CN106832778A - 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
- CN106832778A CN106832778A CN201710075125.4A CN201710075125A CN106832778A CN 106832778 A CN106832778 A CN 106832778A CN 201710075125 A CN201710075125 A CN 201710075125A CN 106832778 A CN106832778 A CN 106832778A
- Authority
- CN
- China
- Prior art keywords
- halogen
- free
- epoxy
- flame retardants
- free flameproof
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004593 Epoxy Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000003063 flame retardant Substances 0.000 claims abstract description 62
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000003822 epoxy resin Substances 0.000 claims abstract description 33
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 33
- 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 32
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 19
- 150000008065 acid anhydrides Chemical class 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- -1 hydroxyl halogen-free flame Chemical compound 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 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
- 239000000945 filler Substances 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000003085 diluting agent Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 150000002460 imidazoles Chemical class 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 150000004941 2-phenylimidazoles Chemical class 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
- 230000004044 response Effects 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 claims description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 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
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 claims description 2
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-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
- 101710130081 Aspergillopepsin-1 Proteins 0.000 claims description 2
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical group CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-UHFFFAOYSA-N 0.000 claims description 2
- 230000006872 improvement Effects 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
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000011973 solid acid Substances 0.000 claims description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 238000002485 combustion reaction Methods 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000007711 solidification Methods 0.000 claims 1
- 230000008023 solidification Effects 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 class 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 12
- 239000000463 material Substances 0.000 description 7
- 239000012212 insulator Substances 0.000 description 6
- 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
- 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
- 239000000203 mixture 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
- 230000000979 retarding effect Effects 0.000 description 3
- 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
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000002156 mixing Methods 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
- 239000000758 substrate Substances 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
- 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
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 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
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides a kind of preparation method of halogen-free flameproof epoxy systems.Halogen-free flame retardants using hydroxyl or amino distinguishes modified epoxy and anhydride curing agent；Preparation process of the invention is simple, has taken into account inexpensive, excellent physical property and processing characteristics, it is adaptable to traditional pouring technology and automatic pressure gelation process (APG) technique of electronic component bonding, encapsulation and electrical equipment major insulation material；The Halogenless fire retarded epoxy resin UL 94-V0 1.5mm above thickness for preparing is fire-retardant.
Description
Technical field
The present invention relates to Halogenless fire retarded epoxy resin preparation field, and in particular to a kind of halogen-free flameproof epoxy systems and its system
Preparation Method.
Background technology
Epoxy resin has preferable insulating properties, caking property, good mechanical property, building-up property and relative because of it
The advantages such as low cost, are widely used in the main body insulating materials of the bonding, encapsulation and electrical equipment of electronic component.But
Inflammable epoxy resin applies the encapsulation and the base material of printed substrate in the major insulation, electronic component of electrical equipment, exists
Huge disaster hidden-trouble.Therefore, scientific circles have done very many basic research works [1-3] to the fire resistance of epoxy resin,
And some technology is applied in production practices.The fire-retardant research of epoxy resin and practice from brominated flame retardant epoxy tree
Fat 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 substrate,
Research shows [4] that brominated epoxy resin can discharge noxious material in burning, such as highly acid gas, in causing people in fire
Poison and cannot flee from；In waste treatment again there may be strong carcinogens such as such as polybrominated dibenzo-furans.So the prosperity such as European Union
Country proposes Rosh and Reach authentication procedures, it is desirable to which the field such as electric prohibits the use of brominated halogenated flame retardant to prepare
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, halogen-free flameproof is realized approximately by using three kinds of strategies：First, using or use with various phosphor-containing structures ring
Oxygen tree fat and curing agent [5-6].This strategy can take into account flame retardant effect and the physical property for preparing really.But phosphorous knot
The epoxy resin of structure and the preparation process of curing agent are complicated, the electric insulation epoxy resin high cost of preparation.Second, addition contains
Phosphorus or nitrogenous organic molecule realize the flame retardant effect of product in epoxy resin or hardener formula system.This strategy
The epoxy resin insulating material flame retardant effect prepared using halogen-free flame retardants is excellent, but due to most of small molecule Halogen
Fire retardant has volatility big, the shortcomings of heat endurance difference and water absorption rate high so that the epoxy resin insulating material of preparation
At the aspect such as mechanical performance, wet-hot aging performance and insulating properties existing defects [7].3rd, addition inorganic anti-flaming material is in epoxy
The flame retardant effect of product is realized in resin formula system.Realize that this strategy needs to add substantial amounts of inorganic filler so that with cube
The viscosity of system raises influence processing characteristics, and the Formulaion of epoxy resin system of filler high causes that its mechanical performance drastically declines.
