CN114656596A - Method for stably storing isocyanate composition - Google Patents
Method for stably storing isocyanate composition Download PDFInfo
- Publication number
- CN114656596A CN114656596A CN202011532123.1A CN202011532123A CN114656596A CN 114656596 A CN114656596 A CN 114656596A CN 202011532123 A CN202011532123 A CN 202011532123A CN 114656596 A CN114656596 A CN 114656596A
- Authority
- CN
- China
- Prior art keywords
- chloride
- polyurethane
- reaction system
- acid chloride
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 96
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 93
- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229920002635 polyurethane Polymers 0.000 claims abstract description 63
- 239000004814 polyurethane Substances 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 52
- 239000003999 initiator Substances 0.000 claims description 37
- 150000003077 polyols Chemical class 0.000 claims description 34
- 239000005056 polyisocyanate Substances 0.000 claims description 33
- 229920001228 polyisocyanate Polymers 0.000 claims description 33
- 229920005862 polyol Polymers 0.000 claims description 31
- 150000003254 radicals Chemical class 0.000 claims description 31
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 20
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 17
- 229920005749 polyurethane resin Polymers 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- WTQHNWLXESYFAM-UHFFFAOYSA-N 3,5-dimethylidenecyclohexene Chemical compound C=C1CC=CC(=C)C1 WTQHNWLXESYFAM-UHFFFAOYSA-N 0.000 claims description 8
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 8
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 8
- 239000012346 acetyl chloride Substances 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- XURVRZSODRHRNK-UHFFFAOYSA-N o-quinodimethane Chemical compound C=C1C=CC=CC1=C XURVRZSODRHRNK-UHFFFAOYSA-N 0.000 claims description 8
- NRNFFDZCBYOZJY-UHFFFAOYSA-N p-quinodimethane Chemical compound C=C1C=CC(=C)C=C1 NRNFFDZCBYOZJY-UHFFFAOYSA-N 0.000 claims description 8
- 239000001294 propane Substances 0.000 claims description 8
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 claims description 8
- PNQBEPDZQUOCNY-UHFFFAOYSA-N trifluoroacetyl chloride Chemical compound FC(F)(F)C(Cl)=O PNQBEPDZQUOCNY-UHFFFAOYSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 4
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001263 acyl chlorides Chemical class 0.000 claims description 4
- 239000012212 insulator Substances 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 238000009408 flooring Methods 0.000 claims 1
- 230000002035 prolonged effect Effects 0.000 claims 1
- -1 aromatic isocyanates Chemical class 0.000 description 24
- 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 20
- 238000003860 storage Methods 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 11
- 238000005829 trimerization reaction Methods 0.000 description 11
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000004721 Polyphenylene oxide Substances 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 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 8
- 239000000463 material Substances 0.000 description 7
- 229920005906 polyester polyol Polymers 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000012644 addition polymerization Methods 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000010526 radical polymerization reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 3
- 239000007806 chemical reaction intermediate Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000006082 mold release agent Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229960004063 propylene glycol Drugs 0.000 description 3
- 235000013772 propylene glycol Nutrition 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical group ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- MKUXAQIIEYXACX-UHFFFAOYSA-N aciclovir Chemical compound N1C(N)=NC(=O)C2=C1N(COCCO)C=N2 MKUXAQIIEYXACX-UHFFFAOYSA-N 0.000 description 2
- 229960004150 aciclovir Drugs 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- QAEKNCDIHIGLFI-UHFFFAOYSA-L cobalt(2+);2-ethylhexanoate Chemical compound [Co+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O QAEKNCDIHIGLFI-UHFFFAOYSA-L 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-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
- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical compound O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-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
- 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
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000006677 Appel reaction Methods 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
- 239000004604 Blowing Agent Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical group [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001330498 Corsia Species 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
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Images
Classifications
-
- 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
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a method for stably storing an isocyanate composition, the stably stored isocyanate composition and a polyurethane reaction system comprising the isocyanate composition.
Description
Technical Field
The present invention relates to a method for stably storing an isocyanate composition, the stably stored isocyanate composition, and a polyurethane resin produced from the isocyanate composition.
Background
The trimerization catalytic reaction of isocyanate is a curing and crosslinking method commonly used in the application field of polyurethane materials. The isocyanurate six-membered ring rigid structure generated by trimerization can provide high crosslinking degree to enhance the mechanical strength of the cured polyurethane material, and meanwhile, due to the high carbon-nitrogen-oxygen content of the isocyanurate six-membered ring and the excellent flame retardance generated by the conjugated aromatic structure, the integral flame retardance of the polyurethane material can be improved. For these reasons, the trimerization of isocyanate functions is widely used in the field of polyurethane materials. Generally, the trimerization reaction of isocyanates takes place in the presence of a trimerization catalyst. We have found that in the presence of a free radical initiator, the isocyanate can trimerize even in the absence of a trimerisation catalyst, i.e. an isocyanate composition to which a free radical initiator is added will not be stable on storage because of the trimerisation reaction. It is not known in the art how to make the trimerization of isocyanates with added free radical initiators slower or suppressed and to control the trimerization of isocyanates to occur either not or more controllably, so as to make the corresponding isocyanate compositions storage stable.
CN109694460A discloses an isocyanate trimer having polyfunctional unsaturated groups, wherein A, B, C independently represents aliphatic group, aromatic group, amide group, lactone or ester group, alcohol ether or phenol ether group, preferably disubstituted benzene group, substituted formate group, cycloalkyl group, straight chain alkyl group, each group containing 1-15 carbons.
CN1036404C discloses a thermoplastic polyurethane elastomer interpenetrating network adhesive. The thermoplastic polyurethane elastomer is prepared by synthesizing an acrylate monomer containing active double bonds, organic isocyanate, linear polyester, an initiator and a catalyst, and a solvent and a modifier thereof.
