CN106832778B - A kind of halogen-free flameproof epoxy systems and preparation method thereof - Google Patents
A kind of halogen-free flameproof epoxy systems and preparation method thereof Download PDFInfo
- Publication number
- CN106832778B CN106832778B CN201710075125.4A CN201710075125A CN106832778B CN 106832778 B CN106832778 B CN 106832778B CN 201710075125 A CN201710075125 A CN 201710075125A CN 106832778 B CN106832778 B CN 106832778B
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- China
- Prior art keywords
- halogen
- free
- flame retardants
- epoxy
- free flameproof
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003063 flame retardant Substances 0.000 claims abstract description 68
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000003822 epoxy resin Substances 0.000 claims abstract description 33
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 23
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000005516 engineering process Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 14
- -1 hydroxyl halogen-free flame Chemical compound 0.000 claims description 14
- 150000008065 acid anhydrides Chemical class 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003085 diluting agent Substances 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- 150000002460 imidazoles Chemical class 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 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 4
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 3
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical class O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 claims description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 2
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 2
- 150000004714 phosphonium salts Chemical class 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000011973 solid acid Substances 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 125000001302 tertiary amino group Chemical group 0.000 claims 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 7
- 238000005538 encapsulation Methods 0.000 abstract description 5
- 239000012774 insulation material Substances 0.000 abstract description 3
- 238000001879 gelation Methods 0.000 abstract description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 16
- 239000012212 insulator Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- CSHJJWDAZSZQBT-UHFFFAOYSA-N 7a-methyl-4,5-dihydro-3ah-2-benzofuran-1,3-dione Chemical class C1=CCCC2C(=O)OC(=O)C21C CSHJJWDAZSZQBT-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011810 insulating material Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 235000012254 magnesium hydroxide Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- LYQARTBYZUZKPJ-UHFFFAOYSA-N [Na].CO.CO Chemical compound [Na].CO.CO LYQARTBYZUZKPJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RIWRFSMVIUAEBX-UHFFFAOYSA-N n-methyl-1-phenylmethanamine Chemical compound CNCC1=CC=CC=C1 RIWRFSMVIUAEBX-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4238—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof heterocyclic
-
- 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
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/508—Amines heterocyclic containing only nitrogen as a heteroatom having three nitrogen atoms in the ring
- C08G59/5086—Triazines; Melamines; Guanamines
-
- 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
- C08G59/62—Alcohols or 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
- C08G59/18—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
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
The present invention provides a kind of preparation methods of halogen-free flameproof epoxy systems.Modified epoxy and anhydride curing agent are distinguished using the halogen-free flame retardants of hydroxyl or amino；Preparation process of the invention is simple, has taken into account low cost, excellent physical property and processing performance, the traditional pouring technology and automatic pressure gelation process (APG) technique suitable for electronic component bonding, encapsulation and electrical equipment major insulation material；The above thickness of Halogenless fire retarded epoxy resin UL 94-V0 1.5mm being prepared is fire-retardant.
Description
Technical field
The present invention relates to Halogenless fire retarded epoxy resin preparation fields, and in particular to a kind of halogen-free flameproof epoxy systems and its system
Preparation Method.
