CN107337694A - A kind of phosphazene compound with silanol, fire retardant, composition epoxy resin and composite metal substrate - Google Patents
A kind of phosphazene compound with silanol, fire retardant, composition epoxy resin and composite metal substrate Download PDFInfo
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- CN107337694A CN107337694A CN201610290196.1A CN201610290196A CN107337694A CN 107337694 A CN107337694 A CN 107337694A CN 201610290196 A CN201610290196 A CN 201610290196A CN 107337694 A CN107337694 A CN 107337694A
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- Prior art keywords
- epoxy resin
- substituted
- unsubstituted
- combination
- group
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 185
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 185
- -1 phosphazene compound Chemical class 0.000 title claims abstract description 77
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000003063 flame retardant Substances 0.000 title claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 title claims abstract description 15
- 239000000758 substrate Substances 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 33
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 16
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 15
- 229920002627 poly(phosphazenes) Polymers 0.000 claims abstract description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229940106691 bisphenol a Drugs 0.000 claims description 18
- 238000006467 substitution reaction Methods 0.000 claims description 17
- 125000001072 heteroaryl group Chemical group 0.000 claims description 16
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 125000004171 alkoxy aryl group Chemical group 0.000 claims description 14
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 14
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 13
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 13
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 125000004647 alkyl sulfenyl group Chemical group 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 9
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 9
- 150000002118 epoxides Chemical class 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000010426 asphalt Substances 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 125000004446 heteroarylalkyl group Chemical group 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 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 claims description 7
- 229910015900 BF3 Inorganic materials 0.000 claims description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 7
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000005587 carbonate group Chemical group 0.000 claims description 6
- 150000002460 imidazoles Chemical group 0.000 claims description 6
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 6
- 150000003512 tertiary amines Chemical class 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-methyl phenol Natural products CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- 239000011188 CEM-1 Substances 0.000 claims description 4
- 239000011190 CEM-3 Substances 0.000 claims description 4
- 101100257127 Caenorhabditis elegans sma-2 gene Proteins 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- 125000005114 heteroarylalkoxy group Chemical group 0.000 claims description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004843 novolac epoxy resin Substances 0.000 claims description 4
- 125000005429 oxyalkyl group Chemical group 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 239000012745 toughening agent Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- TZVNKGYBJLFHGA-UHFFFAOYSA-N C=O.NC(=O)N.OC1=C(C)C=CC=C1 Chemical compound C=O.NC(=O)N.OC1=C(C)C=CC=C1 TZVNKGYBJLFHGA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000011152 fibreglass Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims 1
- 125000003107 substituted aryl group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 6
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical group CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 241000894007 species Species 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 229910018540 Si C Inorganic materials 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 150000002825 nitriles Chemical group 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UXJHQBVRZUANLK-UHFFFAOYSA-N azanylidyne(dichloro)-$l^{5}-phosphane Chemical compound ClP(Cl)#N UXJHQBVRZUANLK-UHFFFAOYSA-N 0.000 description 3
- 150000001555 benzenes Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- 125000005248 alkyl aryloxy group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000005326 heteroaryloxy alkyl group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- GPRDLRZMTVQCHM-UHFFFAOYSA-L magnesium;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Mg+2] GPRDLRZMTVQCHM-UHFFFAOYSA-L 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PEJQKHLWXHKKGS-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octachloro-1,3,5,7-tetraza-2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraphosphacycloocta-1,3,5,7-tetraene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 PEJQKHLWXHKKGS-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910021295 PNCl2 Inorganic materials 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical group C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XCLIHDJZGPCUBT-UHFFFAOYSA-N dimethylsilanediol Chemical compound C[Si](C)(O)O XCLIHDJZGPCUBT-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- LWIGVRDDANOFTD-UHFFFAOYSA-N hydroxy(dimethyl)silane Chemical class C[SiH](C)O LWIGVRDDANOFTD-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical class C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
- H05K1/056—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an organic insulating layer
-
- 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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0166—Polymeric layer used for special processing, e.g. resist for etching insulating material or photoresist used as a mask during plasma etching
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Engineering & Computer Science (AREA)
- Molecular Biology (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of phosphazene compound with silanol, fire retardant, composition epoxy resin and composite metal substrate.The phosphazene compound has the molecular structure as shown in formula I, and wherein M is the phosphonitrile base of ring three, the phosphonitrile base of ring more than four or one kind in non-annularity polyphosphazene base or at least two combination；R is any reactive end-capping group for meeting its chemical environment；R1And R2It independently is any reactive or non-reacted end-capping group for meeting its chemical environment；Y is any non-reacted end-capping group for meeting its chemical environment；A is the integer more than or equal to zero, and b is the integer more than or equal to 1, a and b sums are 2 times of number of phosphorus atoms in M groups.So that the phosphazene compound has good anti-flammability, its solidfied material has good heat resistance, water resistance, cohesiveness and mechanical performance, electrical property.In addition, said composition, which is applied to composite metal substrate and wiring board, can improve its anti-flammability and dielectricity.
Description
Technical field
The invention belongs to the technical field of fire retardant matter, more particularly to a kind of phosphazene compound with silanol, resistance
Fire agent, composition epoxy resin and composite metal substrate.
Background technology
The electronic products such as mobile phone, computer, video camera, electronic game machine, air-conditioning, refrigerator, television image,
The family expenses such as sound equipment articles for use, office electric equipment products and the various products that use of other field, for safety, all
Need to have different degrees of fire resistance.
Traditional technology is typically using addition aluminium hydroxide hydrate, magnesium hydroxide hydrate into material system
Deng the inorganic fire-retarded material such as the metal hydroxides containing the crystallization water, and bromination pair is added into material system
The method of the higher organic fire-resisting material of the content of halogen such as phenol A, brominated bisphenol a type epoxy resin, makes production
Product reach required fire resistance or grade.In order to improve the resistance of these organic chemicals for containing halogen
Combustion property, such as antimony oxide inorganic fire-retarded material disagreeableness to environment is also usually added into system.
Halogen-containing fire retardant matter can produce no degradability or noxious material (such as two evils of difficult degradation in burning
English class organic halogen chemical substance), pollution environment, influence the mankind and animal health.
For the purpose of environmental protection, people are replaced halogen using the not halogen-containing compound such as phosphorous, nitrogenous
Plain compound is as fire retardant, particularly on electronics, electric, Electric Industrial, using with reactivity
Simple function (there was only an active reactive group in a molecule) flame-retardant composition, such as 9,10- dihydro-9-oxy
Miscellaneous -10- phospho hetero phenanthrenes -10- oxides (hereinafter referred to as DOPO), it is more the derivative compounds using DOPO
Thing, addition or does not add aluminium hydroxide hydrate, magnesium hydroxide hydrate to reach flame retardant effect.
In electronic applications, usually used DOPO and novolac type epoxy resin, o-cresol aldehyde asphalt mixtures modified by epoxy resin
The high costs such as fat, bisphenol-A phenolic type epoxy resin, the product (abbreviation of polyfunctional epoxy resin reaction
DOPO epoxy resin), the epoxide resin material as copper-clad plate purposes.These use DOPO asphalt mixtures modified by epoxy resin
Copper-clad plate manufactured by fat, there is good fire resistance, but cohesiveness, heat resistance, processability etc. are present
The defects of many, be not suitable for manufacture modern communicationses need high multilayer, high reliability, high cohesiveness,
The product of excellent machinability.Simultaneously because cost is higher, it is unfavorable for spreading to the low cost consumption electricity such as mobile phone
The civil goods such as son field.