CN110078881A relates to a polymer expansion material in a seepage or seepage water environment and a preparation process thereof, belonging to the technical field of polymer expansion foam materials. The feed comprises the following raw materials in parts by weight: 20-30 parts of rosin polyester polyol, 20-50 parts of isocyanate, 220-40 parts of Phireguard MB-51220, 5-10 parts of 1, 1-dichloro-1-fluoroethane, 1-2 parts of surfactant, 0.01-1 part of catalyst and 0.01 part of benzoyl chloride.
CN109810237A discloses a single slurry bearable reaction material and a preparation method thereof, the prepared single slurry bearable reaction material is flame retardant, has low viscosity, is suitable for most general fluid conveying equipment, can bear load, and is convenient for repairing underground pipeline leakage in water environment, especially for repairing underground pipeline leakage in non-excavation manner in water environment.
Despite the above disclosures, there is still a great need in the industry for a method of stably storing isocyanate compositions.
Disclosure of Invention
In one aspect of the present invention, there is provided a method for stably storing an isocyanate composition comprising:
A1) one or more polyisocyanates;
A2) at least one free radical initiator;
said method is to add A3) at least one acid chloride to the isocyanate composition.
Preferably, the polyisocyanate is selected from aromatic isocyanates, preferably diphenylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or combinations thereof, particularly preferably diphenylmethane diisocyanate or (poly) diphenylmethane diisocyanate.
Preferably, the a2) free radical initiator is present in an amount of 0.1 to 5 wt.%, preferably 0.2 to 4 wt.%, more preferably 0.4 to 3 wt.%, based on the total weight of the isocyanate composition in 100 wt.%.
Preferably, the a3) at least one acid chloride is present in an amount of 0.001 to 3.5 wt.%, preferably 0.003 to 3.0 wt.%, more preferably 0.005 to 2.0 wt.%, based on the total weight of the isocyanate composition, in 100 wt.%.
Preferably, said a3) at least one acid chloride is selected from the group consisting of formyl chloride, acetyl chloride, benzoyl chloride, phthaloyl chloride, oxalyl chloride, chloroacetyl chloride, trichloroacetyl chloride, trifluoroacetyl chloride or combinations thereof.
Preferably, the isocyanate composition comprising at least one acid chloride is stable for longer than or equal to 5 days, preferably longer than or equal to 7 days, more preferably longer than or equal to 14 days at 50 ℃ than an isocyanate composition not comprising at least one acid chloride.
In yet another aspect of the present invention, there is provided an isocyanate composition comprising:
A1) one or more polyisocyanates;
A2) at least one free radical initiator;
A3) at least one acid chloride.
Preferably, the polyisocyanate is selected from aromatic isocyanates, preferably diphenylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or combinations thereof, particularly preferably diphenylmethane diisocyanate or (poly) diphenylmethane diisocyanate.
Preferably, the a2) free radical initiator is present in an amount of 0.1 to 5 wt.%, preferably 0.2 to 4 wt.%, more preferably 0.4 to 3 wt.%, based on the total weight of the isocyanate composition in 100 wt.%.
Preferably, the a3) at least one acid chloride is present in an amount of 0.001 to 3.5 wt.%, preferably 0.003 to 3.0 wt.%, more preferably 0.005 to 2.0 wt.%, based on the total weight of the isocyanate composition, of 100 wt.%.
Preferably, said a3) at least one acid chloride is selected from the group consisting of formyl chloride, acetyl chloride, benzoyl chloride, phthaloyl chloride, oxalyl chloride, chloroacetyl chloride, trichloroacetyl chloride, trifluoroacetyl chloride or combinations thereof.
Preferably, the isocyanate composition comprising at least one acid chloride is stable for storage at 50 ℃ for a period of time of 7 days or longer, preferably 14 days or longer, more preferably 20 days or longer, than an isocyanate composition not comprising at least one acid chloride.
In a further aspect of the invention there is provided the use of an acid chloride to inhibit the trimerisation reaction of isocyanates catalysed by a free radical initiator. The use is to add at least one acid chloride to an isocyanate composition comprising:
A1) one or more polyisocyanates;
A2) at least one free radical initiator.
Preferably, the a3) at least one acid chloride is present in an amount of 0.001 to 3.5 wt.%, preferably 0.003 to 3.0 wt.%, more preferably 0.005 to 2.0 wt.%, based on the total weight of the isocyanate composition, in 100 wt.%.
Preferably, said a3) at least one acid chloride is selected from the group consisting of formyl chloride, acetyl chloride, benzoyl chloride, phthaloyl chloride, oxalyl chloride, chloroacetyl chloride, trichloroacetyl chloride, trifluoroacetyl chloride or combinations thereof.
In still another aspect of the present invention, there is provided a method for preparing a polyurethane resin by reacting a polyurethane reaction system comprising:
component A) comprising:
A1) one or more polyisocyanates;
A2) a free radical initiator;
A3) at least one acid chloride;
component B) comprising:
B1) one or more organic polyols in an amount of 21 to 60 wt.%, based on 100 wt.% of the total weight of the polyurethane reaction system;
B2) one or more compounds having the structure of formula (I)
Wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6.
Preferably, the B2) is present in an amount of 4 to 33 wt.%, based on 100 wt.% of the total weight of the polyurethane reaction system.
Preferably, the B2) component is selected from: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or combinations thereof.
Preferably, the organic polyol is selected from the group consisting of polyols having a functionality of from 1.7 to 6, preferably from 1.9 to 4, more preferably from 1.9 to 2.8, and a hydroxyl number of 150 and 1100 mgKOH/g.