[1] Zhang Wenchao, puts out fire retarding epoxide resin mechanism and application study [D] Beijing:Beijing Institute of Technology, 2013
[2] China, the synthesis of heat resistance, fire retarding epoxide resin and curing agent and performance study [D] Hangzhou are appointed:Zhejiang is big
Learn, 2008.
[3] Li Hongxia, the preparation of halogen-free fire-retardant epoxy resin electronic package material and performance study [D] Harbin:Breathe 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.
The content of the invention
Low cost, physical property and processing characteristics are taken into account it is an object of the invention to provide one kind excellent, it is adaptable to electronics
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 UL 94-V0 1.5mm above thickness.
Another object of the present invention is to provide a kind of preparation method simply, low cost is adapted to industrialization large-scale application
Halogen-free flameproof epoxy systems preparation method.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of preparation method of halogen-free flameproof epoxy systems, using hydroxyl or amino halogen-free flame retardants respectively be modified ring
Oxygen tree fat and anhydride curing agent；
Wherein, modified epoxy process is：
Under vacuum, according to the hydroxyl or amino in halogen-free flame retardants and the mol ratio of the isocyano of isocyanates
It is not equal to 1 to mix halogen-free flame retardants and isocyanates containing amino or hydroxyl, I is reacted at a temperature of 40-120 DEG C, prepares
The prepolymer containing terminal hydroxy group, Amino End Group or end isocyanic acid is obtained, room temperature is cooled to；Epoxy resin and catalyst are subsequently adding, are controlled
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, adds relative response to produce
Thing carries out viscosity regulation for the reactive diluent of 2-25 mass %, and halogen-free flameproof agent content is not less than 5% in making whole system, obtains
To halogen-free flame retardants modified epoxy；
During halogen-free flame retardants modified anhydride curing agent：
In parts by mass,
Containing 5-15 parts of amino or hydroxyl halogen-free flame retardants
5-30 parts of solid or liquid acid anhydrides
55-75 parts of liquid acid anhydrides
Under vacuum, halogen-free flame retardants and solid or liquid acid anhydrides containing amino or hydroxyl are mixed, is warming up to
120 DEG C -220 DEG C, III is reacted, be cooled to 60 DEG C -100 DEG C, add liquid acid anhydrides to carry out viscosity regulation, be subsequently adding relatively anti-
The accelerator of product 0.05-5 mass % is answered, is stirred, cooling obtains halogen-free flameproof anhydride curing agent；
It is 5-85 according to mass ratio by halogen-free flameproof powder and 200-800 mesh silica flour：15-95 mixes, stirring, 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 than being 1:1:3.0-4.5 is well mixed under conditions of being 25 DEG C -80 DEG C in temperature, after carrying out vacuum defoamation under vacuum
Halogen-free flameproof epoxy systems are prepared by APG techniques or pouring technology.
During modified epoxy, reacted using halogen-free flame retardants and the isocyanates of amino or hydroxyl and prepare the hydroxyl containing end
The prepolymer of base, Amino End Group or end isocyanic acid, and prepolymer is carried out in the presence of catalyst with epoxy resin be grafted anti-
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 regulation is carried out using liquid acid anhydrides.
The present invention further includes following preferred technical scheme：
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 improvement preaceleration milky to light yellow solvent-free acid anhydrides liquid curing
Agent；The halogen-free flameproof filler is white to slightly yellow 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 adding accelerator.
The product data of the halogen-free flame retardants modified epoxy are：
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：
In preferred scheme, the hydroxyl halogen-free flame retardants include but is not limited to N- hexamethylol amino rings phosphonitrile,
One or more in the 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, THPA, HHPA or inclined
One or more in benzenetricarboxylic anhydride；
In preferred scheme, liquid acid anhydrides include but is not limited to one kind in methyl tetrahydro phthalic anhydride or methyl hexahydrophthalic anhydride or
Two kinds.
In preferred scheme, the reactive diluent includes but is not limited to PPG, PEPA or vegetable oil
Or derivatives thereof, epoxy radicals reactive diluent or other containing epoxy radicals lowering viscousity compounds in one or more；
In preferred scheme, the catalyst includes but is not limited to methanol solution of sodium methylate, 2- phenylimidazoles solution or miaow
Azoles homologue solution etc..
