CN1053924A - 有机膦或胂与弱亲核酸形成的化合物或配合物,含有它们的含环氧化合物和酚式羟基化合物的组合物 - Google Patents
有机膦或胂与弱亲核酸形成的化合物或配合物,含有它们的含环氧化合物和酚式羟基化合物的组合物 Download PDFInfo
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- CN1053924A CN1053924A CN91100768A CN91100768A CN1053924A CN 1053924 A CN1053924 A CN 1053924A CN 91100768 A CN91100768 A CN 91100768A CN 91100768 A CN91100768 A CN 91100768A CN 1053924 A CN1053924 A CN 1053924A
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- 239000000203 mixture Substances 0.000 title claims abstract description 91
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 150000001875 compounds Chemical class 0.000 title claims abstract description 39
- 230000000269 nucleophilic effect Effects 0.000 title claims abstract description 34
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 33
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 150000007513 acids Chemical group 0.000 title claims description 4
- -1 phenolic hydroxyl compound Chemical class 0.000 title description 30
- 239000004593 Epoxy Substances 0.000 title description 29
- 239000002253 acid Substances 0.000 claims abstract description 68
- 125000000129 anionic group Chemical group 0.000 claims abstract description 32
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 24
- 239000011707 mineral Substances 0.000 claims abstract description 24
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000011877 solvent mixture Substances 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- PWMZYSHRRDICHT-UHFFFAOYSA-N [As](O)(O)(O)=O.[F] Chemical compound [As](O)(O)(O)=O.[F] PWMZYSHRRDICHT-UHFFFAOYSA-N 0.000 claims description 4
- WPGUUPJOAVPZBQ-UHFFFAOYSA-N [Cl].OP(O)(O)=O Chemical compound [Cl].OP(O)(O)=O WPGUUPJOAVPZBQ-UHFFFAOYSA-N 0.000 claims description 4
- BMASNNCVYJEPAE-UHFFFAOYSA-N [Cl].[As](O)(O)(O)=O Chemical compound [Cl].[As](O)(O)(O)=O BMASNNCVYJEPAE-UHFFFAOYSA-N 0.000 claims description 4
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 4
- 229940005991 chloric acid Drugs 0.000 claims description 4