Preferably, said a3) at least one acid chloride is selected from the group consisting of formyl chloride, acetyl chloride, benzoyl chloride, phthaloyl chloride, oxalyl chloride, chloroacetyl chloride, trichloroacetyl chloride and trifluoroacetyl chloride.
Preferably, the polyurethane reaction system is operable for a time of 60 minutes or more, preferably 65 minutes or more, more preferably 70 minutes or more at 35 ℃.
Preferably, the open time at 35 ℃ of the polyurethane reaction system comprising at least one acid chloride increases by more than or equal to 30%, preferably more than or equal to 40%, more preferably more than or equal to 50% of the open time stability at 35 ℃ of the polyurethane reaction system not comprising at least one acid chloride.
In yet another aspect of the present invention, there is provided a polyurethane reaction system comprising:
component A) comprising:
A1) one or more polyisocyanates;
A2) a free radical initiator;
A3) at least one acid chloride;
component B) comprising:
B1) one or more organic polyols in an amount of 21 to 60 wt.%, based on 100 wt.% of the total weight of the polyurethane reaction system;
B2) one or more compounds having the structure of formula (I)
Wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6.
In a further aspect of the present invention, there is provided the use of an acid chloride to improve the stability of the polyurethane reaction system over the operating time.
Preferably, the acid chloride is selected from the group consisting of formyl chloride, acetyl chloride, benzoyl chloride, phthaloyl chloride, oxalyl chloride, chloroacetyl chloride, trichloroacetyl chloride, trifluoroacetyl chloride or combinations thereof.
Preferably, the polyurethane reaction system comprises:
component A) comprising:
A1) one or more polyisocyanates;
A2) a free radical initiator;
A3) at least one acid chloride;
component B) comprising:
B1) one or more organic polyols in an amount of 21 to 60 wt.%, based on 100 wt.% of the total weight of the polyurethane reaction system;
B2) one or more compounds having the structure of formula (I)
Wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6.
In yet another aspect of the present invention, there is provided a method for stabilizing the operable time of a polyurethane reaction system comprising:
component A) comprising:
A1) one or more polyisocyanates;
component B) comprising:
B1) one or more organic polyols in an amount of 21 to 60 wt.%, based on 100 wt.% of the total weight of the polyurethane reaction system;
B2) one or more compounds having the structure of formula (I)
Wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6; and
component C), a free-radical initiator;
the method is characterized in that at least one acyl chloride of the component D) is added into the polyurethane reaction system, preferably into the component A) and/or the component B).
Preferably, the B2) content is 4 to 33 wt.%, based on the total weight of the polyurethane reaction system, in 100 wt.%.
Preferably, the B2) component is selected from: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or combinations thereof.
Preferably, the organic polyol is selected from the group consisting of polyols having a functionality of from 1.7 to 6, preferably from 1.9 to 4, more preferably from 1.9 to 2.8, and a hydroxyl number of 150 and 1100 mgKOH/g.
Preferably, said component D) at least one acid chloride is selected from the group consisting of formyl chloride, acetyl chloride, benzoyl chloride, phthaloyl chloride, oxalyl chloride, chloroacetyl chloride, trichloroacetyl chloride and trifluoroacetyl chloride, preferably benzoyl chloride.
Preferably, the polyurethane reaction system is operable for a time of 60 minutes or more, preferably 65 minutes or more, more preferably 70 minutes or more at 35 ℃.
Preferably, the open time at 35 ℃ of the polyurethane reaction system comprising at least one acid chloride increases by more than or equal to 30%, preferably more than or equal to 40%, more preferably more than or equal to 50% of the open time at 35 ℃ of the polyurethane reaction system not comprising at least one acid chloride.
Preferably, said D) at least one acid chloride is present in an amount of 0.001 to 3.5 wt.%, preferably 0.003 to 3.0 wt.%, more preferably 0.005 to 2.0 wt.%, based on the total weight of said component a) in 100 wt.%.
In still another aspect of the present invention, there is provided a polyurethane resin obtained by the method for preparing a polyurethane resin according to the present invention.
In still another aspect of the present invention, there is provided a polyurethane product comprising the polyurethane resin according to the present invention, wherein the polyurethane product is selected from cable bridges, door and window curtain wall frames, ladder frames, tent poles or tubes, antiglare sheets, floors, sucker rods, utility poles and crossarms, guardrails, grilles, architectural profiles, container profiles and sheets, bicycle frames, fishing poles, cable cores, insulator mandrels, radomes, single-layer or sandwich continuous sheets, and shells, webs, caps, joists, and blade roots of turbine fan blades.
As described above, isocyanates to which a radical initiator is added are liable to undergo trimerization to form (poly) isocyanurates, and it can be said that the radical initiator catalyzes the trimerization. If the free-radical initiator is mixed directly into the isocyanate, this has an adverse effect on the transport and long-term storage of the isocyanate mixture. Particularly, under the condition of direct sunlight at high temperature in summer, the internal temperature of the common van-type transport vehicle can reach 50-60 ℃ in a sealed environment, so that the trimerization reaction of isocyanate can be promoted to occur in advance, and the quality of an isocyanate product is influenced. During some long haul shipping, ships may travel near the equator of the tropics for several weeks, and it is more difficult to ensure the quality of the isocyanate mixture to which the free radical initiator is added under such long term high temperature conditions.
Surprisingly, we have found that the addition of an appropriate amount of acid chloride to an isocyanate mixture effectively extends the storage time without having to worry about quality problems even during transport under hot weather conditions. It can be seen from the experimental data that the storage stability of the isocyanate compositions with the addition of acid chloride is greatly extended. In the preferred embodiment of the present invention, the right amount of acid chloride gives better and longer storage stability. For example, in a certain range, the larger the content of acid chloride, the better the effect of stable storage may be.