In preferred scheme, the accelerator include but is not limited to tertiary amine and salt, acetyl acetone salt, imidazoles or its
One or more in homologue, Qi phosphonium salts of triphenylphosphine Huo or organic carboxylate；
In preferred scheme, the halogen-free flameproof powder include but is not limited to APP, phosphonitrile, red phosphorus, white phosphorus or its
One or more in coating, magnesium hydroxide or aluminium hydroxide.
The present invention further includes 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.Such as can specifically enumerate insulator.
Beneficial effects of the present invention：
First, reacted using the reactive group and epoxy resin of halogen-free flame retardants, solve conventional flame retardant epoxy resin system
The product phenomenon that fire retardant is separated out in use.
Second, using the combination of the halogen-free flame retardants containing specific groups and special accelerator, make it in the curing process
Even closer network structure can be formed with epoxy resin, improve the fire resistance of system.
3rd, the use of halogen-free flameproof powder can reduce the consumption 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, the halogen-free flame retardants using hydroxyl or amino distinguishes modified epoxy and anhydride curing agent；And pass through
The combination of subsequent reactions, has obtained having concurrently the electrical insulation product of 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 fire resistance is good.Have
Excellent combination property.
6th, preparation process of the invention is simple, has taken into account low cost, excellent fire resistance, excellent physical property
And processing characteristics.Suitable for electronic component bond, encapsulation and electrical equipment major insulation material traditional pouring technology and from
Dynamic pressure gel process (APG) technique.Common addition flame-retardant formulations, general physical properties are poor.
7th, the product surface for preparing is without bright stock dirt shape material, the viscous hand phenomenon of nothing.
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- phosphas
Phenanthrene -10- oxides) it is dissolved into 80 mass parts epoxy resin DER331.Then 60 DEG C are cooled to and adds above-mentioned substance weight
12% PPG, stirs, and is cooled to normal 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 is added at 60 DEG C, cools down normal temperature, system
It is standby to obtain halogen-free flameproof curing agent.Under normal temperature, the mesh activated quartz powder of 70 mass parts 400 and 30 mass parts magnesium hydroxides are mixed equal
It is even, it is prepared into halogen-free flameproof powder.Then according to 100：100：370 exist epoxy resin and anhydride curing agent and halogen-free flameproof powder
Mix 1 hour at 40 DEG C, vacuumize 1.5 hours, 145 DEG C of mold temperature, vacuum 4.5mbar, 145 DEG C of pressurizes 15 minutes take off
Mould draws an insulator (model：8JS-608), then 140 DEG C of solidify afterwards 8 hours.
DSC curve tests glass transition temperature at 85 DEG C.- 40 DEG C of -100 DEG C of cold cyclings have for 5 times a product to ftracture
Phenomenon.Bending strength is 6500MPa, and impact strength is 12kJ/m2, flame retardant test reaches 4mm UL 94V1It is fire-retardant.Key issue
Problem be that there is one layer of greasy dirt shape material of light on the surface of insulator after cooling, have viscous hand phenomenon at 100 DEG C or so.
Embodiment 1：
By 70 mass parts DOPO-HQ, (10- (2,5- dihydroxy phenyls) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrenes -10- is aoxidized
Thing) and 30 mass parts 2, the mixing of 4- toluene di-isocyanate(TDI)s, reacted 1 hour at a temperature of 100 DEG C, prepare terminal hydroxy group and gather
Urethane prepolymer, is cooled to normal temperature.By in 10 mass parts, the 90 mass parts epoxy resin of addition of above-mentioned reactant, addition quality is divided
The 30 mass parts Methanol sodium methanol solutions for 0.01% are counted as catalyst, is reacted 2 hours at 160 DEG C.Room temperature is cooled to, will
The mass parts of above-mentioned reactant 90 are well mixed with 10 mass parts PPGs (GE 204), obtain halogen-free flameproof modified epoxy tree
Fat.
Under vacuum, by 35 mass parts DOPO-HQ (10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phosphorus
Miscellaneous phenanthrene -10- oxides) and 65 mass parts THPAs 160 DEG C react 2 hours.Reaction end is cooled to 80 DEG C.Will be above-mentioned anti-
Answer the mass parts of thing 50 and 49.55 mass parts methyl tetrahydro phthalic anhydrides to mix, be subsequently adding the BDMA (two of relative response product 0.45%
Methylbenzylamine) accelerator, stir, normal temperature is cooled to, it is prepared into halogen-free flameproof modified anhydride curing agent.
