CN107337696A - Phosphazene compound, curing agent, phosphonitrile epoxy resin and composite metal substrate and plastic packaging material with aldehyde radical - Google Patents
Phosphazene compound, curing agent, phosphonitrile epoxy resin and composite metal substrate and plastic packaging material with aldehyde radical Download PDFInfo
- Publication number
- CN107337696A CN107337696A CN201610290670.0A CN201610290670A CN107337696A CN 107337696 A CN107337696 A CN 107337696A CN 201610290670 A CN201610290670 A CN 201610290670A CN 107337696 A CN107337696 A CN 107337696A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- combination
- unsubstituted
- bisphenol
- substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 199
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 199
- -1 Phosphazene compound Chemical class 0.000 title claims abstract description 87
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 47
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000000758 substrate Substances 0.000 title claims abstract description 11
- 239000002131 composite material Substances 0.000 title claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 10
- 239000002184 metal Substances 0.000 title claims abstract description 10
- 239000005022 packaging material Substances 0.000 title claims abstract description 7
- 239000004033 plastic Substances 0.000 title claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 12
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 8
- 229920002627 poly(phosphazenes) Polymers 0.000 claims abstract description 6
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 4
- 125000000962 organic group Chemical group 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 50
- 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 42
- 150000001875 compounds Chemical class 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 29
- 239000003063 flame retardant Substances 0.000 claims description 23
- 229940106691 bisphenol a Drugs 0.000 claims description 22
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 18
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 18
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 16
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 16
- 235000013824 polyphenols Nutrition 0.000 claims description 16
- 239000004593 Epoxy Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 13
- 125000001072 heteroaryl group Chemical group 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229910015900 BF3 Inorganic materials 0.000 claims description 9
- 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
- 150000002118 epoxides Chemical class 0.000 claims description 9
- 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 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 8
- 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 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
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000001118 alkylidene group Chemical group 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229920001568 phenolic resin Polymers 0.000 claims description 8
- 239000005011 phenolic resin Substances 0.000 claims description 8
- 150000001412 amines Chemical group 0.000 claims description 7
- 239000010426 asphalt Substances 0.000 claims description 7
- 125000004171 alkoxy aryl group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group 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
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 6
- 230000006870 function Effects 0.000 claims description 6
- 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 6
- 150000002460 imidazoles Chemical group 0.000 claims description 6
- 239000004843 novolac epoxy resin Substances 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
- 239000010949 copper Substances 0.000 claims description 5
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical group C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- 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 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
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 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
- 125000003118 aryl group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 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
- 239000001301 oxygen Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-methyl phenol Natural products CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 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
- 239000012745 toughening agent Substances 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 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
- 239000004642 Polyimide Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000003849 aromatic solvent Substances 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
- 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
- 229920001721 polyimide Polymers 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims 4
- 239000002585 base Substances 0.000 description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000047 product Substances 0.000 description 14
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 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 9
- 229960003742 phenol Drugs 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- SPWIPDSCASBWFH-UHFFFAOYSA-N [P].N#CC#N Chemical compound [P].N#CC#N SPWIPDSCASBWFH-UHFFFAOYSA-N 0.000 description 6
- 241000894007 species Species 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- UXJHQBVRZUANLK-UHFFFAOYSA-N azanylidyne(dichloro)-$l^{5}-phosphane Chemical group ClP(Cl)#N UXJHQBVRZUANLK-UHFFFAOYSA-N 0.000 description 5
- 150000001555 benzenes Chemical group 0.000 description 5
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical group C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 150000002825 nitriles Chemical group 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 4
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 0 CC(C)(*Oc1c(C=[U])cccc1)C=O Chemical compound CC(C)(*Oc1c(C=[U])cccc1)C=O 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 239000000460 chlorine Substances 0.000 description 3
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 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
- 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
- 229910021295 PNCl2 Inorganic materials 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
- 125000003710 aryl alkyl group Chemical group 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
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 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
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000004446 heteroarylalkyl group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229940100595 phenylacetaldehyde Drugs 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
- 230000009257 reactivity 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
- 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
- OOVPKTABSPKFLL-UHFFFAOYSA-N 2-(4-aminophenyl)acetaldehyde Chemical compound NC1=CC=C(CC=O)C=C1 OOVPKTABSPKFLL-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- BRARRAHGNDUELT-UHFFFAOYSA-N 3-hydroxypicolinic acid Chemical compound OC(=O)C1=NC=CC=C1O BRARRAHGNDUELT-UHFFFAOYSA-N 0.000 description 1
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- IOZQIRHHXVJIDH-UHFFFAOYSA-N O=CCC(C=C1)=CCC1Cl Chemical compound O=CCC(C=C1)=CCC1Cl IOZQIRHHXVJIDH-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- TXAHPQBGJGJQME-UHFFFAOYSA-N acetaldehyde;phenol Chemical compound CC=O.OC1=CC=CC=C1 TXAHPQBGJGJQME-UHFFFAOYSA-N 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 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
- 230000008901 benefit Effects 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 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
- 238000001212 derivatisation Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 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
- 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
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229940091250 magnesium supplement Drugs 0.000 description 1
- GPRDLRZMTVQCHM-UHFFFAOYSA-L magnesium;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Mg+2] GPRDLRZMTVQCHM-UHFFFAOYSA-L 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
- 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
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical group OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005829 trimerization reaction Methods 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a kind of phosphazene compound with aldehyde radical, curing agent, phosphonitrile epoxy resin and composite metal substrate and plastic packaging material, the phosphazene compound with aldehyde radical has the structure shown in Formulas I, wherein R1、R2It independently is any organic group for meeting its chemical environment；X is In any one；Y is any inertia nucleophilic group for meeting its chemical environment；M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2, non-annularity polyphosphazene base M3In one kind and its any combination；A, b is integer more than zero, and 2 times of number of phosphorus atoms on a+b=M groups.The copper-clad plate that phosphazene compound provided by the invention with aldehyde radical enables to be prepared by it has high heat-resisting, good fire resistance and low-dielectric.
