WO2021031343A1 - Résine époxyde ignifuge à faible coefficient de dilatation thermique contenant du phosphore, son procédé de préparation et son utilisation - Google Patents
Résine époxyde ignifuge à faible coefficient de dilatation thermique contenant du phosphore, son procédé de préparation et son utilisation Download PDFInfo
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- WO2021031343A1 WO2021031343A1 PCT/CN2019/114286 CN2019114286W WO2021031343A1 WO 2021031343 A1 WO2021031343 A1 WO 2021031343A1 CN 2019114286 W CN2019114286 W CN 2019114286W WO 2021031343 A1 WO2021031343 A1 WO 2021031343A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phosphorus
- epoxy resin
- expansion coefficient
- thermal expansion
- chemical formula
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 89
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 89
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000003063 flame retardant Substances 0.000 title claims abstract description 84
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 84
- 239000011574 phosphorus Substances 0.000 title claims abstract description 84
- 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 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 16
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 15
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 239000000853 adhesive Substances 0.000 claims abstract description 4
- 230000001070 adhesive effect Effects 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 52
- -1 quinone compound Chemical class 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 37
- 125000003118 aryl group Chemical group 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 28
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 239000013067 intermediate product Substances 0.000 claims description 17
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 5
- 229930192627 Naphthoquinone Natural products 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 150000004056 anthraquinones Chemical class 0.000 claims description 5
- 150000002791 naphthoquinones Chemical class 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 239000005022 packaging material Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 150000004053 quinones Chemical class 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000011810 insulating material Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 239000013557 residual solvent Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 239000011889 copper foil Substances 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 239000012776 electronic material Substances 0.000 abstract description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 7
- 125000005561 phenanthryl group Chemical group 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
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- 125000003944 tolyl group Chemical group 0.000 description 7
- 125000005023 xylyl group Chemical group 0.000 description 7
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 6
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
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- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 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
- 239000004566 building material Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012772 electrical insulation material Substances 0.000 description 1
- ZBGRMWIREQJHPK-UHFFFAOYSA-N ethenyl 2,2,2-trifluoroacetate Chemical compound FC(F)(F)C(=O)OC=C ZBGRMWIREQJHPK-UHFFFAOYSA-N 0.000 description 1
- DYQQYVVTRHEFOU-UHFFFAOYSA-N ethylphosphonoylbenzene Chemical compound CCP(=O)C1=CC=CC=C1 DYQQYVVTRHEFOU-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FPCQAGJPTDBCEP-UHFFFAOYSA-N naphthalene-1,2-dione Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1.C1=CC=C2C(=O)C(=O)C=CC2=C1 FPCQAGJPTDBCEP-UHFFFAOYSA-N 0.000 description 1
- IWXWFPGJAZUXBL-UHFFFAOYSA-N naphthalene-1,4-dione Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1.C1=CC=C2C(=O)C=CC(=O)C2=C1 IWXWFPGJAZUXBL-UHFFFAOYSA-N 0.000 description 1
- SLBHRPOLVUEFSG-UHFFFAOYSA-N naphthalene-2,6-dione Chemical compound O=C1C=CC2=CC(=O)C=CC2=C1 SLBHRPOLVUEFSG-UHFFFAOYSA-N 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- POZPGRADIOPGIR-UHFFFAOYSA-N phenanthrene-1,4-dione Chemical compound C1=CC2=CC=CC=C2C2=C1C(=O)C=CC2=O POZPGRADIOPGIR-UHFFFAOYSA-N 0.000 description 1
- FTDXCHCAMNRNNY-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1 FTDXCHCAMNRNNY-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- LKOCAGKMEUHYBV-UHFFFAOYSA-N tris(3-bromo-3-chloropropyl) phosphate Chemical compound ClC(Br)CCOP(=O)(OCCC(Cl)Br)OCCC(Cl)Br LKOCAGKMEUHYBV-UHFFFAOYSA-N 0.000 description 1
Images
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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
-
- 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3229—Esters of aromatic acids (P-C aromatic linkage)
-
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/025—Polycondensates containing more than one epoxy group per molecule characterised by the purification methods used
-
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
-
- 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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
Definitions
- the invention relates to the technical field of resin materials, and more specifically, it relates to a phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin, a preparation method thereof, and related intermediate products and applications.
- plastics are widely used in various industrial fields such as electrical equipment, transportation equipment, and building materials.