Under normal temperature, the mesh activated quartz powder of 70 mass parts 400 and the mesh magnesium hydroxide of 30 mass parts 400 are well 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 at DEG C, vacuumize 1.5 hours, 145 DEG C of mold temperature, vacuum 4.5mbar, 145 DEG C of pressurizes 15 minutes, the demoulding
Draw an insulator (model：8JS-608), then 140 DEG C of solidify afterwards 8 hours.
DSC curve test glass transition temperature is 105 DEG C.- 40 DEG C of -100 DEG C of cold cyclings ftracture now for 5 times without any
As.Bending strength is 8500MPa, and impact strength is 15kJ/m2, flame retardant test reaches 4mm UL 94V0It is fire-retardant.Surface is without light
Greasy dirt shape material.
Embodiment 2：
By 60 mass parts melamines and 40 mass parts 2, the mixing of 4- toluene di-isocyanate(TDI)s is anti-at a temperature of 100 DEG C
Answer 1 hour, prepare amino-terminated polyurethane prepolymer, be cooled to normal temperature.15 mass parts of above-mentioned reactant are added into 85 matter
Amount part epoxy resin in, addition mass fraction be 0.01% 2- phenylimidazoles as catalyst, at 160 DEG C react 2 hours.
1,2%0 two to myristyl glycidol ether (AGE) of above-mentioned reactant weight is added, it is stand-by to be cooled to normal 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 normal temperature is stand-by.Prepare halogen-free flameproof epoxy hardener.
Under normal temperature, the mesh activated quartz powder of 60 mass parts 400 and the mesh aluminium hydrate powder of 40 mass parts 600 are well 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, 145 DEG C of mold temperature, vacuum 4.5mbar, 155 DEG C of pressurizes
15 minutes, the demoulding drew an insulator (model：8JS-608), then 150 DEG C of solidify afterwards 10 hours.
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 are mixed
Close, reacted 1 hour at a temperature of 100 DEG C, prepare end phenolic group polyurethane prepolymer, be cooled to normal temperature.By above-mentioned reaction
The mass parts of thing 10 are added to 95 mass parts epoxy resin, addition mass fraction be 0.01% 2- phenylimidazoles as catalyst,
Reacted 2 hours at 150 DEG C.Room temperature is cooled to, the mass parts of above-mentioned reactant 90 are shunk sweet with 10 mass parts polypropylene glycols two
Oily ether (PPGDGE) is well 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 normal temperature is stand-by.
Under normal temperature, the mesh activated quartz powder of 90 mass parts 400 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, 145 DEG C of mold temperature, vacuum 4.5mbar, 155 DEG C of 15 points of pressurizes
Clock, the demoulding draws an insulator (model：8JS-608), then 150 DEG C of solidify afterwards 10 hours.
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 (10)
1. a kind of preparation method of halogen-free flameproof epoxy systems, it is characterised in that use hydroxyl or the halogen-free flame retardants of amino
Difference modified epoxy and anhydride curing agent；
Wherein, modified epoxy process is：
Under vacuum, according to the hydroxyl or amino in halogen-free flame retardants and the mol ratio of the isocyano of isocyanates
Halogen-free flame retardants and isocyanates containing amino or hydroxyl are mixed in 1, I is reacted at a temperature of 40-120 DEG C, prepared
Prepolymer containing terminal hydroxy group, Amino End Group or end isocyanic acid, is cooled to room temperature；Epoxy resin and catalyst are subsequently adding, control is pre-
Polymers accounts for 7-25% in whole system, is heated to 40 DEG C -170 DEG C, reacts II, is cooled to room temperature, and addition relative response product is
The reactive diluent of 2-25 mass % carries out viscosity regulation, and halogen-free flameproof agent content is not less than 5% in making whole system, obtains nothing
Halogen fire retardant modified epoxy；
During halogen-free flame retardants modified anhydride curing agent：
In parts by mass,
Containing 5-15 parts of amino or hydroxyl halogen-free flame retardants
5-30 parts of solid or liquid acid anhydrides
55-75 parts of liquid acid anhydrides
Under vacuum, halogen-free flame retardants and solid or liquid acid anhydrides containing amino or hydroxyl are mixed, is warming up to 120
DEG C -220 DEG C, III is reacted, be cooled to 60 DEG C -100 DEG C, add liquid acid anhydrides to carry out viscosity regulation, be subsequently adding relative response product
The accelerator of thing 0.05-5 mass %, stirring, cooling obtains halogen-free flameproof anhydride curing agent；
It is 5-85 according to mass ratio by halogen-free flameproof powder and 200-800 mesh silica flour：15-95 mixes, stirring, obtains Halogen
Fire-retardant filler；
By halogen-free flame retardants modified epoxy, halogen-free flame retardants modified anhydride curing agent and halogen-free flameproof filler according to mass ratio
It is 1:1:3.0-4.5 is well mixed under conditions of being 25 DEG C -80 DEG C in temperature, passes through after carrying out vacuum defoamation under vacuum
APG techniques or pouring technology prepare halogen-free flameproof epoxy systems.
