CN1639174A - 羟基封端的低聚膦酸酯 - Google Patents
羟基封端的低聚膦酸酯 Download PDFInfo
- Publication number
- CN1639174A CN1639174A CNA028194071A CN02819407A CN1639174A CN 1639174 A CN1639174 A CN 1639174A CN A028194071 A CNA028194071 A CN A028194071A CN 02819407 A CN02819407 A CN 02819407A CN 1639174 A CN1639174 A CN 1639174A
- Authority
- CN
- China
- Prior art keywords
- arylidene
- acid ester
- epoxy
- phosphonic acid
- phenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 title 1
- 239000004593 Epoxy Substances 0.000 claims abstract description 23
- 239000003063 flame retardant Substances 0.000 claims abstract description 23
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims abstract description 4
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 150000003008 phosphonic acid esters Chemical class 0.000 claims description 12
- 229930185605 Bisphenol Natural products 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 claims 5
- 239000002648 laminated material Substances 0.000 claims 1
- 229920001187 thermosetting polymer Polymers 0.000 claims 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 abstract description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 18
- 229960003742 phenol Drugs 0.000 description 18
- HPUPGAFDTWIMBR-UHFFFAOYSA-N [methyl(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(C)OC1=CC=CC=C1 HPUPGAFDTWIMBR-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- -1 aromatic diol Chemical class 0.000 description 14
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 7
- 238000004448 titration Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 150000004646 arylidenes Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 125000005499 phosphonyl group Chemical group 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 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
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- NGPGYVQZGRJHFJ-UHFFFAOYSA-N chembl1604790 Chemical compound OC1=CC(O)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1 NGPGYVQZGRJHFJ-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003918 potentiometric titration Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 3