With the further raising of people's multiple stratification, high reliability request short to electronic product, small, thin, high,
The factor such as the popularization of civilian consumer electronics and increasingly severeer pollution pressure, there is an urgent need to have in market
There is the copper-clad plate material of good anti-flammability, heat resistance, good mechanical performance and dielectric properties.
The content of the invention
In consideration of it, one aspect of the present invention provides a kind of phosphazene compound with silanol, fire retardant, epoxy resin
Composition and composite metal substrate.
To achieve these goals, present invention employs following technical scheme：
On the one hand, the present invention provides a kind of phosphazene compound with silanol, and it has as shown in formula (I)
Molecular structure：
Wherein, M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2Or non-annularity polyphosphazene base M3In
One kind or at least two combination；R is any reactive end-capping group for meeting its chemical environment；R1
And R2It independently is any reactive or non-reacted end-capping group for meeting its chemical environment；Y is satisfaction
Any non-reacted end-capping group of its chemical environment；A is the integer more than or equal to zero, and b is to be more than or wait
In 1 integer, a and b sums are 2 times of number of phosphorus atoms in M groups.
In the present invention, the silane epoxide containing reactive end-capping group R is carried on phosphazenium groups M so that
Reactive end-capping group R can be used as chain extension group, by the reaction between other organic matters come spreading carbon
Chain, the phosphazene compound with silanol can be used for cured epoxy resin, to be used as the resistance of epoxy resin simultaneously
Agent and curing agent are fired, assigns composition epoxy resin excellent anti-flammability, heat resistance and good mechanicalness
Energy and dielectric properties.
In the present invention, it is preferred to R is with-OH ,-CN ,-NH2,-SH ,-COOH ,-CHO or
-CONH2For the reactive group of END CAPPED GROUP.
Preferably, R is selected from-OH ,-CN ,-NH2、-SH、-COOH、-CHO、-CONH2、-R3-OH、
-R4-CN、-R5-NH2、-R6-NH2、-R7-SH、-R8-COOH、-R9- CHO or-R10-CONH2、
In any one；R3、R4、R5、R6、R7、R8、R9And R10It independently is substituted or unsubstituted
Straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted oxyalkyl, substitution
Or unsubstituted oxygen cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substitution or
Unsubstituted aryl alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted alkoxy aryl,
It is substituted or unsubstituted oxyalkyl aryl, substituted or unsubstituted heteroaryl alkyl, substituted or unsubstituted
In miscellaneous alkyl aryl, substituted or unsubstituted alkoxy heteroaryl or substituted or unsubstituted oxyalkyl heteroaryl
Any one.
In the present invention, specifically, R can be-OH ,-CN ,-NH2、-SH、-COOH、-CHO、
-CONH2、-CH2OH、-CH2CH2SH、-CH2CH2COOH、-CH2CH2CHO、
-OCH2CH2CH2OH or-SCH2CH2CN etc..
In the present invention, R1And R2It independently is reactive or non-reacted end-capping group, i.e. R1And R2
It can be each reactive end-capping group, such as can be with-OH ,-CN ,-NH2、-SH、-COOH、
- CHO or-CONH2Isoreactivity group be END CAPPED GROUP group, R1And R2It can also be each non-reaction
Property end-capping group, such as can be alkyl, alkoxy (such as CH3O-)。
Preferably, R1And R2Independently selected from substituted or unsubstituted straight chained alkyl or branched alkyl, substitution
Or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkyl sulfenyl, substitution
Or unsubstituted cycloalkyloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substitution or
Unsubstituted aryl alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted alkoxy aryl,
It is substituted or unsubstituted heteroaryl alkyl, substituted or unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted
Alkoxy heteroaryl, substituted or unsubstituted heteroarylalkoxy, substituted or unsubstituted heteroaryl oxygen alkane
Base ,-OH ,-CN ,-NH2、-SH、-COOH、-CHO、-CONH2、-R3-OH、-R4-CN、
-R5-NH2、-R6-NH2、-R7-SH、-R8-COOH、-R9- CHO or-R10-CONH2In it is any one
Kind；R3、R4、R5、R6、R7、R8、R9And R10Independently be substituted or unsubstituted straight chained alkyl or
It is branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted oxyalkyl, substituted or unsubstituted
Oxygen cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted virtue
Base alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted alkoxy aryl, substitution do not take
The oxyalkyl aryl in generation, substituted or unsubstituted heteroaryl alkyl, substituted or unsubstituted miscellaneous alkyl aryl,
Any one in substituted or unsubstituted alkoxy heteroaryl or substituted or unsubstituted oxyalkyl heteroaryl.
Specifically, R1And R2- OH ,-CN ,-NH can independently be2、-SH、-COOH、-CHO、
-CONH2、-CH2OH、-CH2CH2SH、-CH2CH2COOH、-CH2CH2CHO、
-OCH2CH2CH2OH、-SCH2CH2CN、-CH3、-OCH3Or-OCH2- Ph (Ph represents phenyl)
Deng.
Preferably, Y be substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substitution or
Unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroaryl, substitution
Or unsubstituted alkyl sulfenyl, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group,
Any one in substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group；The alcoxyl
Base, cycloalkyloxy, aryloxy group, alkoxy aryl, heteroaryl, carbonate group, sulfonate group or phosphonate ester
The substituent of base independently be straight or branched alkyl, alkoxy, aryloxy group, alkoxy aryl, heteroaryl,
Any one in alkyl sulfenyl, carboxylic acid ester groups, carbonate group, sulfonate group or phosphonate group or at least two
Kind combination, the substituent do not contain reactive end-capping group, for example, the substituent for do not contain OH,
-CN、-NH2、-SH、-COOH、-CHO、-CONH2Isoreactivity group；Illustrated with instantiation,
When substituent is carboxylic acid ester groups, it is impossible to be the formic acid ester group that one end still carries carboxyl.The combination refers to Y
The non-reacted end-capping group described at least two can be included, i.e., is connected with two on the phosphorus atoms in M
Individual or more than two non-reacted end-capping groups, such as when being connected with an alkane on the phosphorus atoms in M
Epoxide and an alkyl sulfenyl, now a value regard as 2, and for example connected when on the phosphorus atoms in M
There are two alkoxies and an alkyl sulfenyl, now a value regards as 3, by that analogy.
For example, specifically, Y can be CH3O-、CH3CH2O-、CH3S-、CH3CH2CH2S-、
CH3In COO- or PhO- (Ph represents phenyl) any one or at least two combination.
In the present invention, substituted or unsubstituted straight chained alkyl or branched alkyl are preferably substituted or unsubstituted
C1~C12 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11) straight chain
Alkyl or branched alkyl, further preferred C1~C8 straight chained alkyls or branched alkyl, when carbon number is 1
When be methyl, when carbon number is 2, as ethyl.
Substituted or unsubstituted cycloalkyl be preferably substituted or unsubstituted C3~C12 (such as C4, C5,
C6, C7, C8, C9, C10 or C11) cycloalkyl.
Substituted or unsubstituted alkoxy be preferably substituted or unsubstituted C1~C12 (such as C2, C3,
C4, C5, C6, C7, C8, C9, C10 or C11) alkoxy.
Substituted or unsubstituted alkyl sulfenyl be preferably C1~C10 (such as C2, C3, C4, C5, C6,
C7, C8 or C9) alkoxy.
Substituted or unsubstituted cycloalkyloxy be preferably substituted or unsubstituted C3~C12 (such as C4, C5,
C6, C7, C8, C9, C10 or C11) cycloalkyloxy.
Substituted or unsubstituted aryl be preferably phenyl, benzyl, naphthyl, OrDeng.