- plastics are composed of organic materials containing carbon, oxygen, hydrogen and other elements and have flammable characteristics.
- fuel, oxygen, and energy are necessary factors for a fire.
- one of the flame-retardant methods of plastics is achieved by eliminating some of the three factors in fire.
- Flame retardants refer to compounds that have high flame retardancy such as halogen-based, phosphorus-based, nitrogen-based or metal products added by chemical or physical methods to flammable polymer materials to delay fire and prevent expanded combustion substance.
- Flame retardants can be divided into various types according to their types and uses, and can be roughly classified into reactive and additive types.
- Reactive flame retardant refers to a type that has a functional group in the molecule and undergoes a chemical reaction, and is rarely affected by external conditions and maintains the flame retardant effect.
- Additive flame retardant refers to a type that obtains a flame retardant effect by mixing, adding, and dispersing materials in a plastic or epoxy resin composition, and is mainly used in a thermoplastic resin composition.
- Additive flame retardant materials include tricresyl phosphate, toluene diphenyl phosphate, tributyl phosphate, tris(bromochloropropyl) phosphate, Tris (dichloropropyl) phosphate and the like.
- Reactive flame retardant materials include bromophenol, bromophenyl allyl ether, vinyl trifluoroacetate, ethylene glycol antimony, tetrabromobisphenol A and so on.
- the additive flame-retardant resin composition does not chemically react with the flame-retardant material and the polymer matrix. Therefore, the added flame-retardant material is usually simply dispersed or dissolved in the matrix, and is often lost from the matrix. .
- epoxy resin has excellent electrical characteristics, stability, high temperature and solvent resistance, low price, adhesiveness, etc., and is most suitable as a material for printed circuit boards and integrated circuits.
- epoxy resins are as easy to burn as plastic materials and are potentially dangerous. Therefore, the flame retardancy of electronic materials is strictly regulated all over the world, especially epoxy resin containing bromine. Although it is suitable as a resin for flame-retardant circuit boards, it releases corrosive harmful substances such as tetrabromodibenzodioxin and tetrabromodibenzofuran during the combustion process.
- the traditional non-halogen flame-retardant epoxy resin has sufficient flame retardancy, it is not easy to inject a large amount of phosphorus raw materials, and will cause gelation as the molecular weight increases, or even if no gelation occurs, the molecular weight
- the increase of Zn will lead to a decrease in curing density, resulting in a significant decrease in inherent physical properties such as heat resistance, adhesion, and thermal stability. At the same time, the thermal expansion coefficient will rise sharply.
- SLP Substrate-like PCB
- SLP substrate is a technology that applies packaging substrate technology to smartphone HDI substrates, thereby reducing the area and width of the plate, increasing the number of layers, and improving volume efficiency.
- the technology was originally developed to be applied to flexible displays, but in order to improve the utilization of space in mobile phones, it has recently been widely used in smart phone configurations. In order to manufacture and process such a thin substrate, it is necessary to reduce the difference in thermal expansion coefficient between the resin cured product and the substrate. Therefore, the demand for low CTE epoxy resins with flame retardancy is increasing.
- the present invention provides a phosphorus-containing flame-retardant epoxy resin with low thermal expansion coefficient, as shown in chemical formula 1.
- m, n, o, p, q are integers selected from 0 to 5, m, n, o, p, q are not 0 at the same time, and m, q are not 0 at the same time;
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , X, Y, and Z are independent of each other and represent each, Wherein R 1 , R 2 , R 10 , and R 11 are the same or different, and are respectively selected from C1-C3 alkoxy, or C6-C10 aryl or aralkyl;
- R 3 , R 4 , R 12 and R 13 are the same or different, and are selected from -H or C1-C3 hydrocarbon groups;
- R 5 , R 7 , and R 8 are the same or different, and are respectively selected from -H, a C1-C3 hydrocarbon group, a C5-C6 cycloalkyl group, or a C6-C18 aryl group;
- R 6 , R 9 and Z are the same or different, and each represents a divalent aryl group
- X and Y are the same or different, and are respectively selected from chemical bonds, or —O—, or
- R 0 represents -H, C1-C5 alkyl, or C6-C10 aryl or aralkyl
- R 14 and R 15 are the same or different and are respectively selected from -H, C1-C3 hydrocarbon group, C5-C6 cycloalkyl group or C6-C18 aryl group.