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 2
- CGOXUOAIOULNBN-UHFFFAOYSA-N 9h-fluorene;phenol Chemical class OC1=CC=CC=C1.C1=CC=C2CC3=CC=CC=C3C2=C1 CGOXUOAIOULNBN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 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
- 230000031709 bromination Effects 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- 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 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 206010009866 Cold sweat Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920004935 Trevira® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HPGJOUYGWKFYQW-UHFFFAOYSA-N diphenyl benzene-1,4-dicarboxylate Chemical group C=1C=C(C(=O)OC=2C=CC=CC=2)C=CC=1C(=O)OC1=CC=CC=C1 HPGJOUYGWKFYQW-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- QWHOEDUCBAGOAM-UHFFFAOYSA-N phenol toluene Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.C1(=CC=CC=C1)C.C1(=CC=CC=C1)O QWHOEDUCBAGOAM-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4084—Esters with hydroxyaryl compounds
-
- 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
- C08G59/40—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 curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
-
- 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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31515—As intermediate layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
- Y10T428/31515—As intermediate layer
- Y10T428/31522—Next to metal
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
本发明涉及适于形成满足UL－94分级为V－0的环氧层压材料的环氧树脂，该树脂包含羟基封端的低聚膦酸酯作为阻燃剂，该膦酸酯包含重复结构－OP(＝O)(R)O－亚芳基－，其中R为烷基。
Description
膦酰二氯与二醇的反应在大多数情况下产生脂族膦酸结构(1)，其聚合物具有低熔点且是亲水性的。工业上的兴趣集中在由芳族二醇或芳族膦酰二氯生产的聚膦酸酯。早前的研究表明高分子量聚酯可通过小心提纯的反应物和精确的化学计量而获得。
由于苯基膦酰二氯(BPOD)的商业利用性，对该中间体作了大量工作以制备聚膦酸酯，包括聚对苯二甲酸乙二醇酯(2)、聚苯醚-聚苯乙烯共混物(3)和其它热塑性塑料的阻燃添加剂。
聚苯基膦酸酯可由氢醌或间苯二酚(4-8)、四溴双酚A(9)、四溴双酚和磺酰基双酚(10)、新戊二醇(11)、4，4’-二羟基联苯基芴或4，4，-双(4-羟基苯)芴(12)和2，2’-双(溴甲基)-1，3-丙二醇(13)制备。各种双酚的聚烷基膦酸酯和聚芳基膦酸酯促进了聚丙烯腈和尼龙-6，6(14)的阻燃性。间苯二酚和苯基膦酰二氯和二氯化磷酰苯基酯的共缩聚产物是热塑性聚酯(14，15)的阻燃剂。Toyobo在日本引进了该聚合物以用于聚酯纤维，以满足有关家俱(16，17)的日本阻燃剂法规。
合成聚膦酸酯的界面缩聚非常迅速，并且在有利条件下得到高分子量(18)。