Substituted or unsubstituted heteroaryl is five yuan or six membered heteroaryl, and the heteroaryl is to contain hetero atom
The aromatic radical of (such as O, S, N etc.), preferably substituted or unsubstituted furyl or pyridine radicals.
Substituted or unsubstituted aryl alkyl is preferably C7-C13 (such as C8, C9, C10, C11 or C12)
Aryl alkyl.
Substituted or unsubstituted alkylaryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12)
Alkylaryl.
Substituted or unsubstituted alkoxy aryl be preferably C7-C13 (such as C8, C9, C10, C11 or
C12) alkoxy aryl.
Substituted or unsubstituted heteroaryl alkyl be preferably C7-C13 (such as C8, C9, C10, C11 or
C12) heteroaryl alkyl.
Substituted or unsubstituted miscellaneous alkyl aryl be preferably C7-C13 (such as C8, C9, C10, C11 or
C12) miscellaneous alkyl aryl.
Substituted or unsubstituted alkoxy heteroaryl is C7-C13 (such as C8, C9, C10, C11 or C12)
Alkoxy heteroaryl.
Substituted or unsubstituted heteroarylalkoxy is C7-C13 (such as C8, C9, C10, C11 or C12)
Heteroarylalkoxy.
Substituted or unsubstituted heteroaryl oxyalkyl is C7-C13 (such as C8, C9, C10, C11 or C12)
Heteroaryl oxyalkyl.
Substituted or unsubstituted alkyl sulfenyl be C1-C8 (such as C1, C2, C3, C4, C5, C6,
C7 or C8) alkyl sulfenyl.
Substituted or unsubstituted cycloalkyloxy is C3-C8 (such as C4, C5, C6, C7 or C8) cycloalkanes
Epoxide.
Substituted or unsubstituted aralkoxy is C7-C12 (such as C8, C9, C10 or C11) aralkyl oxygen
Base.
Substituted or unsubstituted alkyl-aryloxy is C7-C12 (such as C8, C9, C10 or C11) alkyl
Aryloxy group.
Term " substituted " used in the present invention refers to any one or more hydrogen atoms on specified atom
Substituted by the substituent selected from designated groups, condition is that the specified atom is no more than normal valency, and is substituted
Result be to produce stable compound.When substituent is oxo group or ketone group (i.e.=O), then
2 hydrogen atoms on atom are substituted.Ketone substituent is not present on aromatic rings." stable compound "
It is to refer to that sufficiently strong separation to effective purity and is configured to effective chemical combination from reactant mixture strongly
Thing.
In the present invention, a can be the integer more than or equal to zero, when a is zero, formula (I) of the present invention
The phosphazene compound with silanol do not contain Y group, b is the integer more than or equal to 1, i.e., institute of the present invention
State the phosphazene compound with silanol and contain silane epoxide shown at least one formula (I), and a and b
Sum is 2 times of number of phosphorus atoms in M groups.
In the structural formula I of the present invention, a is the integer more than or equal to 0, and b is the integer more than or equal to 1,
Such as a can be but be not limited to 0,1,2,3,4,5,6,7,8,9 or 10, b can be but not
It is limited to 1,2,3,4,5,6,7,8,9 or 10, and 2 times of number of phosphorus atoms on a+b=M groups,
Ensure that phosphorus atoms reach the saturation state that chemical valence is pentavalent on M.
In the present invention, M1、M2And M3Mass percent sum is 100%.
Preferably, M includes at least 50wt%M1, at most 48wt%M2And at most 48wt%M3。
In the present invention, M1Content is at least 50wt%, i.e. M1Content can be 50wt~100wt%,
M1For bulk composition.Work as M1When content is 100wt%, then M is not contained2And M3.Typical case of the invention but
Nonrestrictive M1Content can be 50wt%, 51wt%, 55wt%, 58wt%, 60wt%,
65wt%, 70wt%, 74wt%, 75wt%, 80wt%, 85wt%, 90wt%, 92wt%, 95wt%,
98wt% or 100wt%.
In the present invention, M2Content is at most 48wt%, that is, is referred to, M2Content can be 0~48wt%.When
M2When content is 0wt%, that is, refers to, do not contain M2.The typical but non-limiting M of the present invention2Content can be with
For 0wt%, 2wt%, 5wt%, 8wt%, 11wt%, 14wt%, 17wt%, 20wt%, 23wt%,
26wt%, 29wt%, 32wt%, 35wt%, 38wt%, 42wt%, 45wt% or 48wt%.
In the present invention, M3Content is at most 48wt%, that is, is referred to, M3Content can be 0~48wt%.When
M3When content is 0wt%, that is, refers to, do not contain M3.The typical but non-limiting M of the present invention3Content can be with
For 0wt%, 2wt%, 5wt%, 8wt%, 11wt%, 14wt%, 17wt%, 20wt%, 23wt%,
26wt%, 29wt%, 32wt%, 35wt%, 38wt%, 42wt%, 45wt% or 48wt%.
In the present invention, if M1Content is less than 50wt%, or M2More than 48wt%, then with asphalt mixtures modified by epoxy resin
The reacted product of fat can damage heat resistance, water resistance and mechanical performance in use.If M3Content
More than 48%, then would be possible to cause because viscosity is excessive in use with the reacted product of epoxy resin
It is inconvenient for use, and its performance the bad result such as is suffered damage because molecular weight is excessive.
In the present invention, it is preferred to M1、M2And M3Structure is respectively：
M1Structure is：
M2Structure is：
Wherein, x is more than or equal to 4.
M3Structure is：
Wherein, y is more than or equal to 3.
It should hand over, in M1And M2In the expression of structural formula, there is symbolOnly
Only it is that one kind of " ring-type " structure is illustrated.M1、M2And M3InMiddle P atoms
The key of upper connection only represents substituent substitution in three and occurred on P atoms, is not to be construed as the table of methyl
Show.
In the flame-retardant compound of the present invention, it should be understood that the group being connected with M is to be connected to M
Phosphorus atoms on, i.e. M1、M2And M3The side base on phosphorus atoms in structure.Further illustrate,
M1、M2And M3Two singly-bounds occurred in structure on P atoms are not to be construed as two methyl, and this two
Individual singly-bound is merely representative of M1、M2And M3Side base is connected by P atoms.
Preferably, the phosphazene compound with silanol is one kind or extremely in the compound with following structure
Few two kinds combination：
OrWherein M is the phosphonitrile base of ring three.
Second aspect, the present invention provides a kind of preparation method of the phosphazene compound with silanol, by the party
Phosphazene compound with silanol prepared by method has good flame-retardance and heat resistance.
The above-mentioned phosphazene compound with silanol can be prepared using method well known in the art, such as phosphonitrile chloride
Have solvent or it is solvent-free under the conditions of, use with the metal chlorides such as zinc chloride, magnesium chloride, aluminium chloride,
Boron trifluoride and its complex compound etc. are catalyst, with the silanol containing reactivity end-capping group or its metal salt
(or other nucleopilic reagents for being free of reactivity end-capping group can also be included, such as alcohol or its metal
Salt) etc. in the basic conditions reaction obtain.These catalyst can one or more be used in mixed way, the present invention
In have no special regulation.Here " phosphonitrile chloride ", which refers to M groups in formula (I) and be connected with Cl, forms
Compound.As for phosphonitrile chloride known solvent, catalyst can be used to be closed in known reaction scheme
Into can also be synthesized phosphonitrilic chloride compound according to known methods using phosphorus pentachloride and ammonium chloride
Afterwards, handle purification by physical method or do not purify direct manufacture, its chemical equation is PCl5+NH4Cl
→1/n(NPCl2) n+4HCl, it is mainly tripolymer (PNCl in the reaction product2)3(that is, chlordene ring three
Phosphonitrile) and the tetramer (PNCl2)4, reaction product can be obtained pure by slow distillation in 60 DEG C of vacuum again
Hexachlorocyclotriph,sphazene.The phosphonitrile of chloro ring more than four and chloro non-annularity polyphosphazene can also be by prior art systems
It is standby to obtain.