- BRCRFYDCLUTJRQ-UHFFFAOYSA-N chloroboronic acid Chemical compound OB(O)Cl BRCRFYDCLUTJRQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims 4
- 238000003860 storage Methods 0.000 claims 4
- 230000004927 fusion Effects 0.000 claims 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims 1
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 claims 1
- 229960005222 phenazone Drugs 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 35
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 29
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 17
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 13
- 229940106691 bisphenol a Drugs 0.000 description 11
- 150000002118 epoxides Chemical class 0.000 description 11
- 229930185605 Bisphenol Natural products 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 9
- 235000010755 mineral Nutrition 0.000 description 9
- 229920003986 novolac Polymers 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 6
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 150000002440 hydroxy compounds Chemical class 0.000 description 6
- 239000005011 phenolic resin Substances 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 230000029936 alkylation Effects 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- ONDPGJBEBGWAKI-UHFFFAOYSA-N diphenylphosphane;propane Chemical compound CCC.C=1C=CC=CC=1PC1=CC=CC=C1 ONDPGJBEBGWAKI-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical class OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000013032 Hydrocarbon resin Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000001475 halogen functional group Chemical group 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229920006270 hydrocarbon resin Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012434 nucleophilic reagent Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical group CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical group OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- GBSGXZBOFKJGMG-UHFFFAOYSA-N 