2. the preparation method of halogen-free flameproof epoxy systems according to claim 1, it is characterised in that the hydroxyl or ammonia
The halogen-free flame retardants of base is selected from the phosphorous and/or nitrogen compound of hydroxyl or amino.
3. the preparation method of halogen-free flameproof epoxy systems according to claim 1 and 2, it is characterised in that the Halogen resistance
Combustion agent modified epoxy is milky to light yellow solvent-free liquid epoxy resin；The halogen-free flame retardants modified anhydride solidification
Agent is improvement preaceleration milky to light yellow solvent-free acid anhydrides liquid curing-agent；The halogen-free flameproof filler is micro- for white is arrived
Yellow powder.
4. the preparation method of halogen-free flameproof epoxy systems according to claim 1 and 2, it is characterised in that the reaction I's
Reaction time is 30min-2h；
The reaction time of the reaction II is 1-3h；
The reaction time of the reaction III is 2-4h；
Stirred 30-120 minutes after adding accelerator.
5. the preparation method of halogen-free flameproof epoxy systems according to claim 1 and 2, it is characterised in that the Halogen resistance
The combustion agent modified epoxy product data that are are：
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。
6. the preparation method of halogen-free flameproof epoxy systems according to claim 1 and 2, it is characterised in that the Halogen resistance
Fire agent modified anhydride curing agent product data be：
7. the preparation method of halogen-free flameproof epoxy systems according to claim 1 and 2, it is characterised in that the hydroxyl
Halogen-free flame retardants is selected from, but not limited to, the phosphoric acid of N- hexamethylol amino rings phosphonitrile, DOPO-HQ, phosphorus-containing polyol or hydroxyl
One or more in ester oligomer；
The halogen-free flame retardants containing amino is selected from, but not limited to, melamine and its esters, butylated melamine-formaldehyde resin.
8. the preparation method of halogen-free flameproof epoxy systems according to claim 1 and 2, it is characterised in that the solid acid
Acid anhydride is selected from phthalic anhydride, cis-butenedioic anhydride, THPA, one or more in HHPA or trimellitic anhydride；
Liquid acid anhydrides is selected from one or two in methyl tetrahydro phthalic anhydride or methyl hexahydrophthalic anhydride.
9. the preparation method of halogen-free flameproof epoxy systems according to claim 1 and 2, it is characterised in that the activity is dilute
Release agent for PPG, PEPA or vegetable oil or derivatives thereof, epoxy radicals reactive diluent or other contain epoxy radicals
Lowering viscousity compound in one or more；
The catalyst includes but is not limited to methanol solution of sodium methylate, 2- phenylimidazoles solution or imidazoles homologue solution；
The accelerator be tertiary amine and salt, acetyl acetone salt, imidazoles or its homologue, Qi phosphonium salts of triphenylphosphine Huo or
One or more in organic carboxylate；
During the halogen-free flameproof powder is APP, phosphonitrile, red phosphorus, white phosphorus or its coating, magnesium hydroxide or aluminium hydroxide
One or more.
10. the halogen-free flameproof epoxy systems product that preparation method described in any one of claim 1-9 is prepared.
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| CN112143429A (en) * | 2020-10-16 | 2020-12-29 | 冯国旭 | Environment-friendly structural adhesive and preparation method thereof |
| CN113480832A (en) * | 2021-08-03 | 2021-10-08 | 安徽众博新材料有限公司 | 180 ℃ vacuum infusion epoxy resin-based composite material with TG of 170- |
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