The third aspect, the present invention provide a kind of fire retardant of epoxy resin, and the fire retardant includes above-mentioned band silicon
The phosphazene compound of alcohol.
Fourth aspect, the present invention provide it is a kind of have good flame-retardance, heat resistance, good mechanical performance and
The composition epoxy resin of dielectric properties.
A kind of composition epoxy resin, comprising epoxy resin, and the fire retardant as described in the third aspect.
Preferably, the epoxy resin is two functional epoxy resins or trifunctional above epoxy resin.
Preferably, two functional epoxy resins are liquid bisphenol A types epoxy resin, liquid bisphenol F types
Epoxy resin, solid-state bisphenol A type epoxy resin fat, solid-state bisphenol f type epoxy resin fat and bisphenol S type epoxy
One kind or at least two combination in resin or biphenyl type epoxy resin.
Preferably, the epoxy resin more than trifunctional is phenol aldehyde type epoxy resin, o-cresol aldehyde epoxy
One kind or at least two group of resin or bisphenol-A phenolic epoxy resin or acyclic isoprenoid type epoxy resin
Close.
Herein, it will be readily appreciated by those skilled in the art that when being necessary certainly, alicyclic ring can also be used
The relatively low asphalt mixtures modified by epoxy resin of ratio of viscosities such as formula epoxy resin, chain type aliphatic type epoxy resin or ester formula epoxy resin
Fat, these epoxy resin can be used alone can also two or more be used together, the present invention to this
Special regulation is had no, the present invention is also not specially provided to the amount of these epoxy resin proportioning, ensures to reach
Purpose thing is obtained on the premise of safe and environment-friendly and required performance.
Preferably, the composition epoxy resin is also included by the phosphazene compound and asphalt mixtures modified by epoxy resin with silanol
The phosphonitrile epoxy resin that fat is generated by condensation reaction, and fire-retarded epoxy resin.
Preferably, the fire-retarded epoxy resin content of halogen is not higher than 0.2%.
Preferably, the fire-retarded epoxy resin be DOPO types epoxy resin, phosphorus-containing phenolic aldehyde epoxy resin or
One kind or at least two combination in nitrogenous novolac epoxy resin containing phosphorous.
Preferably, the fire-retarded epoxy resin be phosphorous type epoxy resin, it is nitrogenous type epoxy resin, nitrogenous
Phosphorous type epoxy resin or silicon-contained type epoxy resin or one kind in sulfur-type epoxy resin or at least two
Combination.
Preferably, the composition epoxy resin also includes curing accelerator.
The addition of curing accelerator is for rapid curing.The present invention is to used curing accelerator without special
Regulation, using common epoxy resin curing accelerator, such as imidazoles, triphenylphosphine and its spread out
One kind or at least two group in biological species, tertiary amines, quaternary ammonium salts or boron trifluoride and its derivative species
Close, these accelerator both can be used alone, can also two or more be used in mixed way.
Preferably, the dosage of the curing accelerator is account for epoxy resin gross mass 0.001~2.5%, is entered
One step is preferably 0.03~1.2%.
Preferably, the composition epoxy resin also includes solvent.
For the type and quantity using solvent, the present invention has no special regulation, for example, can be acetone,
Butanone, DMF, DMAC, ethanol, methanol, cyclohexanone, 1,4- dioxane, petroleum solvent, toluene,
The organic solvents such as dimethylbenzene, dichloromethane, dimethyl carbonate, ensure safe and environment-friendly and institute to reach
Purpose thing is obtained on the premise of the performance needed.Preferably, had from each composition such as such as butanone good
Dissolubility, the organic solvent that toxicity is not strong, boiling point is more moderate；If containing double in epoxy resin ingredient
The material that the crystallinity such as cyanamide not readily dissolve, part or all of nitrogenous class such as DMF, DMAC can be used
Deng organic solvent.It is understood that solvent can improve volatilization by heating in solidification process
Speed.
Preferably, the composition epoxy resin also includes supporting material and filler；
Preferably, the supporting material is one kind or at least two in glass fibre, carbon fiber and polyester fiber
Kind, supporting material can improve the mechanical property of final solidfied material.
Filler is to increase its some function, property or reduce cost, it is preferable that the filler is dioxy
One in SiClx, diatomite, kaolin, calcium carbonate, mica, titanium dioxide, magnesium hydroxide, aluminium hydroxide
Kind or at least two；These inorganic fillers can be used alone, can also two kinds or it is several be used in mixed way, it is excellent
Selection of land, the dosage of the filler are no more than 500phr for epoxy resin gross mass.
Preferably, the composition epoxy resin also includes auxiliary agent, the auxiliary agent be defoamer, coupling agent,
One kind in toughener and levelling agent or at least two.The present invention is not done to the species and addition of adding auxiliary agent
Special regulation, can be as needed, is defined by the safe and environment-friendly purpose thing that obtains.
5th aspect, the present invention provide it is a kind of have good flame-retardance, heat resistance, good mechanical performance and
The phosphonitrile epoxy resin with silanol of dielectric properties.
A kind of phosphonitrile epoxy resin with silanol, it is by non-halogen epoxy resin and the phosphorus with silanol as described above
Nitrile compound is generated under conditions of the epoxy radicals surplus of epoxy resin by reacting obtained epoxy resin
Thing.
" epoxy radicals of epoxy resin is superfluous " is with the epoxide equivalent of epoxy resin product in below 3585g/eq
It is defined, more preferably in below 1520g/eq.
Preferably, the reaction is carried out under conditions of catalyst without catalyst or have.
Preferably, the catalyst is imidazoles, triphenylphosphine and its derivative species, tertiary amines and quaternary amine
A kind of exclusive use or at least two in class catalyst are used in mixed way.
Preferably, the dosage of the catalyst be relative to 0.01~2.5% of the phosphazene compound with silanol,
More preferably 0.02%~0.5%.
Preferably, the temperature of the reaction is 40~250 DEG C, more preferably 60~180 DEG C.
Preferably, the reaction is solvent-free or have and carry out under conditions of solvent, the solvent be ketones solvent,
Aromatic solvents, chlorinated solvents, ether solvent, ether alcohols solvent, alcohols solvent or petroleum solvent naphtha
In one kind or at least two combination.
Preferably, the dosage of the solvent is that the phosphonitrile epoxy resin solid content with silanol can be made to be 5~100%
Dosage, more preferably make the phosphonitrile epoxy resin solid content with silanol be 20~100% dosage.
Preferably, the non-halogen epoxy resin is asphalt mixtures modified by epoxy resin more than two functional epoxy resins or trifunctional
Fat.
Preferably, the epoxy resin of two function is liquid bisphenol A types epoxy resin, liquid bisphenol F
Type epoxy resin, solid-state bisphenol A type epoxy resin fat, solid-state bisphenol f type epoxy resin fat, bisphenol S type ring
One kind or at least two combination in oxygen tree fat or biphenyl type epoxy resin.
Preferably, the epoxy resin more than trifunctional is phenol aldehyde type epoxy resin, o-cresol aldehyde epoxy
One kind or at least two group of resin, bisphenol-A phenolic epoxy resin or acyclic isoprenoid type epoxy resin
Close.