3-propan-2-yloxypropan-1-ol Chemical group CC(C)OCCCO GBSGXZBOFKJGMG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- VQNIOZLNRYKVEF-UHFFFAOYSA-N decylphosphane Chemical class CCCCCCCCCCP VQNIOZLNRYKVEF-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- AAKDVDDBABPPKC-UHFFFAOYSA-N dodecylphosphane Chemical compound CCCCCCCCCCCCP AAKDVDDBABPPKC-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- SCCLFGAYCGKMEI-UHFFFAOYSA-N heptylphosphane Chemical class CCCCCCCP SCCLFGAYCGKMEI-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CZRKJHRIILZWRC-UHFFFAOYSA-N methyl acetate;propane-1,2-diol Chemical compound COC(C)=O.CC(O)CO CZRKJHRIILZWRC-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OYFFQMKVQYLFTC-UHFFFAOYSA-N nonylphosphane Chemical class CCCCCCCCCP OYFFQMKVQYLFTC-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000020030 perry Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- BPLUKJNHPBNVQL-UHFFFAOYSA-N triphenylarsine Chemical compound C1=CC=CC=C1[As](C=1C=CC=CC=1)C1=CC=CC=C1 BPLUKJNHPBNVQL-UHFFFAOYSA-N 0.000 description 1
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 1
- UNONUKLLXITFPT-UHFFFAOYSA-N undecylphosphane Chemical compound CCCCCCCCCCCP UNONUKLLXITFPT-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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Abstract
有机膦或胂与具有弱亲核阴离子的无机酸接触
形成产物,与每分子平均有一个以上环氧基以及还可
能有一个以上酚式羟基的化合物混合,可提供稳定的
组合物。
Description
本发明涉及潜在的,可固化的,含环氧化合物和含芳羟基化合物的催化混合物。本发明还涉及潜在催化剂和含有它们的环氧树脂组合物。
用鏻和其它化合物预催化环氧树脂以提供潜在的组合物,当与含芳羟基化合物混合时,形成分子量较高的高级环氧树脂(见Perry的U.S.3,948,855和Can.893,191;Dante等人的U.S.3,477,990;Mueller等人的U.S.3,547,881;Tyler等人的U.S.4,366,295和Cragar的Can.858,648)。
尽管含有这些催化剂和环氧树脂的组合物有一定的稳定性,但同时含有芳羟基化合物的该组合物则缺乏稳定性。
本发明的一方面是关于新的环氧树脂潜在催化剂,其特征在于该催化剂是一种加合物,配合物或化合物,产生于(1)使(a)至少一种有机膦或有机胂与(b)一种带有弱亲核酸阴离子的有机酸或这类酸的混合物接触;或(2)使(a)至少一种带有较强亲核性阴离子的酸和有机膦或有机胂的加合物与一种带有弱亲核性阴离子的无机酸或其金属盐接触,或与这类酸的混合物或其金属盐的混合物接触;其中组分(a)和(b)的接触量为组分(a)与组分(b)的摩尔比在0.6∶1至1.4∶1之间;条件是当组分(1-a)是膦时,它是除三苯膦以外的膦。
本发明的另一方面是关于新的环氧树脂潜在催化剂,其特征在于该催化剂是一种加合物,配合物或化合物,以下式Ⅰ或Ⅱ表示。