- the C1-C3 alkoxy represents methoxy, ethoxy, propoxy or isopropoxy
- C1 ⁇ C3 hydrocarbon group means chain or cyclic alkyl, alkenyl, alkynyl, such as: methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, ethynyl, propenyl, alkene Propyl, isopropenyl, cyclopropenyl, propynyl or propargyl;
- the C1-C5 alkyl group means methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, etc.;
- C5-C6 cycloalkyl means cyclopentyl, cyclohexyl or methyl substituted cyclopentyl, etc.
- the aryl or aralkyl group of C6 ⁇ C10 means phenyl, hydroxyphenyl, tolyl, Xylyl, Ethylphenyl, ⁇ -naphthyl ( ⁇ -naphthyl, ⁇ -naphthyl, indenyl, Benzyl, Phenethyl, etc.;
- C6 ⁇ C18 aryl groups represent phenyl, hydroxyphenyl, tolyl, xylyl, ethylphenyl, biphenyl, triphenyl, ⁇ -naphthyl, ⁇ -naphthyl, anthracene Base (anthracyl), phenanthryl (phenanthryl), indenyl (indenyl), fluorenyl (fluorenyl), acenaphthenyl (acenaphthenyl), pyrenyl (pyrenyl), ⁇ (chrysenyl) etc.;
- the divalent aryl group means divalent phenyl, tolyl, xylyl, hydroxyphenyl, biphenyl, terphenyl, ⁇ -naphthyl, ⁇ -naphthyl, anthryl, phenanthryl, and the like.
- the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin of the present invention has a flame-retardant phosphorus element structure located on the side chain of the epoxy resin structure, instead of the existing halogen-containing epoxy resin composition as a flame-retardant component. It has good processability when added to epoxy resin composition. Correspondingly, due to the presence of the side chain structure, the fluidity of the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin is reduced, the molecular stability is high at high temperature, it has the characteristics of low thermal expansion coefficient and good heat resistance.
- the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin of the present invention is suitable for the fields of electrical insulation materials, electronic insulation materials, semiconductor packaging materials and the like due to its excellent heat resistance and flame resistance.
- Another object of the present invention is to provide a preparation method of the above phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin, which specifically includes the following steps:
- the alkali catalyst is weighed at a ratio of 1:(1-2), and the alkali catalyst is added dropwise to the solution obtained in step P4 under stirring. The dripping is completed within ⁇ 5h, and the reaction mixture is obtained;
- the phosphorus-containing compound in step P1 is selected from one or more of the compounds shown in Chemical Formula 2 and Chemical Formula 3.
- R 16 and R 17 are independent of each other and each represents, R 16 is -H, C1-C5 alkyl, C1-C5 alkoxy, C5-C6 cycloalkyl, or C6-C18 aryl ; R 17 is -H, C1-C5 alkyl, C5-C6 cycloalkyl or C6-C18 aryl; wherein C1-C5 alkyl represents methyl, ethyl, propyl, isopropyl , Butyl, isobutyl, pentyl and other linear or branched alkyl groups; C1-C5 alkoxy represents methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy Straight-chain or branched alkoxy groups such as C5 ⁇ C6 cycloalkyl group; C5-C6 cycloalkyl group means cyclopentyl, methyl-substituted cyclopentyl and cycl
- the aromatic compound in step P2 is selected from one or more of quinone compounds, chemical formula 4 and chemical formula 5,
- R 18 and R 19 are independent of each other and represent each
- R 18 and R 19 are the same or different, and are respectively selected from -H, -OH, C1-C3 hydrocarbon group, C5-C6 cycloalkyl group or C6-C18 aryl group;
- R 20 and R 21 are independent of each other and represent each
- R 20 and R 21 are the same or different, and are respectively selected from -H, -OH, C1-C3 hydrocarbon group, C5-C6 cycloalkyl group or C6-C18 aryl group;
- the quinone compound is selected from one or more of benzoquinone, naphthoquinone, anthraquinone and phenanthrenequinone;
- C1 ⁇ C3 hydrocarbon group means chain or cyclic alkyl, alkenyl, alkynyl, such as: methyl, ethyl, propyl, isopropyl, cyclopropyl, vinyl, ethynyl, propenyl, alkene Propyl, isopropenyl, cyclopropenyl, propynyl or propargyl;
- C5-C6 cycloalkyl means cyclopentyl, methyl-substituted cyclopentyl and cyclohexyl;
- C6-C18 aryl means benzene Group, hydroxyphenyl, tolyl, xylyl, ethylphenyl, biphenyl, terphenyl, ⁇ -naphthyl, ⁇ -naphthyl, anthracenyl, phenanthryl, indenyl, fluorenyl, acenap
- the quinone compound may specifically be: 1,4-Benzuoquinone, 1,2-Benzuoquinone, 1,4-Naphthoquinone (1,4-Naphthoquinone) , 1,2-Naphthoquinone (1,2-Naphthoquinone), 2,6-Naphthoquinone (2,6-Naphthoquinone), 1,2-anthraquinone (1,2-Anthraquinone), 2,6-anthraquinone ( 2,6-Anthraquinone), 1,4-anthraquinone (1,4-Anthraquinone), 9,10-anthraquinone (9,19-Anthraquinone), 1,4-phenanthrenequinone (1,4-Phenanthrenequinone) or 2 , 3-Phenanthrenequinone (2,3-Phenanthrenequin-one).