More surprisingly, we have found that the isocyanate compositions of the present invention comprising an isocyanate, a free radical initiator and an acid chloride can achieve a stable open time after addition of the isocyanate reactive component, i.e., the polyurethane reaction systems of the present invention comprising an acid chloride and an isocyanate composition, a polyol, etc., compatible therewith, have a stable open time. Therefore, the polyurethane product with more uniform filling and excellent quality can be prepared, the production efficiency and the yield can be improved, raw materials are saved, and the cost is saved.
At the same time, we have found that the addition of acid chlorides to the polyurethane reaction system, either the isocyanate component or the isocyanate-reactive component, allows the polyurethane reaction system to remain stable for a useful period of time. That is, the polyurethane reaction system of the present invention can be made stable in working time regardless of whether the isocyanate component or the isocyanate-reactive component of the present invention is stored, transported for a long period of time, and the acid chloride is added in accordance therewith.
The method of the invention simply and effectively realizes the stable storage of the isocyanate composition, thereby simplifying the production process of the polyurethane resin, particularly the polyurethane resin used for producing large products such as fan blades and the like, and the polyurethane composite material, and improving the production efficiency. In particular, the method for stably storing an isocyanate composition, the polyurethane reaction system or the method for preparing a polyurethane resin according to the present invention solves the problems in the art, realizes a long and stable operation time, and further improves the production efficiency and yield of the related large polyurethane products, such as fan blades and ships, thereby promoting the commercialization and business explosion of the related industrial innovation.
Drawings
The invention is illustrated below with reference to the accompanying drawings:
FIG. 1 shows infrared spectra of examples of the present invention and comparative examples. Wherein curve s1 in FIG. 1 represents the system spectrum for isocyanate 44V20 alone; curve s2 in fig. 1 shows that after 2 wt.% of TBPB based on the total weight of isocyanate was added to isocyanate 44V20, the viscosity had not changed in the initial stage; curve s3 in fig. 1 shows the spectrum after 56 days of addition of 2 wt.% of TBPB to isocyanate 44V20, based on the total weight of the isocyanate.
Detailed Description
The following terms used in the present invention have the following definitions or explanations.
pbw is the mass part of each component of the reaction system;
functionality, means according to the industry formula: functionality as measured by hydroxyl number molecular weight/56100; wherein the molecular weight is determined by GPC high performance liquid chromatography;
isocyanate index, which means a value calculated by the following formula:
as mentioned above, the present invention provides a process for the stable storage of isocyanate compositions by adding A3) at least one acid chloride to an isocyanate and a free radical initiator. The isocyanate composition of the present invention comprises:
A1) one or more polyisocyanates;
A2) a free radical initiator;
A3) at least one acid chloride.
The polyurethane reaction system comprises the following components:
component A) comprising:
A1) one or more polyisocyanates;
A2) a free radical initiator;
A3) at least one acid chloride;
component B) comprising:
B1) one or more organic polyols in an amount of 21 to 60 wt.%, based on 100 wt.% of the total weight of the polyurethane reaction system;
B2) one or more compounds having the structure of formula (I)
Wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6.
In particular, any organic polyisocyanate may be used in the foregoing methods of the invention, including aromatic, aliphatic, and cycloaliphatic polyisocyanates and combinations thereof. The polyisocyanates can be represented by the general formula R (nco) n, wherein R represents an aliphatic hydrocarbon group having 2 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 15 carbon atoms, an araliphatic hydrocarbon group having 8 to 15 carbon atoms, and n is 2 to 4.
Useful polyisocyanates include, preferably but are not limited to, vinyl diisocyanate, tetramethylene 1, 4-diisocyanate, Hexamethylene Diisocyanate (HDI), dodecyl 1, 2-diisocyanate, cyclobutane 1, 3-diisocyanate, cyclohexane-1, 4-diisocyanate, 1-isocyanato-3, 3, 5-trimethyl-5-isocyanatomethylcyclohexane, hexahydrotoluene-2, 4-diisocyanate, hexahydrophenyl-1, 3-diisocyanate, hexahydrophenyl-1, 4-diisocyanate, perhydrodiphenylmethane 2, 4-diisocyanate, perhydrodiphenylmethane 4, 4-diisocyanate, phenylene-1, 3-diisocyanate, phenylene-1, 4-diisocyanate, diphenylene-1, 4-diisocyanate, 3-dimethyl-4, 4-diphenyldiisocyanate, toluene-2, 4-diisocyanate (TDI), toluene-2, 6-diisocyanate (TDI), diphenylmethane-2, 4 '-diisocyanate (MDI), diphenylmethane-2, 2' -diisocyanate (MDI), diphenylmethane-4, 4 '-diisocyanate (MDI), mixtures of diphenylmethane diisocyanates and/or homologues of diphenylmethane diisocyanates having more than one ring, polyphenylmethane polyisocyanates (polymeric MDI), naphthylene-1, 5-diisocyanate (NDI), their isomers, mixtures of diphenylene-1, 4-diisocyanate, diphenylene-2, 6-diisocyanate (TDI), diphenylmethanes-2, 4' -diisocyanate (MDI), diphenylmethanes, Any mixtures thereof with their isomers.
Useful polyisocyanates also include isocyanates obtained by modification with carbodiimide, allophanate, etc., preferably, but not limited to, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, isomers thereof, mixtures thereof with isomers thereof.
When used in the present invention, the polyisocyanate includes an isocyanate dimer, trimer, tetramer or a combination thereof.
In certain embodiments of the present invention, the isocyanate is selected from an aromatic isocyanate, preferably diphenylmethane diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate or a combination thereof, particularly preferably diphenylmethane diisocyanate or (poly) diphenylmethane diisocyanate.
In a preferred embodiment of the invention, the polyisocyanate component is selected from polymeric MDI.