式中R,R1,R2,R3,R4,R5和R6各自独立地为具有1-18个碳原子的烃基或者R,R1或R2中的两个基团或R3和R4或R5和R6可结合形成一个杂环;每个x为较弱亲核性酸的阴离子部分;Z为P或AS;Z′为具有1-10个碳原子的二价烃基;m的值与阴离子X的价数相等;条件是式Ⅰ中R,R1或R2至少之一是除苯基以外的基团,并且当Z′为-CH2-CH2-时,式Ⅱ中R3,R4,R5或R6至少之一是除甲基以外的基团。
本发明的另一方面是关于其特征为含有(A)至少一种每分子包含平均多于1个环氧基的化合物;和(B)产物(1)或(2)至少之一的组合物,产物(1)产生于使(a)至少一种有机膦或胂与(b)一种带有弱亲核性阴离子的无机酸或这类酸的混合物接触;产物(2)产生于使(a)至少一种带有较强亲核性阴离子的酸和有机膦或胂化合物的加合物与(b)一种带有弱亲核性阴离子的无机酸或其金属盐接触,或与这类酸的混合物或其金属盐混合物接触;其中(ⅰ)组分(a)和(b)的接触量使得组合物在50℃下存放14天后可满足其粘度要求;(ⅱ)组分(A)和(B)的混合物,当溶于20~40%(重量)适宜溶剂或溶剂混合物时,在25℃下测得的粘度与含有只由组分(a)组成的催化剂的同类组合物的粘度相比为75%或更低,较好为10%或更低,最好为1%或更低,所述的粘度是在50℃下存放14天后测定的。
本发明的另一方面是关于其特征为含有(A)、(B)和(C)的组合物,其中(A)至少一种每分子包含平均多于1个环氧基的化合物;(B)选自下列的至少一种催化剂:(1)使(a)至少一种有机膦或胂与(b)一种带有弱亲核性阴离子的无机酸或这类酸的混合物接触而得到的产物;和(2)使(a)至少一种带有较强亲核性阴离子的酸和有机膦或胂化合物的加合物与(b)一种带有弱亲核性阴离子的无机酸或其金属盐接触,或与这类酸的混合物或其金属盐的混合物接触而得到的产物;(C)至少一种每分子包含平均多于1个芳羟基的化合物;其中(ⅰ)组分(a)和(b)的接触量使得组合物在50℃下存放14天后可满足其粘度要求;(ⅱ)组分(A)和(C)的存在量使芳羟基与环氧基之比为0.05∶1~20∶1,(ⅲ)组分(A),(B)和(C)的混合物,当溶于20~40%(重量)适宜溶剂或溶剂混合物时,在25℃下所测得的粘度与含有只由组分(a)组成的催化剂的同类组合物的粘度相比为75%或更低,较好为10%或更低,最好为1%或更低,所述的粘度是在50℃下存放14天后测定的。
本文所用的术语弱亲核性是指化合物的亲核性值“n”为0至小于2.5(见C.G.Swain and C.B.Scott.J.Am.Chem.Soc.,Vol75,P.141(1953),在此援引以供参考)。弱亲核试剂的亲核性值“n”可为1至小于2.7,较好为1.1至2.5;最好为1.1至2。
本文所用的术语较强的亲核性是指亲核性值“n”为2.5或大于2.5(见C.G.Swain and C.B.Scott.J.Am.Chem.Soc.,Vol.75,P.141(1953),在此援引以供参考)。强亲核试剂的亲核性值为2.7至约6.6,较好为2.8至5.5,最好为3至5。
本发明所用的催化剂制备如下:将膦或胂化合物与带有弱亲核性阴离子的酸或酸的盐以所需比例简单混合并搅拌以确保达到密切接触。可在0℃~100℃,宜在20℃~60℃下接触足够一段时间以完成可发生的任何反应。接触时间的长短取决于温度,但通常为1-120分钟,以5-60分钟为宜。在混合各组分时所采用的压力为低于一大气压至高于一大气压,较好为1mmHg-7,600mmHg,更好为200mmHg~2,280mmHg(绝对压力)。
制备催化剂所用各组分的混合比为每摩尔膦或胂化合物(a)与0.6~1.4,较好为0.75~1.35,最好为0.95~1.2摩尔的酸(b)混合,或带有弱亲核性阴离子的无机酸或这类酸的金属盐(b)与带有较强亲核性阴离子的酸和有机膦或胂的加合物(a)的摩尔比为0.6~1.4,较好为0.75~1.35,最好为0.95~1.2。
当加热到至少75℃~250℃,较好是90℃~225℃,最好是100℃~200℃时,催化剂的用量应是以催化含氧化合物,即组分(A)和含芳羟基化合物,即组分(C)之间的反应。在大多数情况下,催化剂的量为每环氧当量0.05~100,较好是0.1~50,更好为0.5~20,最好为1~10毫摩尔催化剂。
可用于制备催化剂的适宜的膦或胂化合物包括以下式Ⅲ或Ⅳ代表的化合物:
式中R,R1,R2,R3,R4,R5和R6各自独立地为碳原子数宜为1~18,较好为1~9,最好为1~6的烃基或烃氧基,或者R,R1,和R2中的两个基团或R3和R4或R5和R6可结合形成一个杂环,Z为P或As。特别适宜的膦化合物包括,例如,三苯膦,三甲基膦,三丙基膦,三丁基膦,三戊基膦,三庚基膦,三辛基膦,三壬基膦,三癸基膦,三(十一烷基)膦,三(十二烷基)膦,双(二苯基膦基)-甲烷,1,2-双(二苯基膦基)-乙烷,1,3-双(二苯基膦基)-丙烷,1,2-双(二甲基膦基)-乙烷,1,3-双(二甲基膦基)-丙烷。或其任意混合物。特别适宜的胂化合物包括,例如,三苯胂,三丁胂,或其混合物。
带有弱亲核性阴离子的特别适宜的无机酸包括,例如,氟硼酸,氟砷酸,氟锑酸,氟磷酸,氯硼酸,氯砷酸,氯锑酸,氯磷酸,高氯酸,氯酸,溴酸,碘酸或其任意混合物。最优选的酸是氟硼酸。以化学式HBF4表示。
无任何有机取代基,带有弱亲核性阴离子的适宜的无机酸金属盐包括,例如Sargent Welch Scientific Company出版的元素周期表(目录号为S-18806)第Ⅰ和第Ⅱ族的那些金属的盐。这类盐的具体实例有碱金属和碱土金属盐、如钠盐,钾盐,锂盐,钙盐,钡盐,和镁盐以及这类无机酸的银盐。
可用于本发明的每分子平均含有多于1个环氧基的适宜化合物包括环氧树脂,例如多元酚,如二羟基酚类,二酚类,双酚类,卤代双酚类,烷基化双酚类,三酚类,酚醛清漆树脂,取代的酚醛清漆树脂,酚烃树脂,取代的酚烃树脂的缩水甘油醚,其任意混合物等。适宜的这类环氧树脂包括,例如,以下式Ⅴ-Ⅸ代表的环氧树脂。
式中A各自独立地为具有1-9个,较好为1~4个碳原子的二价烃基,-O-,-S-,-S-S-,-SO-,-SO2-,或-CO-;A′各自独立地为具有1~9个,较好为1~4个碳原子的二价烃基;Q为具有1~10个碳原子的烃基;Q′为氢,卤素,氰基或具有1~4个碳原子的烷基;R各自独立地为氢,卤素,氰基或具有1~4个碳原子的烷基;X各自独立地为氢,溴,氯,或具有1~9个,较好为1~4个碳原子的烃基或烃氧基;m的平均值为0~12,较好为0~9,最好为0.03~3;m′的平均值为0.01~8,较好为0.2~6,最好为0.5~4;n值为0或1;n′的平均值为0~12,较好为0~9,最好为0.03~3;各P值宜为0~10,较好为0~6,最好为1~3;各P′值宜为0~8,较好为1~6,最好为2~4。以式Ⅸ表示的环氧树脂低聚体也是适宜的。
本文所用的术语烃基是指任何脂族,环脂族,芳族烃基,芳基取代的脂族或环脂族烃基,或脂族或环脂族取代的芳族基团。脂族基团可以是饱和的或不饱和的。同样,术语烃氧基是指在它与相连的碳原子之间具有一个氧键的烃基。
特别适宜的这类环氧树脂包括,例如,间苯二酚,邻苯二酚,对苯二酚,二酚,双酚A,双酚F,双酚K,四溴双酚A,苯酚-甲醛清漆树脂,烷基取代的苯酚-甲醛树脂,苯酚-羟基苯甲醛树脂,甲酚-羟基苯甲醛树脂,二环戊二烯-苯酚树脂,二环戊二烯-取代苯酚树脂,四甲基二酚,四甲基四溴二酚,四甲基三溴二酚,四氯双酚A的二环氧甘油醚,其任意混合物等。
适用于本发明的环氧化合物还包括部分高级的环氧树脂(见Bertram等人的U.S.4,594,291,在此援引以供参考)。
每分子平均具有多于1个脂族羟基的化合物的缩水甘油醚也适作为环氧化合物,例如,脂族二醇,聚醚二醇,聚醚三醇,聚醚四醇的缩水甘油醚,或其任意混合物。每分子平均包含多于1个芳羟基的化合物的烯化氧加合物也是适宜的,例如,二羟基酚类,二酚类,双酚类,卤代双酚类,烷基化双酚类,三酚类,酚醛清漆树脂,卤代酚醛清漆树脂,烷基化酚醛清漆树脂,烃-酚树脂,烃-卤代酚树脂,或烃-烷基化酚树脂的环氧乙烷,环氧丙烷,或环氧丁烷加合物或其任意混合物。
适宜的可用于本发明的含有芳羟基的化合物包括,例如,每分子平均具有多于1个酚羟基的化合物,适宜的这类化合物包括,例如,二羟基酚类,二酚类,双酚类,卤代双酚类,烷基化双酚类,三酚类,酚醛树脂,卤代酚醛清漆树脂,烷基化酚醛清漆树脂,苯酚-羟基苯甲醛树脂,烷基化苯酚-羟基苯甲醛树脂,烃酚树脂,烃-卤代酚树脂,烃-烷基化酚树脂,或其任意混合物。特别适宜的含芳羟基化合物包括,例如,以下式Ⅹ-ⅩⅢ表示的化合物:
式中A,A′,Q,Q′,X,n和m如在式Ⅴ-Ⅸ中所定义。特别适宜的含芳羟基物质包括,例如,二酚,双酚A,双酚K,四溴双酚A,四溴双酚K,间苯二酚,酚醛清漆树脂,甲酚醛清漆树脂,苯酚-羟基苯甲醛树脂,甲酚-羟基苯甲醛树脂,四甲基二酚,四甲基三溴二酚,四甲基四溴二酚,四氯双酚A,或其任意混合物。以式ⅩⅢ所示的多官能酚化合物的低聚物也是适宜的。
1986年6月10日分布的Bertram等人的美国专利4,594,291公开了这些和其它的适宜的含芳羟基化合物。
含芳羟基化合物的用量应使芳羟基与环氧基之比为0.05∶1~20∶1,较好为0.1∶1~10∶1,最好为0.2∶1~5∶1。
若需要,本发明的预催化组合物可含有颜料,填充剂,染料,稀释剂,溶剂,稳定剂,环氧树脂固化剂,或其任意组合。