- the raw materials added in step P4 also include as polymerized monomers, compounds represented by chemical formula 6 and chemical formula 7, quinone compounds, and one or more of the compounds represented by chemical formula 2 and chemical formula 3,
- R 5 , R 7 , and R 8 are the same or different, and are respectively selected from -H, a C1-C3 hydrocarbon group, a C5-C6 cycloalkyl group, or a C6-C18 aryl group;
- R 6 and R 9 are the same or different, and each represents a divalent aryl group
- X and Y are the same or different, and are respectively selected from chemical bonds, or —O—, or
- R 0 represents -H, C1-C5 alkyl, or C6-C10 aryl or aralkyl
- R 14 and R 15 are the same or different and are respectively selected from -H, C1-C3 hydrocarbyl group, C5-C6 cycloalkyl group or C6-C18 aryl group;
- the quinone compound is selected from one or more of benzoquinone, naphthoquinone, anthraquinone and phenanthrenequinone;
- C1-C3 alkyl represents methyl, ethyl, propyl and isopropyl
- C5-C6 cycloalkyl represents cyclopentyl, methyl-substituted cyclopentyl and cyclohexyl
- C6-C18 aryl Group represents phenyl, hydroxyphenyl, tolyl, xylyl, ethylphenyl, biphenyl, terphenyl, ⁇ -naphthyl, ⁇ -naphthyl, anthracenyl, phenanthryl, indenyl, fluorenyl, Acenaphthyl, pyrene
- Divalent aryl group means divalent phenyl, tolyl, xylyl, hydroxyphenyl, biphenyl, terphenyl, ⁇ -naphthyl, ⁇ -naphthyl, anthryl, phenan
- the quinone compound may specifically be: 1,4-benzoquinone, 1,2-benzoquinone, 1,4-naphthoquinone, 1,2-naphthoquinone, 2,6-naphthoquinone, 1,2-anthraquinone , 2,6-anthraquinone, 1,4-anthraquinone, 9,10-anthraquinone, 1,4-phenanthrenequinone or 2,3-phenanthrenequinone.
- the method further includes a refining step of performing the following treatments on the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin prepared through steps P1-P6:
- step P7 Add 50-200wt% of solvent III dropwise to the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin obtained in step P6, heat up to 75-85°C, keep warm and stir to make the phosphorus-containing flame retardant low thermal expansion coefficient epoxy The resin is completely dissolved;
- step P8 Add alkali catalyst under the condition of keeping warm and stirring at 75 ⁇ 85°C.
- the addition amount of alkali catalyst is 1-100wt% of the amount of alkali catalyst in step P5, and the addition is completed within 2 ⁇ 5h, and the refining reaction is carried out to obtain epoxy resin mixture;
- step P9 Add 50-200wt% of water to the epoxy resin mixture, which accounts for the mass of the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin obtained in step P6, stir for 20-40 minutes, and then stand for 20-40 minutes to remove the lower layer of water;
- step P11 Heat the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin obtained in step P10 to ⁇ 150°C, and remove the residual solvent III.
- the type and amount of solvent I, solvent II, and solvent III used in the present invention are based on the principle that they can dissolve the reaction product and can be used under the corresponding reaction temperature conditions, and can be adjusted according to the actual amount of reaction raw materials and performance differences. Considering comprehensively, a solvent with a boiling point of 75-150°C is preferred.