膦酸酯与二醇的酯交换：该方法用膦酸O，O-二烷基酯通过其中膦酸酯作为烷基化剂的副反应而完成。然而，使用膦酸O，O-二芳基酯，酯交换是获得聚膦酸酯(19-22)的有效途径。
高分子量可通过将三元或四元酚或磷酸三芳基酯加入反应混合物(23)中而获得。通过该技术制得的透明的聚甲基膦酸酯热塑性塑料曾经由Bayer在开发中报道过，以用于飞机阻燃应用，以及用于挡风玻璃、风镜和警察控制骚乱用的盾牌(21，24)。它们的机械性能优异，但耐热水性稍微欠缺(21)。可将这些聚膦酸酯与聚碳酸酯混合，以制备阻燃聚合物共混物(22)。通过在酯交换中加入碳酸二苯酯，可制得共缩聚的聚膦酸酯碳酸酯(21)；这些共缩聚酯曾经可开发用于航空应用。通过甲基膦酸二苯酯和间-和对苯二甲酸二苯基酯与双酚的酯交换，可制得具有作为塑料的有利性能的高分子量聚芳基酯(21)。
作为本发明主题的羟基封端的低聚膦酸酯添加剂的含芳基类似物是已知的(25)，但由于其中含有添加剂因而磷含量较低。
溴化的含FR环氧密封剂的问题已经有描述(26)。适于封装(或者密封)半导体的环氧树脂组合物含有单体磷酸酯阻燃剂(27)。
最后，已知通过甲基膦酸二苯酯与间苯二酚的酯交换来合成聚(甲基膦酸间亚苯基酯)(28)。然而，由这种方式制得的产物含有苯基端基，这些苯基端基将排除该产物与环氧聚合物的反应性。
参考文献
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22.美国专利号4,332,921。
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28.美国专利号4,035,442。
必须保证环氧树脂电路板以及例如其它电子环氧树脂应用根据UL-94立式试验达到V-0标准，同时保持可接受的机械性能，例如玻璃化转变温度(Tg)，并保持可接受的抗分层性。这些目的可通过在这种环氧组合物中引入有效量的包含低聚膦酸酯的组合物而实现，该低聚膦酸酯包含重复单元-OP(O)(R)-O-亚芳基-，其磷含量大于约12重量％。该组合物中的膦酸酯包括还含有-OH端基的那些，以及可能的话不含-OH端基的那些。含有-OH端基的各膦酸酯可以是单羟基取代的或二羟基取代的。在含有端羟基的组合物中，膦酸酯的浓度基于可能潜在具有这些端基的末端(“链端”)的总数计为约20％至约100％，优选约50％至约100％。端基可与亚芳基结构部分或磷结构部分连接，它们对其中添加有阻燃剂的组合物中的环氧官能团具有反应性。优选的R基团是甲基，但可以是低级烷基。
“亚芳基”指二元酚的任何基团。二元酚优选应该具有两个非相邻的羟基。实例包括间苯二酚；氢醌；双酚，例如双酚A、双酚F、4，4’-双酚、酚酞、4，4’-硫代二酚或4，4’-磺酰基二酚。还可加入少量具有三个或更多个羟基的多元酚例如线型酚醛清漆或甲苯三酚，以提高分子量。
亚芳基可以是1，3-亚苯基、1，4-亚苯基或双酚二基单元，但优选1，3-亚苯基。
这类没有端羟基的低聚物在本领域中是已知的，并且已经描述成某些热塑性塑料的阻燃剂(如本文现有技术部分所述)。
本发明的低聚物可通过下列任一途径制得：(1)RPOCl2与HO-芳基-OH或其盐的反应，其中R是低级烷基，优选甲基；(2)烷基膦酸二苯酯、优选甲基膦酸二苯酯与HO-亚芳基-OH在酯交换条件下的反应；(3)具有重复结构单元-OP(OR’)-O-亚芳基-的低聚亚磷酸酯使用Arbuzov重排催化剂的反应，其中R’为低级烷基，优选甲基；或者(4)具有重复结构单元-OP(O-Ph)-O-亚芳基的低聚亚磷酸酯与亚磷酸三甲酯使用Arbuzov催化剂或与甲基膦酸二甲酯并任选使用Arbuzov催化剂的反应。-OH端基若与亚芳基相连，则可通过在反应介质中具有受控摩尔过量的HO-亚芳基-OH来制备。若-OH端基为酸型(P-OH)，则可通过水解反应形成。优选低聚物的端基主要是-亚芳基-OH型。
此处所述的膦酸酯阻燃剂的量可在适当的阻燃量中变化，基于用于阻燃的环氧的重量计不超过约50％，优选为环氧树脂重量的约10％至约30％。添加剂可通过用环氧固化(需要的话，以单釜反应)而使用。另外，可使膦酸酯阻燃剂与环氧树脂以与使用四溴双酚A和环氧的情况相似的方式(如美国专利号6,214,468和6,329,474所述)进行预反应。
本发明还可用于其它环氧配制剂，包括在用于电子应用方面代替例如溴化阻燃剂的环氧密封剂组合物。另外，本发明的组合物还可用于结构和涂料环氧树脂配制剂。
需要的话，可根据已知技术通过使用分子量提高量的磷酸酯而制备膦酸酯阻燃添加剂，得到更细分的组合物。
另外，此处所述的膦酸酯组合物可与其它补充的本领域普通技术人员已知的阻燃剂一起使用，这些阻燃剂包括三水合氧化铝、氢氧化镁、多磷酸铵、三聚氰胺、磷酸三聚氰胺酯、焦磷酸三聚氰胺酯、多磷酸三聚氰胺酯、氰尿酸三聚氰胺酯、红磷、磷酸三苯酯或双磷酸酯阻燃剂(如间苯二酚双(磷酸二苯酯)或双酚A双(磷酸二苯酯))。
本发明的环氧树脂可含有常规使用的其它组分，例如聚苯醚、酰亚胺、苯酚和双噁嗪树脂。
下列不应当理解为限制本发明的实施例将进一步说明本发明。