Background technique
Epoxy resin is because it is with preferable insulating properties, caking property, good mechanical property, building-up property and opposite
The advantages such as low cost are widely used in the main body insulating materials of the bonding of electronic component, encapsulation and electrical equipment.But
Inflammable epoxy resin applies the substrate in the major insulation of electrical equipment, the encapsulation of electronic component and printed wiring board, exists
Huge fire hazard.For this purpose, scientific circles have done very more basic research works [1-3] to the flame retardant property of epoxy resin,
And some technical application is in production practice.The fire-retardant research of epoxy resin and practice from brominated flame retardant epoxy tree
Rouge turns to halogen-free flameproof and the unleaded field of non-halogen non-phosphate.Brominated fire retarding epoxide resin is mainly used in the fields such as printed wiring board,
Research shows that [4], brominated epoxy resin can release noxious material in burning, such as highly acid gas, cause in people in fire
Poison and can not flee from；In waste treatment, there may be the strong carcinogens such as such as polybrominated dibenzo-furan again.So the prosperities such as European Union
Country proposes Rosh and Reach authentication procedure, it is desirable that electric that fields is waited to be forbidden to use brominated halogenated flame retardant preparation
Fire retarding epoxide resin, people have turned one's attention to " Halogen " fire-retardant epoxy resin system.In electric insulation epoxy resin body
In system, realize halogen-free flameproof approximately by three kinds of strategies are used: first, using or use the rings of various phosphor-containing structures with
Oxygen resin and curing agent [5-6].This strategy can take into account the physical property of flame retardant effect and preparation really.But phosphorous knot
The epoxy resin of structure and the preparation process of curing agent are complicated, and the electric insulation epoxy resin of preparation is at high cost.Second, addition contains
Phosphorus or nitrogenous small organic molecule realize the flame retardant effect of product in epoxy resin or hardener formula system.This strategy
The epoxy resin electrical insulating material flame retardant effect prepared using halogen-free flame retardants is excellent, but due to most of small molecule Halogen
The disadvantages of fire retardant has volatility big, thermal stability difference and high water absorption rate, so that the epoxy resin electrical insulating material of preparation
Mechanical performance, wet-hot aging performance and in terms of existing defects [7].Third adds inorganic anti-flaming material in epoxy
The flame retardant effect of product is realized in resin formula system.Realize that this strategy needs to add a large amount of inorganic filler, so that formula
The viscosity of system, which increases, influences processing performance, and the Formulaion of epoxy resin system of high filler declines its mechanical performance sharply.
[1] Zhang Wenchao, puts out fire retarding epoxide resin mechanism and the Beijing application study [D]: Beijing Institute of Technology, and 2013
[2] Ren Hua, heat resistance, the synthesis of fire retarding epoxide resin and curing agent and the Hangzhou performance study [D]: Zhejiang is big
It learns, 2008.
[3] it Li Hongxia, the preparation of halogen-free fire-retardant epoxy resin electronic package material and the Harbin performance study [D]: breathes out
That shore Polytechnics, 2015.
[4] Wang C.S., Berman J., Walker L., Mendoza A.J., Appl.Polym.Sci., 2003,
43:1315.
[5]Liu Y.L.,J.Polym.Sci.Part A:Polym.Chem.,2002,40:359.
[6]Wang X.,Zhang Q.,Eur.Polym.J.,2004,40:385.
[7]Green J.J.,Fire.Sci.,1992,10:470.
Summary of the invention
Inexpensive, physical property is taken into account the purpose of the present invention is to provide one kind and processing performance is excellent, is suitable for electronics
The traditional pouring technology and automatic pressure gelation process (APG) work of component bonding, encapsulation and electrical equipment major insulation material
Skill, the fire-retardant halogen-free flameproof epoxy systems of the above thickness of UL 94-V0 1.5mm.