The NCO content of the organic polyisocyanates of the present invention is from 20 to 33 wt.%, preferably from 25 to 32 wt.%, particularly preferably from 30 to 32 wt.%. The NCO content was determined by GB/T12009.4-2016.
The organic polyisocyanates can also be used in the form of polyisocyanate prepolymers. These polyisocyanate prepolymers can be obtained by reacting an excess of the above-mentioned organic polyisocyanate with a compound having at least two isocyanate-reactive groups at a temperature of, for example, 30 to 100 c, preferably about 80 c. The NCO content of the polyisocyanate prepolymers of the present invention is from 20 to 33% by weight, preferably from 25 to 32% by weight. The NCO content was determined by GB/T12009.4-2016.
A radical initiator refers to an agent capable of generating radicals in a radical reaction. Also known as free radical initiators. The process of generating free radicals becomes chain initiation. The radical initiator that can be used in the present invention includes, but is not limited to, peroxide initiators, organic peroxide initiators and inorganic peroxide initiators, azo initiators, redox initiators, and the like.
The general structural formula of the organic peroxide compound is R-O-O-H or R-O-O-R, wherein R is alkyl, acyl, carbonate and the like. It further comprises: acyl peroxides, for example: benzoyl peroxide, lauroyl peroxide; hydroperoxides, such as: cumene hydroperoxide, tert-butyl hydroperoxide; dialkyl peroxides, for example: di-tert-butyl peroxide, dicumyl peroxide; ester peroxides, tert-butyl peroxybenzoate, tert-butyl peroxypivalate; ketone peroxides, for example: methyl ethyl ketone peroxide and cyclohexanone peroxide; dicarbonate peroxides, for example: diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate. The azo initiator may be selected from azobisisobutyronitrile, azobisisoheptonitrile, or a mixture thereof.
The acyl chloride of the invention refers to a compound containing carbonyl chloride functional group, belongs to the category of acyl halide, and is a carboxylic acid derivative formed by replacing hydroxyl in carboxylic acid with chlorine. Generally, acid chlorides can be prepared by reacting thionyl chloride, phosphorus trichloride, phosphorus pentachloride with a carboxylic acid. The thionyl chloride is commonly used, and the products of sulfur dioxide and hydrogen chloride are gases, so the gases are easy to separate, the purity is good, and the yield is high. Thionyl chloride has a boiling point of only 79 ℃ and a slight excess of thionyl chloride can be separated off by distillation. The reaction for preparing the acid chloride with thionyl chloride can be catalyzed by dimethylformamide.
Alternatively, the acid chloride may be prepared by reaction with a carboxylic acid using oxalyl chloride as the chlorinating agent. Catalysis was performed using dimethylformamide. The first step is the reaction of dimethylformamide with oxalyl chloride to form an active imide salt intermediate. The carboxylic acid then reacts with this intermediate to form the acid chloride, and dimethylformamide is again obtained. The acid chloride can also be obtained by the Appel reaction of carboxylic acid, carbon tetrachloride and triphenylphosphine. Carboxylic acids can also be used to react with cyanuric chloride to form acid chlorides.
Acid chlorides suitable for use in the present invention include, but are not limited to, formyl chloride, acetyl chloride, benzoyl chloride (CAS No.98-88-4), phthaloyl chloride, oxalyl chloride, chloroacetyl chloride, trichloroacetyl chloride, trifluoroacetyl chloride, or combinations thereof.
The polyols useful in the present invention may be polyether polyols, polyester polyols, polycarbonate polyols, and/or mixtures thereof. Preference is given to one or more polyether polyols having a functionality of from 2 to 8, preferably from 3 to 6, and a hydroxyl number of from 50 to 1200, preferably from 200-.
Examples of polyether polyols useful in the present invention are aromatic amine-initiated polyether polyols, including propylene oxide-based polyether polyols initiated with diphenylmethanediamine. Part of the polyether polyols useful in the present invention are selected from glycerol, propylene glycol, sucrose, sorbitol initiated polyether polyols.
The polyester polyol is prepared by reacting dicarboxylic acid or dicarboxylic anhydride with polyhydric alcohol. The dicarboxylic acids are preferably, but not limited to, aliphatic carboxylic acids having 2 to 12 carbon atoms, such as: succinic acid, malonic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanecarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and mixtures thereof. The dibasic acid anhydride is preferably, but not limited to, phthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, or a mixture thereof. The polyhydric alcohol is preferably, but not limited to, ethylene glycol, diethylene glycol, 1, 2-propanediol, 1, 3-propanediol, dipropylene glycol, 1, 3-methylpropanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 1, 10-decanediol, glycerol, trimethylolpropane, or a mixture thereof. The polyester polyol also comprises polyester polyol prepared from lactone. The polyester polyol prepared from lactone is preferably, but not limited to, a polyester polyol prepared from epsilon-caprolactone.
The polycarbonate polyol is preferably, but not limited to, a polycarbonate diol. The polycarbonate diol may be prepared by reacting a diol with a dialkyl or diaryl carbonate or phosgene. The diol is preferably, but not limited to, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol, trioxymethylene glycol, or a mixture thereof. The dialkyl or diaryl carbonate is preferably, but not limited to, diphenyl carbonate.
Optionally, the polyurethane reaction system of the invention also comprises one or more compounds B2 having the structure of formula (I)
Wherein R is1Selected from hydrogen, methyl or ethyl; r2Selected from alkylene groups having 2 to 6 carbon atoms; n is an integer selected from 1 to 6.