- the volatilization of the solvent can be minimized to ensure the smooth and efficient reaction. After the reaction, it can be evaporated under reduced pressure. The solvent is removed by other methods to obtain high-purity products.
- solvent I selects any one of organic solvents such as toluene, methyl isobutyl ketone, pyridine, 4-methyl-2-pentanone, butanol, ethylenediamine, acetic acid, etc.;
- the solvent II is water One or more of, isopropanol, butanol, and ethylene glycol dimethyl ether;
- the solvent III is toluene, methyl isobutyl ketone, pyridine, 4-methyl-2-pentanone, butanol , Ethylenediamine, acetic acid and other organic solvents.
- the alkali catalyst used is sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, sodium methoxide or sodium ethoxide, and the specific type is not limited.
- Another object of the present invention is to provide an application of the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin prepared by the above method.
- the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin prepared by the method of the present invention is a kind of Halogen-free compounds, can be used for high-reliability electrical and electronic insulation materials, semiconductor packaging materials, and can be used for PCB boards and insulation boards that require excellent low thermal expansion coefficient, flame retardancy, heat resistance and low dielectric properties, or other related requirements Performance requirements of resin composite materials, adhesives, coating agents, coatings and other fields.
- Another object of the present invention is to provide an intermediate product for preparing the above-mentioned phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin, which is prepared through the steps P1-P3 of the above-mentioned preparation method.
- solvent I can be removed by means of reduced pressure evaporation, or purification process can be used for purification to obtain high-purity intermediate products; it can also be based on the crude intermediate products prepared through steps P1-P3, Continue to add epichlorohydrin, alkali catalyst, etc. to prepare phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin.
- This kind of intermediate product has high flame retardancy and can be used for epoxy resin modification to improve the flame retardant and heat resistance properties of epoxy resin, and it can also be used for modification of other polymer materials.
- Fig. 1 is a process flow diagram of a preparation method of a phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin in an embodiment.
- Example 1 Preparation of phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin
- Example 2 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 1.
- Example 3 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 2.
- Example 4 Preparation of phosphorus-containing flame-retardant epoxy resin with low thermal expansion coefficient
- Example 4 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 3.
- Example 5 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 4.
- Example 6 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 5.
- Example 7 Preparation of phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin
- Example 7 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 6.
- Example 8 Preparation of phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin
- Example 8 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 7.
- Example 9 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 8.
- Example 10 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 9.
- Example 11 Preparation of phosphorus-containing flame-retardant epoxy resin with low thermal expansion coefficient
- Example 11 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 10.
- Example 12 Preparation of phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin
- Example 12 is based on Example 1. The process flow is shown in Figure 1. The difference from Example 1 is that the raw materials added in each step and the amount of raw materials added are different, as shown in Table 11.
- An epoxy resin prepared by the following process To a reactor equipped with a stirrer, a thermometer, and a reflux condenser, 216g DOPO and 817g phenol novolac epoxy resin (Phenol Novoac Epoxy, EEW: 128g/eq) are added, After confirming dissolution at 110°C, 1000 ppm of imidazole catalyst was added. Stir thoroughly and disperse, heat to raise the temperature to 150°C. The equivalent is detected every hour, and when the theoretical equivalent is reached, the reaction is terminated and the solid is taken out to obtain a yellow solid epoxy resin.
- An epoxy resin prepared by the following process Into a reactor equipped with a stirrer, a thermometer, and a reflux condenser, 324g DOPO-HQ and 1100g Bisphenol-A Epoxy (EEW: 187g/eq), after confirming the dissolution at 110°C, 1000ppm imidazole catalyst was added. Stir thoroughly and disperse, heat to raise the temperature to 150°C. The equivalent is detected every hour. When the theoretical equivalent is reached, the reaction is terminated and the solid is taken out to obtain a yellow solid epoxy resin.
- DOPO, DOPO-HQ and DOPO-NQ are all phosphorus flame retardants
- the chemical formula of DOPO is,
- the chemical formula of DOPO-HQ is,
- the following uses the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin of the present invention as a raw material to prepare an epoxy resin composition before performing performance testing. .
- Table 12 and Table 13 below show the amount of each substance used in the preparation process of the epoxy resin composition in Manufacturing Examples 1-12.