Description
Technical field
The present invention relates to the technical field of fire retardant matter, more particularly to a kind of phosphazene compound with aldehyde radical,
Curing agent, phosphonitrile epoxy resin and composite metal substrate and plastic packaging material.
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.
The general use of traditional technology is added such as aluminium hydroxide hydrate, magnesium hydroxide into material system and is hydrated
The inorganic fire-retarded materials such as the metal hydroxides containing the crystallization water such as thing, and bromination is added into material system
The method of the higher organic fire-resisting material of the content of halogen such as bisphenol-A, brominated bisphenol a type epoxy resin, makes
Product reaches required fire resistance or grade.In order to improve these organic chemicals for containing halogen
Anti-flammability, 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
The flame-retardant composition of simple function (there was only an active reactive group in a molecule), such as 9,10- dihydro -9-
Oxa- -10- phospho hetero phenanthrene -10- oxides (hereinafter referred to as DOPO), it is more the derivatization using DOPO
Compound, 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 generation of the high costs such as fat, bisphenol-A phenolic type epoxy resin, polyfunctional epoxy resin and DOPO reactions
Thing (abbreviation DOPO epoxy resin), the epoxide resin material as copper-clad plate purposes.These use DOPO
Copper-clad plate manufactured by epoxy resin, there is good fire resistance, but cohesiveness, heat resistance, processability
Etc. the defects of many being present, high multilayer, high reliability that modern communicationses need, high glutinous are not suitable for manufacturing
Knot property, the product of excellent machinability.Simultaneously because cost is higher, it is unfavorable for spreading to the low costs such as mobile phone
The civil goods field such as consumer electronics.
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 view of this, first aspect present invention provides a kind of phosphazene compound with aldehyde radical, the phosphazene compound
With good flame-retardance and heat resistance.
A kind of phosphazene compound with aldehyde radical, it has the molecular structure as shown in formula I：
In formula I, R is any organic group for meeting its chemical environment；X is-S-、OrIn any one；Y is to meet its chemical environment
Any inertia nucleophilic group；M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2, non-annularity polyphosphazene
Base M3In one kind and its any combination；；A is the integer more than or equal to 1, and b is whole more than or equal to zero
Number, and 2 times of number of phosphorus atoms on a+b=M groups.
Preferably, R be substituted or unsubstituted straight-chain alkyl-sub, substituted or unsubstituted branched alkylidene,
Substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substituted or unsubstituted alkylene
Base arlydene, substituted or unsubstituted arylidene alkylene, substituted or unsubstituted alkylidene Asia heteroaryl
Any one in base or substituted or unsubstituted inferior heteroaryl alkylidene.
Preferably, Y be substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substitution or
Unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy,
Substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group, substituted or unsubstituted sulphonic acid ester
Any one in base or substituted or unsubstituted phosphonate group；The alkoxy, cycloalkyloxy, aryloxy group,
Alkoxy aryl, heteroarylalkoxy, carbonate group, sulfonate group or phosphonate group substituent independently
For straight or branched alkyl, alkoxy, cycloalkyloxy, aryl, aryloxy group, alkoxy aryl, heteroaryl,
In carboxylic acid ester groups, carbonate group, sulfonate group or phosphonate group any one or at least two combination,
The substituent does not contain reactive end-capping group.