实施例1
在该实验中，将124g(0.5mol)甲基膦酸二苯酯、113g(1.03mol)间苯二酚和0.54g甲醇钠加热并于230℃下在反应烧瓶中搅拌。该反应烧瓶装有高约40cm的Vigreux柱，该柱缠有电加热带并隔热以防止苯酚和任何挥发的间苯二酚在该柱中固结化。使真空逐渐由625mmHg降至5mmHg。4小时后使反应停止。在反应过程中苯酚被蒸除，并在冷集液器中收集到93g馏出液(若按苯酚计算为约1mol)，而241g残留在反应烧瓶中。馏出液看起来为基本纯净的苯酚。
表征：试样为深咖啡色但透明粘稠的液体。当温热时可倾倒，它可以溶于2-丁酮和DMSO中。用四丁基氢氧化铵滴定至偶氮紫终点显示当量为158/OH基团。假定存在两个端羟基，则分子量为158×2＝316。理论值为280，这表明形成了聚合度非常低的低聚物。31P NMR光谱显示一系列位于25.7-27.5ppm之间的峰。这些数据支持主要结构为CH3P(＝O)(OC6H4OH)2且一些结构为HOC6H4OP(＝O)(CH3)OC6H4OP(＝O)(CH3)OC6H4OH且仅存在小百分比的残留苯氧基的结构。
实施例2
在该合成中，使200g(0.8mol)甲基膦酸二苯酯(DPMP)、89g(0.8mol)间苯二酚和0.43g甲醇钠于245℃下反应。在3.5小时内将温度逐渐升至260℃。在该反应过程中在集液器中收集到141g冷凝物，发现为基本纯净的苯酚，这通过红外光谱证实。这表明DPMP中94％的苯氧基被间苯二酚替代。反应烧瓶中残留约136g产物。终产物为清澈的浅琥珀色玻璃状固体。
表征：试样可溶于丙酮、甲醇、氯仿和2-丁酮中。它的红外光谱表明在-OH基团吸收区域中具有小峰。
1H NMR显示PCH3(d，3H，1.77ppm，CDCl3)和Ar-H(m，4H，7.0-7.4)存在化学位移。适合该数据的合理解释是重复单元为-OP(＝O)(CH3)OC6H4-且具有HOC6H4-端基和一些C6H5-端基的低聚物。
实施例3
在该合成中，使170g(0.69mol)甲基膦酸二苯酯、72g(0.65mol)、0.20g(0.61×10-3mol)磷酸三苯酯和0.025g甲醇钠于240℃下加热6.5小时。将为除去苯酚而施加的真空由625mmHg逐渐降至0.3mmHg，同时将温度在5小时内逐渐升至260℃。在集液器中收集到约137g苯酚，而在反应烧瓶中残留有103g产物。终产物为清澈的浅黄色固体，它在80℃下可倾倒。
表征：产物可溶于丙酮、2-丁酮和DMF中。用四丁基氢氧化铵对它的DMF溶液的滴定显示OH当量为约650。
实施例4
向装有温度计、磁力搅拌器、蒸馏头和氮气导入口的三颈烧瓶中，加入163g(0.52mol)亚磷酸三苯酯和1.0mL甲基碘。然后于100-110℃下在1小时内滴加32.7g(0.26mol)亚磷酸三甲酯。然后将反应温度升至210℃，观察到有放热反应发生。将反应温度于230℃下保持2小时，分析反应混合物，然后进行酯交换。得到甲基膦酸二苯酯，为液体。31P NMR(CDCl3)表明为95％甲基膦酸二苯酯。其杂质包括磷酸三苯酯(0.8％，δ＝-16.4ppm)、磷酸三甲酯(0.6％，δ＝-10.3ppm)和未知化合物(δ＝19.8，20.4，28.4ppm)。该粗甲基膦酸二苯酯的酸值为5.4mg KOH/g。
然后，将86g(0.78mol)间苯二酚和0.024g(4.4×10-4mol)甲醇钠加入上述反应混合物中。将随后的酯交换反应于215-230℃下进行18小时。施加真空达4小时以除去苯酚。收集苯酚(130g)，而在反应烧瓶中残留148g产物。该终产物为深红色固体，当加热到100℃以上时可倾倒。
表征：试样用四丁基氢氧化铵的滴定显示当量为978，该滴定终点通过偶氮紫指示器或电位滴定法确定。31P NMR显示在δ25-31ppm之间存在多重峰，1H NMR显示在终产物中存在几种甲基膦酸酯结构。
实施例5
向装有温度计、磁力搅拌器、蒸馏头和氮气导入口的三颈烧瓶中，于110℃下加入148g(0.48mol)亚磷酸三苯酯、0.9mL甲基碘和31g(0.25mol)甲基膦酸二甲酯。逐渐升温。在210℃下观察到有快速放热反应发生，并持续约15分钟。将反应混合物于230℃下再搅拌1小时。粗甲基膦酸二苯酯为无色透明液体混合物。31P NMR(CDCl3)表明为93％甲基膦酸二苯酯。其杂质包括磷酸三苯酯(0.3％，δ＝-16.4ppm)和未知化合物(δ＝19.8ppm(2.8％)，20.4ppm(2.8％)，28.4(1.0％)ppm)。该粗甲基膦酸二苯酯的酸值为8.1mg KOH/g。
然后，将80g(0.73mol)间苯二酚和0.040g(7.4×10-4mol)甲醇钠加入上述反应混合物中。将酯交换反应于205-230℃下进行18小时。施加真空达4小时以除去苯酚，收集到130g苯酚。在反应烧瓶中残留约120g产物。
产物为透明的淡黄色粘稠固体，当加热到100℃以上时它可倾倒。试样用四丁基氢氧化铵的滴定显示OH当量为3000，该滴定终点通过偶氮紫指示器或电位滴定法确定。试样的31P NMR显示在δ25-31ppm之间存在小的多重峰，1H NMR显示主要存在三种甲基膦酸酯结构。