It is at low cost another object of the present invention is to provide a kind of preparation method is simple, it is suitble to industrialization large-scale application
Halogen-free flameproof epoxy systems preparation method.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of preparation method of halogen-free flameproof epoxy systems is modified ring using the halogen-free flame retardants of hydroxyl or amino respectively
Oxygen resin and anhydride curing agent；
Wherein, modified epoxy process are as follows:
Under vacuum conditions, according to hydroxyl or amino and isocyanates in halogen-free flame retardants isocyano molar ratio
Not equal to 1 by containing amino or hydroxyl halogen-free flame retardants and isocyanates mix, 40-120 DEG C at a temperature of react I, prepare
It obtains being cooled to room temperature containing terminal hydroxy group, Amino End Group or the prepolymer for holding isocyanic acid；Then epoxy resin and catalyst, control is added
Prepolymer processed accounts for 7-25% in whole system, is heated to 40 DEG C -170 DEG C, reacts II, is cooled to room temperature, and relative response is added and produces
The reactive diluent that object is 2-25 mass % carries out viscosity-adjusting agent, so that halogen-free flameproof agent content in whole system is not less than 5%, obtains
To halogen-free flame retardants modified epoxy；
During halogen-free flame retardants modified anhydride curing agent:
In parts by mass,
Containing amino or 5-15 parts of hydroxyl halogen-free flame retardants
Solid or 5-30 parts of liquid acid anhydrides
55-75 parts of liquid acid anhydrides
Under vacuum conditions, by containing amino or hydroxyl halogen-free flame retardants and solid or liquid acid anhydrides mix, be warming up to
120 DEG C -220 DEG C, III is reacted, is cooled to 60 DEG C -100 DEG C, liquid acid anhydrides is added and carries out viscosity-adjusting agent, is then added relatively anti-
The promotor of product 0.05-5 mass % is answered, is stirred, it is cooling, obtain halogen-free flameproof anhydride curing agent；
Halogen-free flameproof powder is mixed with 200-800 mesh silica flour according to mass ratio for 5-85:15-95, stirs, obtains
Halogen-free flameproof filler；
By halogen-free flame retardants modified epoxy, halogen-free flame retardants modified anhydride curing agent and halogen-free flameproof filler according to matter
Amount is uniformly mixed under conditions of temperature is 25 DEG C -80 DEG C than being 1:1:3.0-4.5, after carrying out vacuum defoamation under vacuum conditions
Halogen-free flameproof epoxy systems are prepared by APG technique or pouring technology.
During modified epoxy, preparation hydroxyl containing end is reacted with isocyanates using the halogen-free flame retardants of amino or hydroxyl
Base, Amino End Group or the prepolymer for holding isocyanic acid, and prepolymer is carried out under the effect of the catalyst to be grafted instead with epoxy resin
The epoxy resin of different phosphate, nitrogen or phosphorus nitrogen content should be prepared；
In the modifying process of anhydride curing agent, halogen-free flame retardants and solid or liquid anhydride reaction containing amino or hydroxyl
The linear anhydride oligomer of different phosphate, nitrogen or phosphorus nitrogen content is prepared, and viscosity adjusting is carried out using liquid acid anhydrides.
The present invention further comprises following preferred technical solution:
In preferred scheme, the halogen-free flame retardants of the hydroxyl or amino be selected from the phosphorous of hydroxyl or amino and/or
Nitrogen compound.
In preferred scheme, the halogen-free flame retardants modified epoxy is milky to light yellow solvent-free liquid epoxy
Resin；The halogen-free flame retardants modified anhydride curing agent is to improve preaceleration milky to light yellow solvent-free acid anhydrides liquid curing
Agent；The halogen-free flameproof filler is that white arrives yellowish powder.
In preferred scheme, the reaction time of the reaction I is 30min-2h；
In preferred scheme, the reaction time of the reaction II is 1-3h；
In preferred scheme, the reaction time of the reaction III is 2-4h；
In preferred scheme, stirred 30-120 minutes after promotor is added.
The product data of the halogen-free flame retardants modified epoxy are as follows:
Viscosity at 25 DEG C: 4,000-15,000MPa.s；
Epoxy content: 3.00-4.40eq/kg；
Density at 25 DEG C: 1.13-1.25g/cm3。
The product data of the halogen-free flame retardants modified anhydride curing agent are as follows:
In preferred scheme, the hydroxyl halogen-free flame retardants include but is not limited to N- hexamethylol amino ring phosphonitrile,
One or more of phosphoric acid ester oligomer of DOPO-HQ, phosphorus-containing polyol or hydroxyl；
In preferred scheme, the amino halogen-free flame retardants include but is not limited to but be not limited to melamine and its esters or
Butylated melamine-formaldehyde resin.
In preferred scheme, the solid acid anhydrides includes but is not limited to phthalic anhydride, cis-butenedioic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or inclined
One or more of benzenetricarboxylic anhydride；
In preferred scheme, liquid acid anhydrides include but is not limited to one of methyl tetrahydro phthalic anhydride or methyl hexahydrophthalic anhydride or
Two kinds.