可用于本发明的适宜的稳定剂和固化剂包括,例如,上述Bertram等人的美国专利4,594,291中公开的那些。
特别适宜的溶剂或稀释剂包括,例如,脂族和芳族烃,醇,酮,乙二醇醚,乙二醇酯,其混合物等。最佳溶剂或稀释剂包括,例如,乙二醇-丁醚(2-丁氧乙醇),二乙二醇一丙醚,二乙二醇一丁醚,二乙二醇一己醚,一丙醚,丙二醇一丙醚,丙二醇一丁醚,丙二醇叔丁醚,丙二醇异丙醚,二丙二醇一丁醚,乙二醇苯醚,丙二醇苯醚,甲苯,二甲苯,丙二醇乙酸甲酯醚,或其任意混合物。
本发明的组合物可用于制备在电和结构层压板和合成物,涂盖层,铸件,模压件,或电器外封胶的制备中所用的制剂。它们可用于常规方法或较新的反应压铸(RTM)和反应注压(RIM)技术。
下列实施例是对本发明的说明,并不以任何方式对本发明的范围构成限制。
实例1
通过将2.98g(0.01906mol)氟硼酸的56.1%水溶液加到5.00g(0.01906mol)三苯膦的14.26g四氢呋喃溶液中,制备1∶1摩尔比的三苯膦/氟硼酸配合物的30%溶液。混合物在25℃搅拌5分钟以确保均匀混合。氟硼酸水溶液的浓度是通过用0.100N氢氧化钾的甲醇溶液进行电势滴定至第一个转折点测定的。在滴定过程中使用MCI GT-05自动滴定器和银/氯化银组合电极(Curtain Matheson Scientific No.201-947)测量pH变化。
实例2
通过将3.28g(0.0210mol)氟硼酸的56.1%水溶液加到5.00g(0.01906mol)三苯膦的14.52g四氢呋喃溶液中,制备1.00∶1.10摩尔比的三苯膦/氟硼酸配合物的30%溶液。混合物在25℃搅拌5分钟以确保均匀混合。氟硼酸水溶液的浓度的测定同实例1。
实例3
通过将1.93g(0.01236mol)氟硼酸的56.1%水溶液加到2.50g(0.01236mol)三苯膦的7.52g四氢呋喃溶液中,制备1∶1摩尔比的三苯膦/氟硼酸配合物的30%溶液。混合物在25℃搅拌5分钟以确保均匀混合。氟硼酸水溶液浓度的测定同实例1。
实例4
通过将1.52g(0.00972mol)氟硼酸的56.1%水溶液加到2.00g(0.00484mol)1,3-双(二苯膦基)丙烷的5.99g四氢呋喃溶液中,制备1∶1摩尔比的1,3-双(二苯膦基)丙烷/氟硼酸配合物的30%溶液。混合物在25℃搅拌5分钟以确保均匀混合。氟硼酸水溶液的浓度的测定同实例1。
实例5
将1.71g(18mmol催化剂/mol环氧化物)实例1所述的30%催化剂溶液加到环氧当量重(EEW)为181.5的双酚A二环氧甘油醚和于1-甲氧-2-乙酰氧丙烷溶剂中的双酚A(80%固体)的30g1∶1摩尔比混合物中。将这一催化了的混合物置于50℃烘箱中,监测其0、0.3、1、7和14天后的25℃粘度,结果示于表Ⅰ。
实例6
将1.75g(18mmol催化剂/mol环氧化物)实例2所述的30%催化剂溶液加到环氧当量重(EEW)为181.5的双酚A二环氧甘油醚和于1-甲氧-2-乙酰氧丙烷溶剂中的双酚A(80%固体)的30.0g1∶1摩尔比的混合物中。将这一催化了的混合物置于50℃烘箱,监测其0、1、7和14天后25℃粘度,结果示于表Ⅰ。
实例7
将1.41g(18mmol催化剂/mol环氧化物)实例3所述的30%催化剂溶液加到环氧当量重(EEW)为181.5的双酚A二环氧甘油醚和于1-甲氧-2-乙酰氧丙烷溶剂中的双酚A(80%固体)的30.0g1∶1摩尔比的混合物中。将这一催化了的混合物置于50℃烘箱,监测其0、0.3、1、7和14天后的25℃粘度,结果示于表Ⅰ。
实例8
将1.43g(18mmol催化剂/mol环氧化物)实例4所述的30%催化剂溶液加到环氧当量重(EEW)为181.5的双酚A二环氧甘油醚和于1-甲氧-2-乙酰氧丙烷溶剂中的双酚A(80%固体)的30.0g1∶1摩尔比的混合物中。将这一催化了的混合物置于50℃烘箱,监测其0、1、7和14天后的25℃粘度,结果示于表Ⅰ。
对比实验A
将环氧当量重为181.5的双酚A二环氧甘油醚与在1-甲氧-2-乙酰氧丙烷溶剂中的双酚A(80%固体)的1∶1摩尔比的混合物置于50℃烘箱,监测其0、0.3、1、7和14天后的25℃粘度,结果示于表Ⅰ。
对比实验B
将1.18g四氢呋喃加到环氧当量重为181.5的双酚A二环氧甘油醚与在1-甲氧-2-乙酰氧丙烷溶剂中的双酚A(80%固体)的30g1∶1摩尔比的混合物中。将该混合物置于50℃烘箱,监测其0、0.3、1、7和14天后的25℃粘度,结果示于表Ⅰ。
对比实验C
将1.28g(18mmol催化剂/当量环氧化物)三苯膦在四氢呋喃中的30%溶液加到环氧当量重(EEW)为181.5的双酚A二环氧甘油醚与在1-甲氧-2-乙酰氧丙烷溶剂中的双酚A(80%固体)的30g1∶1摩尔比的混合物中。将这一催化了的混合物置于50℃烘箱,监测其0、0.3、1、7和14天后的25℃粘度,结果示于表Ⅰ。