In the preferred embodiment of the inventionIn, R2Selected from the group consisting of ethylene, propylene, butylene, pentylene, 1-methyl-1, 2-ethylene, 2-methyl-1, 2-ethylene, 1-ethyl-1, 2-ethylene, 2-ethyl-1, 2-ethylene, 1-methyl-1, 3-propylene, 2-methyl-1, 3-propylene, 3-methyl-1, 3-propylene, 1-ethyl-1, 3-propylene, 2-ethyl-1, 3-propylene, 3-ethyl-1, 3-propylene, 1-methyl-1, 4-butylene, 2-methyl-1, 4-butylene, 3-methyl-1, 4-butylene and 4-methyl-1, 4-butylene, 2-bis (4-phenylene) -propane, 1, 4-dimethylene-benzene, 1, 3-dimethylene-benzene, 1, 2-dimethylene-benzene.
Preferably, the B1) is selected from organic polyols, wherein the organic polyols are selected from polyols having a functionality of from 1.7 to 6, preferably from 1.9 to 4.5, and a hydroxyl number of 150-.
In a preferred embodiment of the invention, said B2) component is selected from: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or combinations thereof.
The compounds of formula (I) can be prepared by methods customary in the art, for example by (meth) acrylic anhydride or (meth) acrylic acid, (meth) acrylic acid halide compounds with HO- (R)2O)n-H is prepared by esterification reactions, the preparation process being well known to the person skilled in the art, for example as described in handbook of polyurethane raw materials and auxiliaries (bang of liu yi jun, published 4/1/2005) third chapter, and chapter ii of polyurethane elastomers (bang of liu yi jun, published 8/2012), the entire contents of which are incorporated herein by reference.
In the method for producing a polyurethane resin of the present invention, in the polyaddition reaction of isocyanate groups with hydroxyl groups, the isocyanate groups may be contained in the isocyanate groups of the organic polyisocyanate (component a), or may be the isocyanate groups contained in the reaction intermediate product of the organic polyisocyanate (component a) with the organic polyol (B1) component) or B2) component, and the hydroxyl groups may be the hydroxyl groups contained in the reaction intermediate product of the organic polyisocyanate (component a) with the organic polyol (B1) component) or B2) component, or may be the hydroxyl groups contained in the reaction intermediate product of the organic polyisocyanate (component a) with the organic polyol (B1) component) or B2) component.
The radical polymerization reaction of the present invention is an addition polymerization reaction of the olefinic bond, wherein the olefinic bond may be the olefinic bond contained in the B2) component or the olefinic bond contained in the intermediate product of the reaction of the B2) component with the organic polyisocyanate.
In the method for producing a polyurethane resin of the present invention, polyurethane addition polymerization (i.e., addition polymerization of isocyanate groups and hydroxyl groups) is carried out simultaneously with radical polymerization. As known to those skilled in the art, suitable reaction conditions can be selected so that the polyurethane addition polymerization reaction and the free radical polymerization reaction are carried out in sequence, but the polyurethane matrix prepared in the way is different from the polyurethane resin matrix prepared by simultaneously carrying out the polyurethane addition polymerization reaction and the free radical polymerization reaction, so that the mechanical properties and the manufacturability of the prepared polyurethane composite material are different.
Optionally, the polyurethane reaction system described above may further comprise auxiliaries or additives including, but not limited to: fillers, internal mold release agents, flame retardants, smoke suppressants, dyes, pigments, antistatic agents, antioxidants, UV stabilizers, diluents, organic acids, inorganic acids, masking agents, organic ligands, defoamers, coupling agents, surface wetting agents, leveling agents, water scavengers, catalysts, molecular sieves, thixotropic agents, plasticizers, blowing agents, foam stabilizers, foam homogenizers, radical reaction inhibitors, accelerators or combinations thereof, which components may optionally be comprised in the isocyanate component a) and/or the isocyanate-reactive component B) of the present invention. These components can also be stored separately as a further component and, when used for the preparation of polyurethane composites, are mixed with the isocyanate component A) and/or the component B) according to the invention before the preparation. Accelerators useful in the present invention include cobalt salt accelerators which can simultaneously accelerate both the addition polymerization and the free radical polymerization of polyurethanes.
In some embodiments of the invention, the filler is selected from: aluminum hydroxide, bentonite, fly ash, wollastonite, perlite powder, cenosphere, calcium carbonate, talcum powder, mica powder, porcelain clay, fumed silica, expandable microspheres, diatomite, volcanic ash, barium sulfate, calcium sulfate, glass microspheres, stone powder, wood powder, sawdust, bamboo powder, bamboo sawdust, rice grains, straw scraps, sorghum straw scraps, graphite powder, metal powder, thermosetting composite material recycled powder, plastic particles or powder or a combination thereof. Wherein the glass microspheres can be solid or hollow.
The internal mold release agent which can be used in the present invention includes any conventional mold release agent used for producing polyurethane, and examples thereof include long-chain carboxylic acids, particularly fatty acids such as stearic acid, amines of long-chain carboxylic acids such as stearamide, fatty acid esters, metal salts of long-chain carboxylic acids such as zinc stearate, or polysiloxanes.
Examples of flame retardants that can be used in the present invention include triaryl phosphate, trialkyl phosphate, triaryl or trialkyl phosphate with halogen, melamine resins, halogenated paraffins, red phosphorus, or combinations thereof.
Other adjuvants useful in the present invention include water scavengers such as molecular sieves; defoamers, such as polydimethylsiloxane; coupling agents, such as monoepoxyethane or organic amine functional trialkoxysilane or combinations thereof. Coupling agents are particularly preferred for improving the adhesion of the resin matrix to the fibrous reinforcement. Finely particulate fillers, such as clays and fumed silicas, are commonly used as thixotropic agents.
Through repeated experiments, the invention unexpectedly discovers that the invention can provide the isocyanate composition with stable storage, the polyurethane reaction system with stable reaction speed and stable operable time, and the method for stably storing the isocyanate composition and obtaining the polyurethane reaction system with stable operable time, thereby not only being capable of preparing polyurethane resin and polyurethane composite materials with excellent quality, but also simplifying the process and improving the production efficiency. Meanwhile, the yield can be improved, the waste of resources is reduced and even avoided, and the method is more environment-friendly.