In the present invention, the inertia end-capping group refers to that performance comparision is stable under the conditions of popular response, no
Continue to participate in the group of reaction；The reactive end-capping group refers to there is active chemical reactivity, can
The group of chemical reaction is participated in, is referred in particular in the present invention containing OH ,-CN ,-NH2、-SH、-COOH、
-CHO、-CONH2The group of isoreactivity group.Because Y is inertia end-capping group in the present invention,
Therefore it is the group for not containing the 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.
As in the structural formula of phosphonitrile, it should be understood that the group being connected with M is the phosphorus for being connected to M
On atom, 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, two singly-bounds
It is merely representative of M1、M2And M3Side base is connected by its P atom.
Pay attention to, M1、M2In the expression of structural formula, there is symbolOnly to " ring-type "
A kind of signal of structure.
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 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 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 straight-chain alkyl-sub be preferably C1-C12 (such as C2, C3, C4, C5,
C6, C7, C8, C9, C10 or C11) straight-chain alkyl-sub.
Substituted or unsubstituted branched alkylidene be preferably C1-C12 (such as C2, C3, C4, C5,
C6, C7, C8, C9, C10 or C11) branched alkylidene.
Substituted or unsubstituted arlydene be preferably C6-C13 (such as C7, C8, C9, C10, C11 or
C12 arlydene).
Substituted or unsubstituted inferior heteroaryl be preferably C5-C13 (such as C6, C7, C8, C9, C10,
C11 or C12) inferior heteroaryl.
Substituted or unsubstituted alkylenearylene is preferably C7-C13 (such as C8, C9, C10, C11
Or C12) alkylenearylene.
Substituted or unsubstituted arylidene alkylene is preferably C7-C13 (such as C8, C9, C10, C11
Or C12) alkylenearylene.
Substituted or unsubstituted alkylidene inferior heteroaryl be preferably C6-C13 (such as C7, C8, C9,
C10, C11 or C12) alkylidene inferior heteroaryl.
Substituted or unsubstituted inferior heteroaryl alkylidene be preferably C6-C13 (such as C7, C8, C9,
C10, C11 or C12) inferior heteroaryl alkylidene.
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, 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.
Preferably, M includes at least 50wt%M1, at most 30wt%M2And at most 45wt%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 30wt%, that is, is referred to, M2Content can be 0~30wt%.
Work as M2When content is 0wt%, that is, refers to, do not contain M2.The typical but non-limiting M of the present invention2Content
Can be 0wt%, 2wt%, 5wt%, 8wt%, 11wt%, 14wt%, 16wt%, 17wt%,
19wt%, 20wt%, 22wt%, 25wt%, 27wt%, 28wt% or 29wt%.
In the present invention, M3Content is at most 45wt%, that is, is referred to, M3Content can be 0~45wt%.
Work as M3When content is 0wt%, that is, refers to, do not contain M3.The typical but non-limiting M of the present invention3Content
Can be 0wt%, 2wt%, 5wt%, 8wt%, 10wt%, 12wt%, 14wt%, 16wt%,
18wt%, 20wt%, 23wt%, 25wt%, 27wt%, 28wt%, 30wt%, 32wt%, 35wt%,
38wt%, 40wt%, 43wt% or 45wt%.
In the present invention, M1、M2And M3Mass percent sum is 100%.
If M1Content is less than 50wt%, or M2More than 30wt%, then with the reacted life of epoxy resin
Heat resistance, water resistance and mechanical performance etc. will be damaged in use into thing must performance；M3Content extremely
Account for the 45% of phosphazenium groups gross mass more.If exceeding the content, exist with the reacted product of epoxy resin
It would be possible in use because viscosity is excessive, inconvenient for use, and its performance is damaged because molecular weight is excessive
The bad results such as evil.
In the structural formula I of the present invention, a is the integer more than or equal to 1, and b is the integer more than or equal to zero,
Such as a can be but be not limited to 1,2,3,4,5,6,7,8,9 or 10, b can be but be not limited to
0th, 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.
Phosphazene compound of the present invention with aldehyde radical is any one in the compound with following structure
Or at least two combination：
Wherein M is the phosphonitrile base of ring three.
Second aspect, the invention provides a kind of preparation method of the phosphazene compound with aldehyde radical, methods described
The phosphazene compound of preparation has good flame-retardance and heat resistance.
A kind of preparation method of the phosphazene compound with aldehyde radical, this method are to utilize to carry aldehyde radical and activity hydroxy
Or amino or the compound of sulfydryl or carboxylic acid group carry out nucleophilic substitution with phosphonitrile chloride and are prepared.
For example, it is described with aldehyde radical and activity hydroxy or amino or the compound of sulfydryl or carboxylic acid group can be but
It is not limited to salicylaldhyde, para hydroxybenzene acetaldehyde, 3-HPA, p-aminophenyl acetaldehyde or para hydroxybenzene
Propionic aldehyde etc..