6th aspect, the present invention provide it is a kind of have good flame-retardance, heat resistance, good mechanical performance and
The fire-retardant combination of dielectric properties.
A kind of fire-retardant combination, include the phosphonitrile epoxy resin with silanol described above.
Preferably, the fire-retardant combination is also comprising flame retardant epoxy fat resin, curing agent, auxiliary agent, solidification
In accelerator or halogen-free flame-retardance filler any one or at least two combination.
Preferably, the fire-retarded epoxy resin be DOPO types epoxy resin, phosphorus-containing phenolic aldehyde epoxy resin or
One kind or at least two combination in nitrogenous novolac epoxy resin containing phosphorous.
Preferably, the fire-retarded epoxy resin be phosphorous type epoxy resin, it is nitrogenous type epoxy resin, nitrogenous
Phosphorous type epoxy resin, silicon-contained type epoxy resin or one kind or at least two group in sulfur-type epoxy resin
Close.
Preferably, the curing agent be more phenol-based compounds, amine compound, benzoxazine colophony, acid anhydrides,
Polyacid or one kind in boron trifluoride and its complex compound or at least two combination.
Preferably, the amine compound is fatty amine and/or aromatic amine.；
Preferably, the fatty amine is dicyandiamide, diethyl triamine, MDA or diaminourea two
One kind or at least two combination in benzene sulfone.
Preferably, more phenol-based compounds be bisphenol-A, Bisphenol F, bisphenol S, linear phenolic resin,
One kind or at least two combination in o-cresol urea formaldehyde or bisphenol A phenolic resin.
Preferably, the dosage of the curing agent and the equivalent proportion of epoxy resin 0.4~1.5.
Preferably, the curing accelerator is imidazoles, triphenylphosphine and its derivative species, tertiary amines, season
One kind or at least two combination in amine salt or boron trifluoride and its derivative species.
Preferably, the dosage of the curing accelerator is account for epoxy resin gross mass 0.001~2.5%, is entered
One step is preferably 0.03~1.2%.
Preferably, the filler is silica, kaolin, calcium carbonate, mica, titanium dioxide, hydroxide
One kind or at least two combination in magnesium or aluminium hydroxide.
Preferably, the dosage of the filler is below the 500phr of epoxy resin gross mass.
Preferably, the auxiliary agent is one kind or at least two in defoamer, coupling agent, toughener or levelling agent
The combination of kind.
7th aspect, the present invention provide a kind of pre-impregnated sheet, and it is by composition epoxy resin described above or fire-retardant
Composition is impregnated with or is coated on base material and forms.
Preferably, the base material is fiberglass substrate, polyester base material, polyimide base material, ceramic base material
Or carbon fiber base material.Here, the concrete technology condition of its impregnation or coating is not particularly limited." pre-impregnated sheet "
Also " bonding sheet " being well known to those skilled in the art.
Eighth aspect, the present invention provide a kind of composite metal substrate, and it includes at least one as described above in advance
Plate is soaked, by carrying out surface metal-clad successively, overlapping, pressing forms.Here, surface metal-clad
Material is the alloy of aluminium, copper, iron and its any combination.The instantiation of composite metal substrate has CEM-1
Copper-clad plate, CEM-3 copper-clad plates, FR-4 copper-clad plates, FR-5 copper-clad plates, CEM-1 aluminium bases, CEM-3
Aluminium base, FR-4 aluminium bases or FR-5 aluminium bases.
9th aspect, the present invention provides a kind of wiring board, in the Surface Machining line of above-mentioned composite metal substrate
Road forms.
The raw material of flame-retardant composition or composition epoxy resin described above is by being solidificated in composition metal base
Formed on plate with good flame-retardance can coating, the anti-flammability of wiring board, heat resistance, good can be improved
Mechanical performance and low-dielectric energy.
In the present invention, term " ××× base or group ", which refers in ××× molecular structure of compounds, sloughs one
Remaining part after individual or multiple hydrogen atoms or other atoms or atomic group.
Relative to prior art, the invention has the advantages that：
The present invention is by using the phosphazene compound containing the siloxane structure with reactivity end-capping group
The phosphazene compound with silanol is formed, makes the phosphazene compound that there is good anti-flammability, its solidfied material
With good heat resistance, water resistance, cohesiveness and mechanical performance and dielectric properties, be it is a kind of also have compared with
Big economy and the fire retardant matter of environmentally friendly friendly.The Tg of the copper-clad plate obtained using the phosphazene compound
Can reach 157 DEG C and more than, T- peel strengths can reach 2.1kg/mm2More than and, interlaminar strength can
Reach 1.87kg/mm2More than and, saturated water absorption can reach less than 0.24%, and heat decomposition temperature can reach
401 DEG C and more than, bending strength can reach 12.4kg/mm2More than and, flammability (UL-90) reaches V-0
Rank.
Embodiment
Technical scheme is further illustrated with reference to embodiment.
Embodiment 1
Hexachlorocyclotriph,sphazene 1mol, acetone are put into three mouthfuls of 2000ml glass reactors with agitating device
250ml, sodium methoxide 3mol, stir, lead to nitrogen, while being warming up to 40 DEG C, use 60min
20% sodium hydroxide solution 300g is instilled, 45 DEG C of temperature is kept, 10 hours of stirring reaction, then adds
Dimethylsilanediol 3mol, continues stirring reaction 5 hours.After reaction, system is removed with the method for physics
Middle inorganic constituents and moisture, solvent in system is distilled, obtain the phosphazene compound 1mol with silanol, will
This product is named as A.
Proton nmr spectra sign is carried out to obtained compound A, it is as a result as follows：
1H NMR(CDCl3,500MHz):δ 5.0 (m, 3H, the hydrogen on hydroxyl), 3.42 (s, 9H,
OCH 3),0.2(m,18H,Si-CH 3)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, phosphorus
P-N 874cm in nitrile skeleton-1, the absworption peak 2995cm of methyl ether-1, P-O-C key absworption peaks 1035cm-1,
Ortho position substituted benzene ring 750cm-1, silicone hydroxyl absworption peak 3447cm-1。
Using above-mentioned phosphazene compound A 85g as fire retardant, the line style that phenolic hydroxyl equivalent is 105g/eq is added
Phenolic resin curative 105g, the o-cresol formaldehyde epoxy resin 200g that epoxide equivalent is 200g/eq is added, Gu
Change accelerator 2-methylimidazole 0.2g, prepare composition epoxy resin.Then the composition epoxy resin is used
The standard copper-clad plate sample for meeting the standards such as national standard, UL, life are made according to general copper-clad plate production process
Entitled a copper-clad plates, test the performance of a copper-clad plates, and its result represents in table -1.
Embodiment 2
Hexachlorocyclotriph,sphazene 1mol, acetone are put into three mouthfuls of 2000ml glass reactors with agitating device
250ml, sodium methoxide 1mol, stir, lead to nitrogen, while being warming up to 40 DEG C, use 60min
20% sodium hydroxide solution 300g is instilled, 45 DEG C of temperature is kept, 6 hours of stirring reaction, then adds
Trimethyl silanol 5mol, continues stirring reaction 8 hours.After reaction, with the method removal system of physics
Inorganic constituents and moisture, solvent in system is distilled, the phosphazene compound 1mol with silanol is obtained, by this
Product is named as B.