实施例6
在该实验中，使146.8g(0.59mol)经提纯的甲基膦酸二苯酯、65.41g(0.59mol)氢醌和0.17g甲醇钠于225℃下反应10.5小时。该反应器装有高约40cm的Vigreux柱，该柱缠有电加热带并隔热以防止苯酚和任何挥发的间苯二酚在该柱中固结化。施加真空以从反应混合物中除去苯酚，并在2小时后将真空由625mmHg逐渐降至5mmHg。在集液器中收集到约106g物料，发现为基本纯净的苯酚，这通过它的NMR光谱来证明。在反应烧瓶中残留约105g物料。终产物为清澈的浅琥珀色玻璃状固体，它在90℃以上时可倾倒。
表征：试样用四丁基氢氧化铵的DMF溶液进行电位滴定，显示OH当量为9200。它通过用醇性KOH滴定至对萘酚苯终点的酸值为9.70mgKOH/g。
实施例7(环氧树脂评价)
层压材料的制备：将实施例1-6的阻燃添加剂和环氧溶于60℃下的30％的2-丁酮中。然后，加入1重量％的2-甲基咪唑(AMI-2牌号，购自AirProducts)。将所得的温热清漆施涂在玻璃纤维毡(7628，BGF，0.17mm)上。将预浸渍体于室温下干燥一夜，并于90℃下干燥30分钟。得到不发粘的透明预浸渍体。将八层预浸渍体堆叠，用铜箔(厚0.035mm)镶边，于130℃和8MPa压力下预固化30分钟，然后于171℃和30MPa压力下固化60分钟。
试验程序：根据标准UL 94试验(立式方案)测定预浸渍体的可燃性。根据IPC TM-650 2.4.24标准通过TMA测定玻璃化转变温度。根据IPCTM-650 2.4.24.1标准通过TMA于260℃下测定分层时间。
这些试验的结果示于下面的表1中。
表1.层压材料的可燃性和热性能
| 7-1 | 7-2 | 7-3 | 7-4 | 7-5 | 7-6 | 7-7 | 7-8 | 7-9 | 7-10 | 7-11 | |
| 环氧1a | 69 | 69 | |||||||||
| 环氧2b | 69 | 69 | 74 | 79 | 69 | ||||||
| 环氧3c | 69 | 69 | 69 | 69 | |||||||
| 产物实施例1 | 30 | 30 | 30 | ||||||||
| 产物实施例2 | 30 | 30 | 25 | 20 | |||||||
| 产物实施例3 | 30 | ||||||||||
| 产物实施例4 | 30 | ||||||||||
| 产物实施例5 | 30 | ||||||||||
| 产物实施例6 | 30 | ||||||||||
| 催化剂AMI-2 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| UL 94 | V-1 | V-0 | V-1 | V-1 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| Tg′℃ | 110 | 135 | 135 | 130 | 160 | 190 | 135 | 163 | 140 | 157 | 140 |
| 分层，260℃ | 合格 | 合格 | 合格 | 合格 | 合格 | 合格 | 合格 | 合格 | 合格 | 合格 | 不合格 |
a双酚A环氧树脂
b可溶可熔酚醛环氧树脂
c甲酚-可溶酚醛环氧树脂
Claims (11)
1.一种包含羟基封端的低聚膦酸酯的组合物，该膦酸酯包含重复结构-OP(＝O)(R)O-亚芳基-，其中R为烷基。
2.如权利要求1所要求的组合物，其中羟基封端的膦酸酯的含量基于潜在具有这些端基的末端的总数计为约20％至约100％，优选约50％至约100％。
3.如权利要求1所要求的组合物，其中亚芳基为1，3-亚苯基。
4.如权利要求1所要求的组合物，其中R为低级烷基。
5.如权利要求1所要求的组合物，其中亚芳基为1，3-亚苯基且R为低级烷基。
6.如权利要求1所要求的组合物，其中亚芳基为1，3-亚苯基且R为甲基。
7.如权利要求1所要求的组合物，其中亚芳基为双酚二基单元。
8.如权利要求1所要求的组合物，其中亚芳基为双酚二基单元且R为甲基。
9.一种热固性树脂组合物，包含如权利要求1-8中任一项所要求的膦酸酯，并任选其中存在另一种阻燃剂。
10.一种含有如权利要求1-8中任一项所要求的膦酸酯的环氧树脂组合物，任选其中使膦酸酯与环氧相互预先反应，并任选其中存在另一种阻燃剂。
11.一种满足阻燃剂UL-94分级为V-0且抗分层的环氧层压材料，其包含阻燃量的如权利要求1-8中任一项所要求的羟基封端的低聚膦酸酯，并任选其中存在另一种阻燃剂。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
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| US32701801P | 2001-10-04 | 2001-10-04 | |