In preferred scheme, the reactive diluent includes but is not limited to polyether polyol, polyester polyol or vegetable oil
Or derivatives thereof, one or more of epoxy group reactive diluent or other low viscosity compounds containing epoxy group；
In preferred scheme, the catalyst includes but is not limited to methanol solution of sodium methylate, 2- phenylimidazole solution or miaow
Azoles homologue solution etc..
In preferred scheme, the promotor include but is not limited to tertiary amine and salt, acetyl acetone salt, imidazoles or its
One or more of homologue, Qi phosphonium salt of triphenylphosphine Huo or organic carboxylate；
In preferred scheme, the halogen-free flameproof powder include but is not limited to ammonium polyphosphate, phosphonitrile, red phosphorus, white phosphorus or its
One or more of coating, magnesium hydroxide or aluminium hydroxide.
The present invention further comprises the halogen-free flameproof epoxy systems that above-mentioned preparation method is prepared.
The halogen-free flameproof epoxy systems can enumerate various electrical insulation products.It such as can specifically enumerate insulator.
Beneficial effects of the present invention:
First, it is reacted using the reactive group of halogen-free flame retardants with epoxy resin, solves conventional flame retardant epoxy resin system
Product in use fire retardant be precipitated the phenomenon that.
Second, using the combination of halogen-free flame retardants and special promotor containing specific groups, make it in the curing process
Even closer network structure can be formed with epoxy resin, improve the flame retardant property of system.
Third, the use of halogen-free flameproof powder can reduce the dosage of organic halogen-free agent, balance adding for epoxy resin
The mechanical performance of work performance (system viscosity) and solidfied material.
4th, organic halogen-free agent and halogen-free flameproof can be adjusted flexibly according to fire-retardant and product physical property requirements
Powder content realizes producing in serial form Halogenless fire retarded epoxy resin system.
5th, modified epoxy and anhydride curing agent are distinguished using the halogen-free flame retardants of hydroxyl or amino；And pass through
The combination of subsequent reactions has obtained the electrical insulation product for having both good flame-retardance energy and physical property.
The glass transition temperature of products obtained therefrom of the present invention is high, and bending strength and impact strength are high, and flame retardant property is good.Have
Excellent comprehensive performance.
6th, preparation process of the invention is simple, has taken into account low cost, excellent flame retardant property, excellent physical property
And processing performance.Suitable for traditional pouring technology of electronic component bonding, encapsulation and electrical equipment major insulation material and oneself
Dynamic pressure gel process (APG) technique.Common addition flame-retardant formulations, general physical properties are poor.
7th, the product surface being prepared is without bright stock dirt shape substance, without viscous hand phenomenon.
Specific embodiment
Comparative example 1
At 100 DEG C, by 20 mass parts DOPO-HQ (10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phospha
Phenanthrene -10- oxide) it is dissolved into 80 mass parts epoxy resin DER331.Then 60 DEG C of addition above-mentioned substance weight are cooled to
12% polyether polyol, stirs evenly, and is cooled to room temperature, is prepared into Halogenless fire retarded epoxy resin.At 120 DEG C, by 7.5 mass
Part DOPO-HQ is added in 92.5 mass parts methyl tetrahydro phthalic anhydrides, and tertiary amines promotion system, cooling room temperature, system are added at 60 DEG C
It is standby to obtain halogen-free flameproof curing agent.Under room temperature, 70 mass parts, 400 mesh activated quartz powder and 30 mass parts magnesium hydroxides are mixed equal
It is even, it is prepared into halogen-free flameproof powder.Then epoxy resin and anhydride curing agent and halogen-free flameproof powder are existed according to 100:100:370
Mix 1 hour, vacuumize 1.5 hours at 40 DEG C, 145 DEG C of mold temperature, vacuum degree 4.5mbar, 145 DEG C pressure maintaining 15 minutes, take off
Mould obtains an insulator (model: 8JS-608), then solidifies 8 hours after 140 DEG C.