Examples
The raw material sources are as follows:
isocyanate 44V 20: NCO%: 30.5-32.5%, viscosity: 160-240mP.s @25 ℃ as purchased from Corsia Polymer (China) Co., Ltd;
tert-butyl peroxybenzoate (TBPB): purchased from acyclovir;
accelerator (NL-49P): purchased from acyclovir;
benzoyl chloride: purchasing the Chinese medicines in Shanghai;
polyol 1: propylene oxide based polyether polyols, initiator component ═ glycerol, functionality ═ 3, hydroxyl number 350, purchased from koste polymers (china) limited;
hydroxypropyl methacrylate: procurement in the Heshi wall chemical industry.
Examples the test methods are illustrated below:
the NCO content, which is the NCO group content of the system, was determined by GB/T12009.4-2016 at room temperature.
And (3) viscosity testing: the test was carried out at 25 ℃ according to GB/T12008.8-1992.
The pot-life is the time from stirring the reaction system components until the viscosity reaches 600 mPa.S. The operable time of the present invention is determined by: respectively carrying out constant temperature treatment on each component of a polyurethane reaction system at 35 ℃, then mixing each component according to the required proportion, stirring for 1 minute until the components are uniformly mixed, keeping the temperature at 35 ℃, measuring the viscosity once every 3 minutes by using a viscometer, and recording the time required until the viscosity of the reaction system reaches 600mPa.S, namely the operable time. The viscometer is a Brook-Field product (model Pro + DV-II).
Stable storage time: the isocyanate composition is subjected to NCO and viscosity tests according to the method (the sample to be detected is subjected to the tests at the corresponding temperature or is adjusted to the corresponding temperature), if the NCO and the viscosity do not change greatly, the isocyanate composition is considered to be stably stored, and the recording time is the stable storage time. The NCO change/decrease is not so great, and in the case of the present invention, it may be that the NCO change/decrease does not exceed 5%; can be calculated by the following formula: percent NCO change/reduction ═ initial NCO-NCO (NCO after a period of storage)/initial NCO. The viscosity change/increase is not significant, and for the purposes of the present invention, may be a viscosity change/increase of no more than 50%, and may be calculated using the following equation: viscosity change/increase — (% viscosity after storage over time-initial viscosity)/initial viscosity.
Comparative example 1
Adding 100 parts by weight of liquid isocyanate raw material 44V20 into a plastic cup, adding 2 parts by weight of TBPB, quickly stirring uniformly, then placing into a 50 ℃ oven, and monitoring the viscosity change and the temperature change of the mixture. At intervals, samples were removed, cooled to room temperature (25 degrees Celsius), and tested for viscosity and NCO content. The test results are shown in Table 1.
TABLE 1 test results of comparative example 1
| Time (sky) | 0 | 7 | 21 | 35 | 49 | 56 |
| Temperature at the onset (. degree. C.) | 50 | 50 | 50 | 50 | 50 | 50 |
| NCO value | 30.21 | 30.13 | 30.1 | 28.19 | 26.33 | 25.7 |
| Viscosity (mPa.S) | 194 | 225 | 250 | 2200 | 17000 | ＞100000 |
| Resin real time temperature in oven (. degree. C.) | 50 | 50 | 50 | 50 | 50 | 50 |
As can be seen from Table 1 above, the viscosity of the isocyanates increases significantly after a few weeks and is already seriously unsatisfactory with respect to the quality standards. After 5 weeks, the NCO had dropped significantly and the viscosity had become too high to be useful.
The infrared spectrum of figure 1 also verifies these changes. Compared with isocyanate without adding free radical initiator, the isocyanate with the free radical initiator has three characteristic peaks (1704.80cm-1, 1409.60cm-1 and 758.36cm-1) after 56 days, shows the existence of isocyanurate group, and verifies that trimerization reaction is carried out to generate the isocyanurate group under the condition of the existence of free radical. (Note: FIG. 1, curve s1 shows the spectrum for the system only with isocyanate 44V 20; FIG. 1, curve s2 shows that the viscosity has not changed in the initial stage after 2 wt.% of TBPB based on the total weight of the isocyanate has been added to isocyanate 44V 20; FIG. 1, curve s3 shows the spectrum after 56 days after 2 wt.% of TBPB based on the total weight of the isocyanate has been added to isocyanate 44V 20.)
Based on this problem, we have found that in this isocyanate mixture, it is attempted to add some auxiliary agents in small amounts, as shown in example 1 below.
Example 1
Adding 100 parts by weight of liquid isocyanate raw material 44V20 into a plastic cup, adding 2 parts by weight of TBPB and 0.02 part by weight of benzoyl chloride, quickly stirring and dissolving uniformly, then placing into an oven at 50 ℃, and monitoring the viscosity change and the temperature change of the liquid isocyanate raw material. At intervals, samples were removed, cooled to room temperature (25 degrees Celsius), and tested for viscosity and NCO content. The test results are shown in Table 2.
TABLE 2 test results of example 1
| Time (sky) | 0 | 14 | 28 | 42 | 56 |
| Temperature at the onset (. degree. C.) | 50 | 50 | 50 | 50 | 50 |
| NCO value | 30.12 | 30.05 | 29.9 | 29.7 | 29.4 |
| Viscosity (mPa.S) | 198 | 209 | 226 | 255 | 279 |
| Resin real-time temperature in oven (. degree. C.) | 50 | 50 | 50 | 50 | 50 |
As can be seen from the data in Table 2, the reaction rate of the isocyanate composition is controlled and the increase in viscosity is very limited, indicating that it can be stored stably with the addition of benzoyl chloride.
