acrylate monomers are methyl (meth) acrylate and hydroxypropyl (meth) acrylate.
4. A polyurethane composition according to claim 3, characterized in that: the weight ratio of the methyl (meth) acrylate to the hydroxypropyl (meth) acrylate is 1: 8-15; preferably, the weight ratio of methyl (meth) acrylate to hydroxypropyl (meth) acrylate is 1: 11.
5. A polyurethane composition as claimed in any one of claims 1 to 3 wherein: the polyol also includes a polyether polyol or a polyester polyol.
6. The polyurethane composition of claim 4, wherein: the weight percentage of the spiro alcohol in the polyol is 10-15%; preferably, the weight percent of spiro alcohol in the polyol is 13%.
7. The polyurethane composition of claim 5, wherein: the weight ratio of the polyhydric alcohol to the acrylate monomer is 1: 1-3; preferably, the weight ratio of polyol to acrylate monomer is 1: 1.5.
8. The polyurethane composition of claim 1, wherein: the white material component also comprises an auxiliary agent, wherein the auxiliary agent is at least one of a free radical polymerization inhibitor, a chain extender, a water removing agent, a surfactant, an accelerant and a gel catalyst.
9. The polyurethane composition of claim 1, wherein: the weight ratio of the white material component to the black material component is 100: 40-130; preferably, the weight ratio of the white material component to the black material component is 100: 85.
10. The polyurethane composition of claim 1, wherein: the white material comprises the following components in parts by weight: 40-60 parts of methyl methacrylate, 400-650 parts of hydroxypropyl methacrylate, 150-250 parts of 3-functional polyether polyol, 100-200 parts of 2-functional polyol, 40-60 parts of spirocyclic alcohol, 0.01-0.5 part of free radical polymerization inhibitor, 1-10 parts of chain extender, 0.1-1 part of water remover, 1-5 parts of surfactant, 0.5-2 parts of cobalt naphthenate and 0.01-0.2 part of gel catalyst; preferably, the white material component consists of the following components in parts by weight: 50 parts of methyl methacrylate, 550 parts of hydroxypropyl methacrylate, 200 parts of 3-functional polyether polyol, 148 parts of 2-functional polyol, 52 parts of spiro alcohol, 0.1 part of free radical polymerization inhibitor, 5 parts of chain extender, 0.5 part of water scavenger, 2 parts of surfactant, 1 part of cobalt naphthenate and 0.1 part of gel catalyst.
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