Proton nmr spectra sign is carried out to obtained compound B, it is as a result as follows：
1H NMR(CDCl3,500MHz):δ3.42(s,3H,OCH 3),0.1(m,45H,Si-CH 3)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, phosphorus
P-N 874cm in nitrile skeleton-1, the absworption peak 2995cm of methyl ether-1, P-O-C key absworption peaks 1035cm-1,
Ortho position substituted benzene ring 750cm-1, Si-CH3Characteristic absorption peak：l261cm-1Place and 795cm-1。
Using above-mentioned phosphazene compound B 70g as fire retardant, the line style that phenolic hydroxyl equivalent is 105g/eq is added
Phenolic resin curative 105g, the o-cresol formaldehyde epoxy resin 200g that epoxide equivalent is 200g/eq is added, Gu
Change accelerator 2-methylimidazole 0.2g, prepare composition epoxy resin.Then the composition epoxy resin is used
The standard copper-clad plate sample for meeting the standards such as national standard, UL, life are made according to general copper-clad plate production process
Entitled b copper-clad plates, test the performance of b copper-clad plates, and its result represents in table -1.
Embodiment 3
Hexachlorocyclotriph,sphazene 1mol, acetone are put into three mouthfuls of 2000ml glass reactors with agitating device
250ml, sodium methoxide 3mol, stir, lead to nitrogen, while being warming up to 40 DEG C, use 60min
20% sodium hydroxide solution 300g is instilled, 45 DEG C of temperature is kept, 6 hours of stirring reaction, then adds
Dimethyl phonyl silanol 3mol, continues stirring reaction 8 hours.After reaction, with the method removing body of physics
Inorganic constituents and moisture in system, distill solvent in system, obtain the phosphazene compound 1mol with silanol,
This product is named as C.
Proton nmr spectra sign is carried out to obtained compound C, it is as a result as follows：
1H NMR(CDCl3,500MHz):δ 7.3 (m, 15H, benzene ring hydrogen), 3.42 (s, 9H,
OCH 3),0.7(m,18H,Si-CH 3)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, phosphorus
P-N 874cm in nitrile skeleton-1, the absworption peak 2995cm of methyl ether-1, P-O-C key absworption peaks 1035cm-1,
Monosubstituted phenyl ring 700cm-1And 750cm-1, Si-CH3Characteristic absorption peak：l261cm-1Place and 795cm-1。
Using above-mentioned phosphazene compound C 115g as fire retardant, the line that phenolic hydroxyl equivalent is 105g/eq is added
Type phenolic resin curative 105g, the o-cresol formaldehyde epoxy resin 200g that epoxide equivalent is 200g/eq is added,
Curing accelerator 2-methylimidazole 0.2g, prepares composition epoxy resin.Then the epoxy composite is used
The standard copper-clad plate sample for meeting the standards such as national standard, UL is made according to general copper-clad plate production process for thing,
C copper-clad plates are named as, test the performance of c copper-clad plates, its result represents in table -1.
Embodiment 4
Hexachlorocyclotriph,sphazene 1mol, acetone are put into three mouthfuls of 2000ml glass reactors with agitating device
250ml, caustic alcohol 3mol, stir, lead to nitrogen, while being warming up to 40 DEG C, use 60min
20% sodium hydroxide solution 300g is instilled, 45 DEG C of temperature is kept, 6 hours of stirring reaction, then adds
(4- methoxyphenyls) dimethyl silanols 3mol, continues stirring reaction 8 hours.After reaction, with physics
Inorganic constituents and moisture in method removal system, distill solvent in system, obtain the phosphonitrile chemical combination with silanol
Thing 1mol, this product is named as D.
Proton nmr spectra sign is carried out to obtained compound D, it is as a result as follows：
1H NMR(CDCl3,500MHz):δ 6.8-7.2 (m, 12H, benzene ring hydrogen), 3.73 (m, 9H,
OCH 3),3.6(m,6H,OCH 2CH3),1.2(m,9H,OCH2CH 3),0.7(m,18H,Si-CH 3)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, phosphorus
P-N 874cm in nitrile skeleton-1, the absworption peak 2995cm of methyl ether-1, P-O-C key absworption peaks 1035cm-1,
Align substituted benzene ring 827cm-1, Si-CH3Characteristic absorption peak：l261cm-1Place and 795cm-1。
Using above-mentioned phosphazene compound D 140g as fire retardant, the line that phenolic hydroxyl equivalent is 105g/eq is added
Type phenolic resin curative 105g, the o-cresol formaldehyde epoxy resin 200g that epoxide equivalent is 200g/eq is added,
Curing accelerator 2-methylimidazole 0.2g, prepares composition epoxy resin.Then the epoxy composite is used
The standard copper-clad plate sample for meeting the standards such as national standard, UL is made according to general copper-clad plate production process for thing,
D copper-clad plates are named as, test the performance of d copper-clad plates, its result represents in table -1.
Comparative example 1
Epoxide equivalent is 200g/eq o-cresol formaldehyde epoxy resin 200g, adds phenolic hydroxyl equivalent and is
105g/eq linear phenol-aldehyde resin curing agent 105g and as fire retardant hexaphenoxycyclotriphosphazene 70g with
And 0.2g 2-methylimidazole, prepare composition epoxy resin.Then pressed using the composition epoxy resin
The standard copper-clad plate sample e for meeting the standards such as national standard, UL is made according to general copper-clad plate production process, covers
Copper e properties represent in table -1.
Comparative example 2
Epoxide equivalent is 200g/eq o-cresol formaldehyde epoxy resin 200g, and adding, there is formula (1) such as to tie
The resin compound 220g of structure, ester equivalent are 220g/eq and the hexaphenoxycyclotriphosphazene as fire retardant
70g and 0.2g pyridine azoles, prepares composition epoxy resin.Then using the composition epoxy resin according to
The standard copper-clad plate sample f for meeting the standards such as national standard, UL is made in general copper-clad plate production process.Cover copper f
Properties represented in table -1.
Embodiment and the test result of comparative example are as shown in following table -1 (in view of specific method of testing has been this area
Known to technical staff, method is no longer described in detail at this).
Table -1
The test data of above table, show the phosphazene compound with silanol and its derivative of the invention when use
When in epoxy resin solidifying system and other systems, there is good anti-flammability, its solidfied material has good
Heat resistance, water resistance, cohesiveness, mechanical performance and electrical property.The fire-retardant compound of the present invention belongs to
The environmental protection of the novel environmental friendly for the energy-saving and emission-reducing that low cost, raw material sources are abundant, properties are good
Type anti-flammability material.
Applicant states that the present invention illustrates the phosphonitrile chemical combination with silanol of the present invention by above-described embodiment
Thing, curing agent and its application, but the invention is not limited in above-described embodiment, that is, do not mean that the present invention must
Above-described embodiment, which must be relied on, to be implemented.Person of ordinary skill in the field is it will be clearly understood that to the present invention's
Any improvement, addition, the choosing of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention
Select, within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of phosphazene compound with silanol, it is characterised in that it has point as shown in formula (I)
Minor structure：
Wherein, M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2Or non-annularity polyphosphazene base M3In
One kind or at least two combination；R is any reactive end-capping group for meeting its chemical environment；R1
And R2It independently is any reactive or non-reacted end-capping group for meeting its chemical environment；Y is satisfaction
Any non-reacted end-capping group of its chemical environment；A is the integer more than or equal to zero, and b is to be more than or wait
In 1 integer, a and b sums are 2 times of number of phosphorus atoms in M groups.