| US60/327,018 | 2001-10-04 | ||
| US40601102P | 2002-08-26 | 2002-08-26 | |
| US60/406,011 | 2002-08-26 |
Publications (2)
| Publication Number | Publication Date |
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| CN1639174A true CN1639174A (zh) | 2005-07-13 |
| CN100546992C CN100546992C (zh) | 2009-10-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028194071A Expired - Fee Related CN100546992C (zh) | 2001-10-04 | 2002-10-04 | 羟基封端的低聚膦酸酯 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US7449526B2 (zh) |
| EP (2) | EP2166013B1 (zh) |
| JP (1) | JP4518538B2 (zh) |
| KR (1) | KR100904566B1 (zh) |
| CN (1) | CN100546992C (zh) |
| WO (1) | WO2003029258A1 (zh) |
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| CN102627772B (zh) * | 2012-04-12 | 2014-03-26 | 南京师范大学 | 一种固液两相反应合成聚合型苯基膦酸酯的方法 |
| CN106459559A (zh) * | 2014-03-04 | 2017-02-22 | Frx聚合物股份有限公司 | 环氧组合物 |
| US10077354B2 (en) | 2014-03-04 | 2018-09-18 | Frx Polymers, Inc. | Epoxy compositions |
| CN104974351A (zh) * | 2015-08-07 | 2015-10-14 | 今创景新材料科技（上海）有限公司 | 一种羧基封端的含磷聚酯及其制备方法和应用 |
| CN104974351B (zh) * | 2015-08-07 | 2019-05-31 | 今创景新材料科技（上海）有限公司 | 一种羧基封端含磷聚酯及其制备方法和应用 |
| CN105330824A (zh) * | 2015-12-09 | 2016-02-17 | 西安元创化工科技股份有限公司 | 一种用于环氧树脂的阻燃固化剂及其制备方法 |
| WO2017148127A1 (zh) * | 2016-03-04 | 2017-09-08 | 广东生益科技股份有限公司 | 一种无卤热固性树脂组合物及使用它的预浸料、印制电路用层压板 |
| CN110337484A (zh) * | 2016-12-14 | 2019-10-15 | 溴化合物有限公司 | 不含锑阻燃性环氧树脂组合物 |
| US11560448B2 (en) | 2016-12-14 | 2023-01-24 | Bromine Compounds Ltd. | Antimony free flame-retarded epoxy compositions |
| CN116333286A (zh) * | 2023-05-08 | 2023-06-27 | 广州光通科技有限公司 | 一种高含磷量阻燃剂及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4518538B2 (ja) | 2010-08-04 |
| KR100904566B1 (ko) | 2009-06-25 |
| US7449526B2 (en) | 2008-11-11 |
| WO2003029258A8 (en) | 2004-05-13 |
| EP2166013A1 (en) | 2010-03-24 |
| EP1432719A1 (en) | 2004-06-30 |
| JP2005507902A (ja) | 2005-03-24 |
| KR20040068920A (ko) | 2004-08-02 |
| WO2003029258A1 (en) | 2003-04-10 |
| CN100546992C (zh) | 2009-10-07 |
| US20050020800A1 (en) | 2005-01-27 |
| EP2166013B1 (en) | 2018-01-24 |
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