- Table 14 below shows the amount of each substance used in the preparation of pure resin hardened products in Comparative Manufacturing Examples 1-3.
- Td The decomposition temperature (Td) was measured using a thermogravimetric analyzer (TGA);
- the lead heat resistance test was carried out in accordance with the JIS-C-6481 method, and the state of the cured epoxy resin product immersed in a lead bath at 300°C for 120s was visually observed. Mark O when swelling and cracking are not observed by naked eyes, and X when observed;
- the epoxy resin prepared by incorporating the phosphorus-containing flame-retardant low thermal expansion epoxy resin of the present invention has a higher naphthalene content, so the glass transition temperature is higher, the dielectric constant is lower, and the thermal expansion coefficient is lower, and it is more suitable for achieving excellent low thermal expansion coefficient performance.
- the phosphorus-containing flame-retardant low thermal expansion coefficient epoxy resin of the present invention is a halogen-free compound, and can be used for high-reliability electrical and electronic materials, and can be used for requirements of excellent low thermal expansion coefficient, flame retardancy, heat resistance and low node characteristics PCB boards and insulating boards as well as other compatible materials, adhesives, coating agents, coatings and other fields that require related performance.
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Abstract
La présente invention concerne une résine époxyde ignifuge à faible coefficient de dilatation thermique contenant du phosphore, et un procédé de préparation, un intermédiaire associé et une utilisation correspondants, et relève du domaine technique des matériaux en résine. Les points clés de la solution technique de la présente invention sont qu'au moins un composé contenant du phosphore et au moins un composé aromatique sont utilisés comme matières premières pour préparer l'intermédiaire, qui est ajouté à de l'épichlorhydrine et polymérisé en présence d'un catalyseur alcalin pour obtenir la résine époxyde ignifuge à faible coefficient de dilatation thermique contenant du phosphore ayant une teneur élevée en phosphore, une bonne ininflammabilité, une faible constante diélectrique et un faible coefficient de dilatation thermique. La résine époxyde peut être utilisée dans des matériaux électroniques électriques à haute fiabilité, des plaques PCB et des plaques isolantes nécessitant d'excellents coefficients de faible dilatation thermique, une excellente ininflammabilité, une excellente résistance à la chaleur et d'excellentes propriétés diélectriques faibles, ainsi que dans d'autres domaines tels que des composites, des adhésifs, des agents de revêtement et des revêtements qui nécessitent des propriétés correspondantes.
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CN1306041A (zh) * | 2000-01-17 | 2001-08-01 | 住友电木株式会社 | 阻燃树脂组合物、以及使用该组合物的预浸材料和层压品 |
WO2002066485A2 (fr) * | 2001-02-15 | 2002-08-29 | Pabu Services, Inc. | Nouveaux oxydes de phosphine hydroxyaryle, ethers glycidyle, compositions epoxy et composites et stratifies derives de ceux-ci |
CN101357999A (zh) * | 2007-07-31 | 2009-02-04 | 晋一化工股份有限公司 | 难燃性树脂及难燃性树脂组合物 |
CN102471534A (zh) * | 2009-09-11 | 2012-05-23 | 科聚亚公司 | 羟基苯基氧化膦混合物和它们作为用于环氧树脂的阻燃剂的应用 |
CN105555866A (zh) * | 2013-09-30 | 2016-05-04 | 新日铁住金化学株式会社 | 含磷环氧树脂组合物和固化物 |
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CN1306041A (zh) * | 2000-01-17 | 2001-08-01 | 住友电木株式会社 | 阻燃树脂组合物、以及使用该组合物的预浸材料和层压品 |
WO2002066485A2 (fr) * | 2001-02-15 | 2002-08-29 | Pabu Services, Inc. | Nouveaux oxydes de phosphine hydroxyaryle, ethers glycidyle, compositions epoxy et composites et stratifies derives de ceux-ci |
CN101357999A (zh) * | 2007-07-31 | 2009-02-04 | 晋一化工股份有限公司 | 难燃性树脂及难燃性树脂组合物 |
CN102471534A (zh) * | 2009-09-11 | 2012-05-23 | 科聚亚公司 | 羟基苯基氧化膦混合物和它们作为用于环氧树脂的阻燃剂的应用 |
CN105555866A (zh) * | 2013-09-30 | 2016-05-04 | 新日铁住金化学株式会社 | 含磷环氧树脂组合物和固化物 |
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