2. the phosphazene compound with silanol as claimed in claim 1, it is characterised in that R be with-OH,
-CN、-NH2,-SH ,-COOH ,-CHO or-CONH2For the reactive group of END CAPPED GROUP；
Preferably, R is selected from-OH ,-CN ,-NH2、-SH、-COOH、-CHO、-CONH2、-R3-OH、
-R4-CN、-R5-NH2、-R6-NH2、-R7-SH、-R8-COOH、-R9- CHO or-R10-CONH2In
Any one；R3、R4、R5、R6、R7、R8、R9And R10It independently is substituted or unsubstituted straight
Alkyl group or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted oxyalkyl, substitution or
Unsubstituted oxygen cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substitution or not
Substituted aryl alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted alkoxy aryl, take
Generation or unsubstituted oxyalkyl aryl, substituted or unsubstituted heteroaryl alkyl, substituted or unsubstituted alkane
In base heteroaryl, substituted or unsubstituted alkoxy heteroaryl or substituted or unsubstituted oxyalkyl heteroaryl
Any one；
Preferably, R1And R2Independently selected from substituted or unsubstituted straight chained alkyl or branched alkyl, substitution
Or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkyl sulfenyl, substitution
Or unsubstituted cycloalkyloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substitution or
Unsubstituted aryl alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted alkoxy aryl,
It is substituted or unsubstituted heteroaryl alkyl, substituted or unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted
Alkoxy heteroaryl, substituted or unsubstituted heteroarylalkoxy, substituted or unsubstituted heteroaryl oxygen alkane
Base ,-OH ,-CN ,-NH2、-SH、-COOH、-CHO、-CONH2、-R3-OH、-R4-CN、
-R5-NH2、-R6-NH2、-R7-SH、-R8-COOH、-R9- CHO or-R10-CONH2In it is any one
Kind；R3、R4、R5、R6、R7、R8、R9And R10Independently be substituted or unsubstituted straight chained alkyl or
It is branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted oxyalkyl, substituted or unsubstituted
Oxygen cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted virtue
Base alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted alkoxy aryl, substitution do not take
The oxyalkyl aryl in generation, substituted or unsubstituted heteroaryl alkyl, substituted or unsubstituted miscellaneous alkyl aryl,
Any one in substituted or unsubstituted alkoxy heteroaryl or substituted or unsubstituted oxyalkyl heteroaryl；
Preferably, Y be substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substitution or
Unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroaryl, substitution
Or unsubstituted alkyl sulfenyl, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group,
Any one in substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group；The alcoxyl
Base, cycloalkyloxy, aryloxy group, alkoxy aryl, heteroaryl, carbonate group, sulfonate group or phosphonate ester
The substituent of base independently be straight or branched alkyl, alkoxy, aryloxy group, alkoxy aryl, heteroaryl,
Any one in alkyl sulfenyl, carboxylic acid ester groups, carbonate group, sulfonate group or phosphonate group or at least two
The combination of kind, the substituent do not contain reactive end-capping group；
Preferably, M1Structure is：
M2Structure is：
Wherein, x is more than or equal to 4.
M3Structure is：
Wherein, y is more than or equal to 3；
Preferably, M includes at least 50wt%M1, at most 48wt%M2And at most 48wt%M3。
3. the phosphazene compound with silanol as claimed in claim 1 or 2, it is characterised in that the band
The phosphazene compound of silanol is one kind or at least two combination in the compound with following structure：
Wherein M is the phosphonitrile base of ring three.
4. a kind of fire retardant of epoxy resin, it is characterised in that the fire retardant includes such as claim 1-3
One of the phosphazene compound with silanol.
5. a kind of composition epoxy resin, it is characterised in that comprising epoxy resin, and such as claim 4
Described fire retardant；
Preferably, the epoxy resin is two functional epoxy resins or trifunctional above epoxy resin；
Preferably, two functional epoxy resins are liquid bisphenol A types epoxy resin, liquid bisphenol F types
Epoxy resin, solid-state bisphenol A type epoxy resin fat, solid-state bisphenol f type epoxy resin fat and bisphenol S type epoxy
One kind or at least two combination in resin, biphenyl type epoxy resin；
Preferably, the epoxy resin more than trifunctional is phenol aldehyde type epoxy resin, o-cresol aldehyde epoxy
One kind or at least two of resin, bisphenol-A phenolic epoxy resin and acyclic isoprenoid type epoxy resin；
Preferably, the composition epoxy resin is also included by the phosphazene compound and asphalt mixtures modified by epoxy resin with silanol
The phosphonitrile epoxy resin that fat is generated by condensation reaction, and fire-retarded epoxy resin；
Preferably, the fire-retarded epoxy resin content of halogen is not higher than 0.2%；
Preferably, the fire-retarded epoxy resin be DOPO types epoxy resin, phosphorus-containing phenolic aldehyde epoxy resin or
One kind or at least two combination in nitrogenous novolac epoxy resin containing phosphorous；
Preferably, the fire-retarded epoxy resin be phosphorous type epoxy resin, it is nitrogenous type epoxy resin, nitrogenous
Phosphorous type epoxy resin or silicon-contained type epoxy resin or one kind in sulfur-type epoxy resin or at least two
Combination；
Preferably, the composition epoxy resin also includes curing accelerator；
Preferably, the curing accelerator is imidazoles, triphenylphosphine and its derivative species, tertiary amines, season
One kind or at least two combination in amine salt or boron trifluoride and its derivative species；
Preferably, the dosage of the curing accelerator is account for epoxy resin gross mass 0.001~2.5%, is entered
One step is preferably 0.03~1.2%；
Preferably, the composition epoxy resin also includes supporting material and filler；
Preferably, the supporting material is one kind or at least two in glass fibre, carbon fiber and polyester fiber
Kind；
Preferably, the filler be silica, diatomite, kaolin, calcium carbonate, mica, titanium dioxide,
One kind in magnesium hydroxide, aluminium hydroxide or at least two；
Preferably, the dosage of the filler is no more than 500phr for epoxy resin gross mass；
Preferably, the composition epoxy resin also includes auxiliary agent, the auxiliary agent be defoamer, coupling agent,
One kind in toughener or levelling agent or at least two.
A kind of 6. phosphonitrile epoxy resin with silanol, it is characterised in that be by non-halogen epoxy resin and
The phosphazene compound with silanol is in the superfluous condition of epoxy resin functional group as described in one of claim 1-3
Under, by reacting obtained epoxy resin product；
Preferably, the epoxide equivalent of the epoxy resin product is in below 3585g/eq；More preferably exist
Below 1520g/eq；
Preferably, the reaction is carried out under conditions of catalyst without catalyst or have；
Preferably, the catalyst is imidazoles, triphenylphosphine and its derivative species, tertiary amines or quaternary amine
A kind of exclusive use or at least two in class catalyst are used in mixed way；
Preferably, the dosage of the catalyst be relative to 0.01~2.5% of the phosphazene compound with silanol,
More preferably 0.02%~0.5%；
Preferably, the temperature of the reaction is 40~250 DEG C, more preferably 60~180 DEG C.
Preferably, the reaction is solvent-free or have and carry out under conditions of solvent, the solvent be ketones solvent,
Aromatic solvents, chlorinated solvents, ether solvent, ether alcohols solvent, alcohols solvent or petroleum solvent naphtha
In one kind or at least two combination；
Preferably, the dosage of the solvent is that the phosphonitrile epoxy resin solid content with silanol can be made to be 5~100%
Dosage, more preferably make the phosphonitrile epoxy resin solid content with silanol be 20~100% dosage；
Preferably, the non-halogen epoxy resin is asphalt mixtures modified by epoxy resin more than two functional epoxy resins or trifunctional
Fat；
Preferably, two functional epoxy resins are liquid bisphenol A types epoxy resin, liquid bisphenol F types
Epoxy resin, solid-state bisphenol A type epoxy resin fat, solid-state bisphenol f type epoxy resin fat, bisphenol S type epoxy
One kind or at least two combination in resin or biphenyl type epoxy resin；
Preferably, the epoxy resin more than trifunctional is phenol aldehyde type epoxy resin, o-cresol aldehyde epoxy
One kind or at least two group of resin, bisphenol-A phenolic epoxy resin or acyclic isoprenoid type epoxy resin
Close.