We premixed polyol 1, HPMA and NL-49P in a weight ratio of 90/73.4/0.15, designated component B (fresh make-up, not stored, specific parts by weight in pbw shown below in Table 5); component B was then allowed to stand at room temperature for an additional 18 months to give component B which was then reacted with 44V20 parts by weight and TBPB as shown in Table 3 and tested for open time at 35 degrees Celsius (pot-life) and the data shown in Table 3.
TABLE 3 test results for comparative example 2C and examples 2-5 (unit: parts by weight in pbw)
| Examples | 2 | 2C | 3 | 4 |
| Component B | 163.5 | / | / | / |
| Component B (B) B (B) B (B) B (B) B (B) B (B) B (B) B (B) B (B) B (B) B (B) B (B) B (B) B (B) B (B) | / | 163.5 | 163.5 | 163.5 |
| 44V20 | 142.9 | 142.9 | 142.9 | 142.9 |
| TBPB | 2.7 | 2.7 | 2.7 | 2.7 |
| Benzoyl chloride | / | / | 0.0292 | 0.0584 |
| Operational time (minutes) | 75 | 47 | 76 | 74 |
As can be seen from examples 2-4 and comparative example 2C of Table 3, the addition of an acid chloride (e.g., benzoyl chloride) stabilizes the pot life of the polyurethane reaction system for longer storage periods. The benzoyl chloride can be premixed with the isocyanate and the free radical initiator, and can also be added into the component B to achieve the same effect. The operable time of the polyurethane reaction system without adding acyl chloride is seriously reduced, and the requirement of actual industrial production can not be met.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (15)
1. A method for stably storing an isocyanate composition comprising:
A1) one or more polyisocyanates;
A2) at least one free radical initiator;
said method is to add A3) at least one acid chloride to the isocyanate composition.
2. The process of claim 1, wherein said a3) at least one acid chloride is selected from the group consisting of formyl chloride, acetyl chloride, benzoyl chloride, phthaloyl chloride, oxalyl chloride, chloroacetyl chloride, trichloroacetyl chloride, trifluoroacetyl chloride, and combinations thereof.
3. Process according to claim 1 or 2, characterized in that the a3) at least one acid chloride is present in an amount of 0.001 to 3.5 wt.%, preferably 0.003 to 3.0 wt.%, more preferably 0.005 to 2.0 wt.%, based on the total weight of the isocyanate composition, of 100 wt.%.
4. An isocyanate composition comprising:
A1) one or more polyisocyanates;
A2) at least one free radical initiator; and
A3) at least one acid chloride.
5. The isocyanate composition according to claim 4, wherein said A3) at least one acid chloride is present in an amount of 0.001 to 3.5 wt.%, preferably 0.003 to 3.0 wt.%, more preferably 0.005 to 2.0 wt.%, based on the total weight of the isocyanate composition, of 100 wt.%.
6. The isocyanate composition according to claim 4 or 5, wherein the isocyanate composition comprising at least one acid chloride has a prolonged shelf life of 5 days or more, preferably 7 days or more, more preferably 14 days or more at 50 ℃ than an isocyanate composition not comprising at least one acid chloride.
7. Use of an acid chloride to inhibit the trimerisation reaction of isocyanates catalysed by a free radical initiator.
8. A method for preparing polyurethane resin, which comprises the following steps of reacting a polyurethane reaction system comprising the following components:
component A) comprising: the isocyanate composition of any one of claims 4 to 6;
component B) comprising:
B1) one or more organic polyols in an amount of 21 to 60 wt.%, based on 100 wt.% of the total weight of the polyurethane reaction system;
B2) one or more compounds having the structure of formula (I)
Wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6.
9. The method as set forth in claim 8, wherein said B2) component is selected from the group consisting of: hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or combinations thereof.
10. Process according to claim 8 or 9, characterized in that the polyurethane reaction system is operable for a time of 60 minutes or more, preferably 65 minutes or more, more preferably 70 minutes or more at 35 ℃.
11. The method according to claim 8 or 9, wherein the stability of the polyurethane reaction system comprising at least one acid chloride at 35 ℃ over the time at 35 ℃ is increased by more than or equal to 30%, preferably more than or equal to 40%, more preferably more than or equal to 50% compared to the stability of the polyurethane reaction system not comprising at least one acid chloride at 35 ℃.
12. Use of an acid chloride to improve the stability of the polyurethane reaction system over the operating time.
13. A method of stabilizing the open time of a polyurethane reaction system comprising:
component A) comprising:
A1) one or more polyisocyanates;
component B) comprising:
B1) one or more organic polyols in an amount of 21 to 60 wt.%, based on 100 wt.% of the total weight of the polyurethane reaction system;
B2) one or more compounds having the structure of formula (I)
Wherein R1 is selected from hydrogen, methyl or ethyl; r2 is selected from alkylene having 2 to 6 carbon atoms, 2-bis (4-phenylene) -propane, 1, 4-bis (methylene) benzene, 1, 3-bis (methylene) benzene, 1, 2-bis (methylene) benzene; n is an integer selected from 1 to 6; and
component C), a free-radical initiator;
the method is characterized in that at least one acyl chloride of the component D) is added into the polyurethane reaction system.
14. A polyurethane resin obtained by the method for producing a polyurethane resin according to claims 8 to 11.
15. A polyurethane product comprising the polyurethane resin of claim 14, wherein the polyurethane product is selected from the group consisting of cable trays, door and window curtain wall frames, ladder frames, tent poles or tubes, antiglare panels, flooring, sucker rods, utility poles and crossarms, guardrails, grilles, architectural profiles, container profiles and sheets, bicycle frames, fishing rods, cable cores, insulator mandrels, radome, single or sandwich continuous sheets, and turbine fan blade shells, webs, beam caps, joists, and blade roots.
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