对比实验D
将0.986g(18mmol催化剂/mol环氧化物)三苯膦在四氢呋喃中的30%溶液加到环氧当量重(EEW)为181.5的双酚A二环氧甘油醚与在1-甲氧-2-乙酰氧丙烷溶剂中的双酚A(80%固体)的30g1∶1摩尔比的混合物中。将这一催化了的混合物置于50℃烘箱,监测其0、0.3、1、7和14天后的25℃粘度,结果示于表Ⅰ。
对比实验E
将1.005g(18mmol催化剂/mol环氧化物)1,3-双(二苯膦基)丙烷的30%溶液加到环氧当量重(EEW)为181.5的双酚A二环氧甘油醚与在1-甲氧-2-乙酰氧丙烷溶剂中的双酚A(80%固体)的30g1∶1摩尔比的混合物中。将这一催化了的混合物置于50℃烘箱,监测其0、1、7和14天后的25℃粘度,结果示于表Ⅰ。
实例9~12
使用实例1~4所述的各引发剂来促进环氧当量重(EEW)为181.5的双酚A二环氧甘油醚与双酚A的1∶1摩尔比混合物(295.5g/当量环氧化物)的聚合反应。加到10.00g环氧/双酚混合物中各催化剂的量都规定在18毫当量引发剂/当量环氧化物。表Ⅱ示出了各引发剂的当量重和四氢呋喃(THF)中18毫当量30%引发剂溶液的重量。表Ⅱ还示出了由差示扫描量热测定的固化样品的玻璃化温度。所有样品都是在200℃固化3.5小时。
对比实验F-H
分别使用三苯膦、三丁基膦和1,3-双(二苯基膦)丙烷的30%四氢呋喃溶液来促进环氧当量重(EEW)为181.5的双酚A二环氧甘油醚与双酚A的1∶1摩尔比混合物(295.5g/当量环氧化物)的聚合反应。加到10.00g环氧/双酚混合物中各催化剂的量都规定在18毫当量引发剂/当量环氧化物。表Ⅱ示出了各引发剂的当量重和四氢呋喃(THF)中18毫当量30%引发剂溶液的重量。表Ⅱ还示出了由差示扫描量热测定的固化样品的玻璃化温度。所有样品都是在200℃固化3.5小时。
Claims (10)
1、一种加合物、配合物或化合物。其特征在于所述物质通过下述步骤得到:(1)使(a)至少一种有机膦或有机肿与(b)具有弱亲核阴离子的无机酸或所述无机酸的混合物接触;或(2)使(a)具有较强亲核阴离子的酸与有机膦或有机肿的至少一种加合物与(b)具有弱亲核阴离子的无机酸或其金属盐或所述酸或金属盐的混合物接触;其中组分(a)与组分(b)的接触数量是使组分(b)与组分(a)的摩尔比为0.6∶1~1.4∶1;且条件是当组分(1-a)是有机膦时。不是三苯膦。
4、一种组合物,其特征在于含有(A)至少一种每分子平均有一个以上环氧基的化合物;和(B)至少一种(1)使(a)至少一种有机膦或有机胂与(b)具有弱亲核阴离子的无机酸或其混合物接触所得的产物;或(2)使(a)具有较强亲核阴离子的酸与有机膦或有机胂的至少一种加合物与(b)具有弱亲核阴离子的无机酸或其金属盐或所述酸或金属盐的混合物接触所得的产物;其中(ⅰ)组分(a)和(b)的接触数量应使组合物在50℃储存14天后满足粘度要求;和(ⅱ)所述(A)和(B)的混合物以20-40%(重量)溶于适当的溶剂或溶剂混合物时,其25℃测得的粘度与催化剂仅由组分(a)组成的同类组合物相比为75%或更低,所述粘度是50℃储存14天后测定的。
5、权利要求4的组合物,其中组分(a)是如下面式Ⅲ或Ⅳ所示的有机膦
式中R、R1、R2、R3、R4、R5和R6各选自宜具有1-18个碳原子的烃基,或R、R1和R2之中两个,R3和R4或R5和R6结合形成杂环;Z是P;Z′是有1-10个碳原子的二价烃基;且其中组分(b)是氟硼酸,氟砷酸、氟锑酸、氟磷酸、氯硼酸、氯砷酸、氯锑酸、氯磷酸、高氯酸、氯酸、溴酸、碘酸、所述酸的Ⅰ族或Ⅱ族金属盐,或其任意混合物。
6、一种组合物,其特征在于含有(A)至少一种每分子平均有一个以上环氧基的化合物;(B)至少一种(l)使(a)至少一种有机膦或有机胂与(b)具有弱亲核阴离子的无机酸或其混合物接触所得的产物;或(2)使(a)具有较强亲核阴离子的酸与有机膦或有机胂的至少一种加合物与(b)具有弱亲核阴离子的无机酸或其金属盐或所述酸或金属盐的混合物接触所得的产物;和(C)至少一种每分子平均含有一个以上芳族羟基的化合物;其中(ⅰ)组分(a)和(b)的接触数量应使组合物在50℃储存14天后满足粘度要求;(ⅱ)组分(A)和(C)的量应使芳族羟基与环氧基的比为0.05∶1至20∶1;和(ⅲ)组分(A)、(B)和(C)的混合物以20-40%(重量)溶于适当的溶剂或溶剂混合物时,其25℃测得的粘度与催化剂仅由组分(a)组成的同类组合物相比为75%或更低,所述粘度是50℃储存14天后测定的。