DSC curve tests glass transition temperature at 85 DEG C.- 40 DEG C have a product cracking for -100 DEG C of cold cyclings 5 times
Phenomenon.Bending strength is 6500MPa, impact strength 12kJ/m2, flame retardant test reaches 4mm UL 94V1It is fire-retardant.Critical issue
The problem of be it is cooling after the surface of insulator have the greasy dirt shape substance of one layer of light, have viscous hand phenomenon at 100 DEG C or so.
Embodiment 1:
By 70 mass parts DOPO-HQ (10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxidation
Object) with 30 mass parts 2, the mixing of 4- toluene di-isocyanate(TDI), 100 DEG C at a temperature of react 1 hour, it is poly- that terminal hydroxy group is prepared
Urethane prepolymer is cooled to room temperature.10 mass parts of above-mentioned reactant are added in 90 mass parts epoxy resin, addition quality point
The 30 mass parts Methanol sodium methanol solutions that number is 0.01% react 2 hours at 160 DEG C as catalyst.It is cooled to room temperature, it will
Above-mentioned 90 mass parts of reactant are uniformly mixed with 10 mass parts polyether polyol (GE 204), obtain halogen-free flameproof modified epoxy tree
Rouge.
Under vacuum conditions, by 35 mass parts DOPO-HQ (10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phosphorus
Miscellaneous phenanthrene -10- oxide) and 65 mass parts tetrahydrophthalic anhydride 160 DEG C react 2 hours.Reaction terminates to be cooled to 80 DEG C.It will be above-mentioned anti-
It answers 50 mass parts of object and 49.55 mass parts methyl tetrahydro phthalic anhydrides to mix, the BDMA (two of relative response product 0.45% is then added
Methylbenzylamine) promotor, it stirs evenly, is cooled to room temperature, be prepared into halogen-free flameproof modified anhydride curing agent.
Under room temperature, 70 mass parts, 400 mesh activated quartz powder and 30 mass parts, 400 mesh magnesium hydroxide are uniformly mixed.Then
According to 100:100:370 by above-mentioned halogen-free flame retardants modified epoxy and modified anhydride curing agent and halogen-free flameproof powder 40
Mix 1 hour, vacuumize 1.5 hours at DEG C, 145 DEG C of mold temperature, vacuum degree 4.5mbar, 145 DEG C pressure maintaining 15 minutes, demoulding
It obtains an insulator (model: 8JS-608), then solidifies 8 hours after 140 DEG C.
It is 105 DEG C that DSC curve, which tests glass transition temperature,.- 40 DEG C of -100 DEG C of cold cyclings 5 times no any crackings are existing
As.Bending strength is 8500MPa, impact strength 15kJ/m2, flame retardant test reaches 4mm UL 94V0It is fire-retardant.Surface is without light
Greasy dirt shape substance.
Embodiment 2:
By 60 mass parts melamines and 40 mass parts 2, the mixing of 4- toluene di-isocyanate(TDI), 100 DEG C at a temperature of it is anti-
It answers 1 hour, amino-terminated polyurethane prepolymer is prepared, is cooled to room temperature.85 matter are added in 15 mass parts of above-mentioned reactant
It measures in part epoxy resin, the 2- phenylimidazole that addition mass fraction is 0.01% reacts 2 hours at 160 DEG C as catalyst.
It is added the 12% 12 to myristyl glycidol ether (AGE) of above-mentioned reactant weight, it is stand-by to be cooled to room temperature, prepares Halogen
Fire retarding epoxide resin.
At 100 DEG C, 15 mass parts melamine cyanurates (MCA) are dissolved in 85 mass parts methyl tetrahydro phthalic anhydrides
In, imidazoles promotion system is added at 60 DEG C, cooling room temperature is stand-by.Prepare halogen-free flameproof epoxy hardener.
Under room temperature, 60 mass parts, 400 mesh activated quartz powder and 40 mass parts, 600 mesh aluminium hydrate powder are uniformly mixed.Nothing
Halogen fireproof powder.