7. a kind of fire-retardant combination, it is characterised in that include phosphorus azo-cycle oxygen tree as claimed in claim 6
Fat；
Preferably, the fire-retardant combination is also comprising flame retardant epoxy fat resin, curing agent, auxiliary agent, solidification
In accelerator or halogen-free flame-retardance filler any one or at least two combination；
Preferably, the fire-retarded epoxy resin be DOPO types epoxy resin, phosphorus-containing phenolic aldehyde epoxy resin or
One kind or at least two combination in nitrogenous novolac epoxy resin containing phosphorous；
Preferably, the fire-retarded epoxy resin be phosphorous type epoxy resin, it is nitrogenous type epoxy resin, nitrogenous
Phosphorous type epoxy resin, silicon-contained type epoxy resin or one kind or at least two group in sulfur-type epoxy resin
Close；
Preferably, the curing agent be more phenol-based compounds, amine compound, benzoxazine colophony, acid anhydrides,
Polyacid or one kind in boron trifluoride and its complex compound or at least two combination；
Preferably, the amine compound is fatty amine and/or aromatic amine；
Preferably, the fatty amine is dicyandiamide, diethyl triamine, MDA or diaminourea two
One kind or at least two combination in benzene sulfone；
Preferably, more phenol-based compounds be bisphenol-A, Bisphenol F, bisphenol S, linear phenolic resin,
One kind or at least two combination in o-cresol urea formaldehyde or bisphenol A phenolic resin；
Preferably, the dosage of the curing agent and the equivalent proportion of epoxy resin 0.4~1.5；
Preferably, the curing accelerator is imidazoles, triphenylphosphine and its derivative species, tertiary amines, season
One kind or at least two combination in amine salt or boron trifluoride and its derivative species；
Preferably, the dosage of the curing accelerator is account for epoxy resin gross mass 0.001~2.5%, is entered
One step is preferably 0.03~1.2%；
Preferably, the filler is silica, kaolin, calcium carbonate, mica, titanium dioxide, hydroxide
One kind or at least two combination in magnesium or aluminium hydroxide；
Preferably, the dosage of the filler is below the 500phr of epoxy resin gross mass；
Preferably, the auxiliary agent is one kind or at least two in defoamer, coupling agent, toughener or levelling agent
The combination of kind.
A kind of 8. pre-impregnated sheet, it is characterised in that its by composition epoxy resin as claimed in claim 5 or
Person's fire-retardant combination as claimed in claim 7, which is impregnated with or is coated on base material, to be formed；
Preferably, the base material is fiberglass substrate, polyester base material, polyimide base material, ceramic base material
Or carbon fiber base material.
9. a kind of composite metal substrate, it is characterised in that it includes more than more than one such as claim 8
The pre-impregnated sheet carries out surface metal-clad successively, overlapping, pressing forms；
Preferably, the material of the surface metal-clad is the alloy of aluminium, copper, iron and its any combination；
Preferably, the composite metal substrate is that CEM-1 copper-clad plates, CEM-3 copper-clad plates, FR-4 cover copper
Plate, FR-5 copper-clad plates, CEM-1 aluminium bases, CEM-3 aluminium bases, FR-4 aluminium bases or FR-5 aluminium bases
Plate.
10. a kind of wiring board, it is characterised in that in the surface of the composite metal substrate described in claim 9
Processing line forms.
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| CN201610290196.1A CN107337694A (en) | 2016-05-03 | 2016-05-03 | A kind of phosphazene compound with silanol, fire retardant, composition epoxy resin and composite metal substrate |
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| CN201610290196.1A CN107337694A (en) | 2016-05-03 | 2016-05-03 | A kind of phosphazene compound with silanol, fire retardant, composition epoxy resin and composite metal substrate |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109134544A (en) * | 2018-07-24 | 2019-01-04 | 潍坊医学院 | A kind of phosphorus nitrile compounds, the composition including the phosphorus nitrile compounds, the fire retardant comprising it and application |
| CN111002399A (en) * | 2019-11-20 | 2020-04-14 | 德华兔宝宝装饰新材股份有限公司 | Low-moisture-absorption high-flame-retardance plywood and preparation method thereof |
| CN111193068A (en) * | 2020-02-16 | 2020-05-22 | 成都市水泷头化工科技有限公司 | Polyphosphazene composite flame retardant additive for lithium battery electrolyte and preparation method thereof |
| CN112673043A (en) * | 2018-09-19 | 2021-04-16 | 喜利得股份公司 | Curing agent composition for epoxy resin compounds, epoxy resin compounds and multi-component epoxy resin systems |
| CN112961363A (en) * | 2020-10-29 | 2021-06-15 | 广东广山新材料股份有限公司 | Polymeric phosphorus-silicon synergistic flame retardant and preparation method and application thereof |
| CN113045758A (en) * | 2021-04-26 | 2021-06-29 | 北京化工大学 | Preparation method of high-tensile halogen-free flame-retardant polyphosphazene elastomer |
| CN114573637A (en) * | 2020-12-02 | 2022-06-03 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of trimethylsiloxy pentafluorocyclotriphosphazene |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109134544A (en) * | 2018-07-24 | 2019-01-04 | 潍坊医学院 | A kind of phosphorus nitrile compounds, the composition including the phosphorus nitrile compounds, the fire retardant comprising it and application |
| CN109134544B (en) * | 2018-07-24 | 2019-08-06 | 潍坊医学院 | A kind of phosphorus nitrile compounds, the composition including the phosphorus nitrile compounds, the fire retardant comprising it and application |
| WO2020019596A1 (en) * | 2018-07-24 | 2020-01-30 | 潍坊医学院 | Phosphazene compound, composition comprising phosphazene compound, flame retardant comprising same, and use thereof |
| CN112673043A (en) * | 2018-09-19 | 2021-04-16 | 喜利得股份公司 | Curing agent composition for epoxy resin compounds, epoxy resin compounds and multi-component epoxy resin systems |
| CN112673043B (en) * | 2018-09-19 | 2024-03-29 | 喜利得股份公司 | Curing agent composition for epoxy resin mixtures, epoxy resin mixtures and multicomponent epoxy resin systems |
| CN111002399A (en) * | 2019-11-20 | 2020-04-14 | 德华兔宝宝装饰新材股份有限公司 | Low-moisture-absorption high-flame-retardance plywood and preparation method thereof |
| CN111193068A (en) * | 2020-02-16 | 2020-05-22 | 成都市水泷头化工科技有限公司 | Polyphosphazene composite flame retardant additive for lithium battery electrolyte and preparation method thereof |
| CN112961363A (en) * | 2020-10-29 | 2021-06-15 | 广东广山新材料股份有限公司 | Polymeric phosphorus-silicon synergistic flame retardant and preparation method and application thereof |
| CN114573637A (en) * | 2020-12-02 | 2022-06-03 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of trimethylsiloxy pentafluorocyclotriphosphazene |
| CN114573637B (en) * | 2020-12-02 | 2023-11-17 | 张家港市国泰华荣化工新材料有限公司 | Preparation method of trimethylsiloxy pentafluoroethyl triphosphazene |
| CN113045758A (en) * | 2021-04-26 | 2021-06-29 | 北京化工大学 | Preparation method of high-tensile halogen-free flame-retardant polyphosphazene elastomer |
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Application publication date: 20171110 |