8、一种制备加合物、配合物或化合物的方法,其特征在于(1)使(a)至少一种有机膦或有机胂与(b)具有弱亲核阴离子的无机酸或所述无机酸的混合物接触;或(2)使(a)具有较强亲核阴离子的酸与有机膦或有机胂的至少一种加合物与(b)具有弱亲核阴离子的无机酸或其金属盐或所述酸或金属盐的混合物接触;其中组分(a)与组分(b)的接触数量是使组分(b)与组分(a)的摩尔比为0.6∶1-1.4∶1;且条件是当组分(1-a)是有机膦时,不是三苯膦。
9、一种制备组合物的方法,其特征在于将下述(A)和(B)掺合:(A)至少一种每分子平均有一个以上环氧基的化合物;和(B)至少一种(1)使(a)至少一种有机膦或有机胂与(b)具有弱亲核阴离子的无机酸或其混合物接触所得的产物;或(2)使(a)具有较强亲核阴离子的酸与有机膦或有机胂的至少一种加合物与(b)具有弱亲核阴离子的无机酸或其金属盐或所述酸或金属盐的混合物接触所得的产物;其中(ⅰ)组分(a)和(b)的接触数量应使组合物在50℃储存14天后满足粘度要求;和(ⅱ)所述(A)和(B)的混合物以20-40%(重量)溶于适当的溶剂或溶剂混合物时,其25℃测得的粘度与催化剂仅由组分(a)组成的同类组合物相比为75%或更低,所述粘度是50℃储存14天后测定的。
10、一种制备组合物的方法,其特征在于将下述(A)、(B)和(C)掺合;(A)至少一种每分子平均有一个以上环氧基的化合合;(B)至少一种(1)使(a)至少一种有机膦或有机胂与(b)具有弱亲核阴离子的无机酸或其混合物接触所得的产物;或(2)使(a)具有较强亲核阴离子的酸与有机膦或有机胂的至少一种加合物与(b)具有弱亲核阴离子的无机酸或其金属盐或所述酸或金属盐的混合物接触所得的产物;和(C)至少一种每分子平均含有一个以上芳族羟基的化合物;其中(ⅰ)组分(a)和(b)的接触数量应使组合物在50℃储存14天后满足粘度要求;(ⅱ)组分(A)和(C)的量应使芳族羟基与环氧基的比为0.05∶1至20∶1;和(ⅲ)组分(A)、(B)和(C)的混合物以20-40%(重量)溶于适当的溶剂或溶剂混合物时,其25℃测得的粘度与催化剂仅由组分(a)组成的同类组合物相比为75%或更低,所述粘度是50℃储存14天后测定的。
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JP (1) | JPH0532766A (zh) |
KR (1) | KR910015614A (zh) |
CN (1) | CN1053924A (zh) |
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CA (1) | CA2035624A1 (zh) |
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US4438254A (en) * | 1983-02-28 | 1984-03-20 | The Dow Chemical Company | Process for producing epoxy resins |
DE68927300T2 (de) * | 1988-02-12 | 1997-04-30 | Dow Chemical Co | Verwendung eines Katalysators für Epoxyharz-Zusammensetzungen |
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1991
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- 1991-01-31 EP EP19910101271 patent/EP0443351A3/en not_active Withdrawn
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EP0443351A2 (en) | 1991-08-28 |
KR910015614A (ko) | 1991-09-30 |
TW205049B (zh) | 1993-05-01 |
AU7026291A (en) | 1991-08-08 |
NO910439L (no) | 1991-08-07 |
CA2035624A1 (en) | 1991-08-07 |
MY105448A (en) | 1994-10-31 |
NO910439D0 (no) | 1991-02-05 |
JPH0532766A (ja) | 1993-02-09 |
BR9100475A (pt) | 1991-10-29 |
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