Then according to 100:100:350 by above-mentioned halogen-free flame retardants modified epoxy and modified anhydride curing agent and Halogen
Fire-retardant powder mixes 1 hour at 40 DEG C, vacuumizes 1.5 hours, and 145 DEG C of mold temperature, vacuum degree 4.5mbar, 155 DEG C of pressure maintainings
15 minutes, demoulding obtained an insulator (model: 8JS-608), then solidified 10 hours after 150 DEG C.
DSC curve tests glass transition temperature at 95 DEG C.Bending strength is 8000MPa.Impact strength is 13kJ/m2,
Flame retardant test reaches 4mm UL 94V0It is fire-retardant.
Embodiment 3:
65 mass parts phosphonate oligomers (CAS 68664-06-2) and 35 mass parts 2,4 toluene diisocyanates is mixed
Close, 100 DEG C at a temperature of react 1 hour, be prepared end phenolic group polyurethane prepolymer, be cooled to room temperature.By above-mentioned reaction
10 mass parts of object are added to 95 mass parts epoxy resin, the 2- phenylimidazole that addition mass fraction is 0.01% as catalyst,
It is reacted 2 hours at 150 DEG C.It is cooled to room temperature, above-mentioned 90 mass parts of reactant is shunk with 10 mass parts polypropylene glycols two sweet
Oily ether (PPGDGE) is uniformly mixed, and prepares halogen-free flameproof modified epoxy.
At 100 DEG C, 10 mass parts butylated melamine-formaldehyde resins are dissolved in 90 mass parts methyl tetrahydro phthalic anhydrides
In, imidazoles promotion system is added at 60 DEG C, cooling room temperature is stand-by.
Under room temperature, 90 mass parts, 400 mesh activated quartz powder and 10 mass parts melamine cyanurates (MCA) are mixed equal
It is even.Then according to 100:100:370 by above-mentioned halogen-free flame retardants modified epoxy and modified anhydride curing agent and halogen-free flameproof
Powder mixes 1 hour at 40 DEG C, vacuumizes 1.5 hours, and 145 DEG C of mold temperature, vacuum degree 4.5mbar, 155 DEG C of pressure maintainings 15 divide
Clock, demoulding obtain an insulator (model: 8JS-608), then solidify 10 hours after 150 DEG C.
DSC curve tests glass transition temperature at 100 DEG C.Bending strength is 9500MPa.Impact strength is 15kJ/m2,
Flame retardant test reaches 4mm UL 94V0It is fire-retardant.
Claims (9)
1. a kind of preparation method of halogen-free flameproof epoxy systems, which is characterized in that use hydroxyl or the halogen-free flame retardants of amino
Modified epoxy and anhydride curing agent respectively；
Wherein, modified epoxy process are as follows:
Under vacuum conditions, it is differed according to the molar ratio of the isocyano of hydroxyl or amino and isocyanates in halogen-free flame retardants
In 1 by containing amino or hydroxyl halogen-free flame retardants and isocyanates mix, 40-120 DEG C at a temperature of react, which is referred to as
To react I, it is prepared containing terminal hydroxy group, Amino End Group or the prepolymer for holding isocyanic acid, is cooled to room temperature；Then epoxy resin is added
And catalyst, control prepolymer account for 7-25% in whole system, are heated to 40-170 DEG C, reaction, the reaction is referred to as to react II,
It is cooled to room temperature, the reactive diluent that relative response product is 2-25 mass % is added and carries out viscosity-adjusting agent, makes in whole system
Halogen-free flameproof agent content is not less than 5%, obtains halogen-free flame retardants modified epoxy；
During halogen-free flame retardants modified anhydride curing agent:
Under vacuum conditions, by halogen-free flame retardants 5-15 mass parts and solid or liquid acid anhydrides 5-30 matter containing amino or hydroxyl
Part mixing is measured, is warming up to 120 DEG C -220 DEG C, reaction, the reaction is referred to as to react III, is cooled to 60 DEG C -100 DEG C, and 55- is added
75 mass parts liquid acid anhydrides carry out viscosity-adjusting agent, and the promotor of relative response product 0.05-5 mass % is then added, and stirring is cold
But, halogen-free flameproof anhydride curing agent is obtained；
Halogen-free flameproof powder is mixed with 200-800 mesh silica flour according to mass ratio for 5-85:15-95, stirs, obtains Halogen resistance
Fire filler；
By halogen-free flame retardants modified epoxy, halogen-free flame retardants modified anhydride curing agent and without fontanel fire-retardant filler according to mass ratio
It is uniformly mixed under conditions of temperature is 25 DEG C -80 DEG C for 1:1:3.0-4.5, passes through after carrying out vacuum defoamation under vacuum conditions
Halogen-free flameproof epoxy systems are prepared in APG technique or pouring technology；
The halogen-free flame retardants of the hydroxyl or amino is selected from the phosphorous and/or nitrogen compound of hydroxyl or amino.
2. the preparation method of halogen-free flameproof epoxy systems according to claim 1, which is characterized in that the halogen-free flame retardants
Modified epoxy is milky to light yellow solvent-free liquid epoxy resin；The halogen-free flame retardants modified anhydride curing agent is
Preaceleration milky is improved to light yellow solvent-free acid anhydrides liquid curing-agent；The halogen-free flameproof filler is that white arrives yellowish powder
Body.
3. the preparation method of halogen-free flameproof epoxy systems according to claim 1, which is characterized in that the reaction I's is anti-
It is 30min-2h between seasonable；
The reaction time of the reaction II is 1-3h；
The reaction time of the reaction III is 2-4h；
It is stirred 30-120 minutes after promotor is added.
4. the preparation method of halogen-free flameproof epoxy systems according to claim 1, which is characterized in that the halogen-free flame retardants
The product data of modified epoxy are as follows:
Viscosity at 25 DEG C: 4,000-15,00MPa.s；
Epoxy content: 3.00-4.40eq/kg；
Density at 25 DEG C: 1.13-1.25g/cm3。
5. the preparation method of halogen-free flameproof epoxy systems according to claim 1, which is characterized in that the halogen-free flame retardants
The product data of modified anhydride curing agent are as follows:
6. the preparation method of halogen-free flameproof epoxy systems according to claim 1, which is characterized in that the hydroxyl Halogen
Fire retardant is selected from N-hexamethylol amino ring phosphonitrile, DOPO-HQ, in the phosphoric acid ester oligomer of phosphorus-containing polyol or hydroxyl
It is one or more of；
The halogen-free flame retardants containing amino is selected from melamine and its esters, butylated melamine-formaldehyde resin.
7. the preparation method of halogen-free flameproof epoxy systems according to claim 1, which is characterized in that the solid acid anhydrides choosing
From one or more of cis-butenedioic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or trimellitic anhydride；
Liquid acid anhydrides is selected from one or both of methyl tetrahydro phthalic anhydride or methyl hexahydrophthalic anhydride.
8. the preparation method of halogen-free flameproof epoxy systems according to claim 1, which is characterized in that the reactive diluent
For one or more of polyether polyol, polyester polyol or vegetable oil, epoxy group reactive diluent；
The catalyst is selected from methanol solution of sodium methylate, 2- phenylimidazole solution or imidazoles homologue solution；
The promotor is tertiary amine, acetyl acetone salt, imidazoles or its homologue, Qi phosphonium salt of triphenylphosphine Huo or organic carboxylic
One or more of hydrochlorate；
The halogen-free flameproof powder be ammonium polyphosphate, phosphonitrile, red phosphorus, in white phosphorus or its coating, magnesium hydroxide or aluminium hydroxide
One or more.
9. the halogen-free flameproof epoxy systems product that any one of the claim 1-8 preparation method is prepared.
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| CN109438673B (en) * | 2018-08-30 | 2021-09-17 | 四川东材科技集团股份有限公司 | Low-hydroxyl phosphorus-containing epoxy resin, composition for copper-clad plate and preparation method of composition |
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