In the present invention using with aldehyde radical and activity hydroxy or amino or the compound of sulfydryl or carboxylic acid group
Active reactive group (hydroxyl or amino or sulfydryl or carboxylic acid group) and phosphonitrile chloride occur nucleophilic displacement of fluorine it is anti-
Should, so as to which aldehyde groups are connected on M.We can be first by phosphonitrile chlorine during real reaction
Compound is reacted with the nucleopilic reagent only with an active group so that is connected on a part of P of M groups
End-capping group Y is connected, then by by the change with aldehyde radical and activity hydroxy or amino or sulfydryl or carboxylic acid group
Compound reacts with phosphonitrile chloride again, so as to obtain the phosphazene compound shown in formula I of target.
In the nucleophilic substitution, the chlorine in phosphonitrile chloride is substituted.Necleophilic reaction can use ability
Method known to domain is completed, such as refers to " progress of polyphosphazene, Zhang Hongwei etc., material Leader
The 7th phase of volume 24 in 2010 ".The instantiation of the catalyst used in necleophilic reaction has zinc chloride, chlorination
The lewis base such as the metal chlorides such as magnesium, aluminium chloride, boron trifluoride and its complex compound, sodium hydroxide.These
Catalyst can one or more be used in mixed way, the present invention in have no special regulation.Here " phosphorus cyanogen chlorination
Thing " refers to the compound that M groups are connected with Cl in formula (I).It can be used as phosphonitrile chloride
Known solvent, catalyst synthesize in known reaction scheme, can also be pressed using phosphorus pentachloride with ammonium chloride
It is synthesized according to known method after phosphorus chloride cyanogen compound, handles purification by physical method or do not purify straight
Manufacture is connect, its PCl5+NH4Cl→1/n(NPCl2) n+4HCl, it is mainly trimerization in the reaction product
Body (PNCl2)3(that is, hexachlorocyclotriph,sphazene) and the tetramer (PNCl2)4, reaction product is again by passing through 60 DEG C
Slowly distillation can obtain pure hexachlorocyclotriph,sphazene in vacuum.The phosphonitrile of chloro ring more than four and chloro non-annularity
Polyphosphazene can also be prepared by prior art.
The third aspect, the invention provides a kind of curing agent of epoxy resin, the ring obtained using the curing agent
Oxygen resin cured matter has good flame-retardance, heat resistance, good mechanical performance and dielectric properties.
A kind of curing agent of epoxy resin, the curing agent include the above-mentioned phosphazene compound with aldehyde radical.
The curing agent of epoxy resin of the present invention can only include the phosphazene compound with aldehyde radical, or
Phosphazene compound of the present invention with aldehyde radical can component epoxy curing agent a part, such a situation
Under, for the reactive group equivalents reacted using same epoxy resin to count, the phosphazene compound with aldehyde radical accounts for curing agent
More than 30%, particularly preferably 55%~100%, for example, 60%, 65%, 70%, 75%, 80%, 85%,
90%th, 95% or 99%.It is understood that term " the reactive group equivalents reacted with same epoxy resin
For meter " refer to the relative usage of both reactive phosphorus nitrile compound, curing agent with both each contained by same ring
The reactive group equivalents of oxygen resin reaction is the benchmark calculated.
In the case of a part for the phosphazene compound composition curing agent with aldehyde radical, it is formed other
Curing agent can use conventional epoxy curing agent, be named as curing agent B.Curing agent B instantiation
The more phenol-based compounds of nitrogen, nitrogenous not phosphorous polyphenol based compound or phosphorous not nitrogenous polyphenol base are free of to be not phosphorous
In compound or nitrogenous phosphorous more phenol-based compounds any one or at least two combination.
Preferably, the curing agent B is amine compound, benzoxazine colophony, acid anhydrides, polyacid and three
One kind or at least two combination in boron fluoride and its complex compound.
Preferably, the amine compound is fatty amine or aromatic amine, for example, dicyandiamide, diethyl triamine,
In MDA or diaminodiphenylsulfone any one or at least two combination.
Preferably, more phenol-based compounds be bisphenol-A, Bisphenol F, bisphenol S, linear phenolic resin,
In o-cresol urea formaldehyde or diaminodiphenylsulfone any one or at least two combination.
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 curing agent 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 and 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 aldehyde radical
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 epoxy resin with anti-flammability be phosphorous type epoxy resin, 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
The combination of kind.
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 solvent primarily to by the curing agent and epoxy resin in composition epoxy resin, it may be such that use
Epoxy composite obtains the pre-impregnated sheet of high quality, bonding sheet.For the type and quantity using solvent, this hair
It is bright to have no special regulation, such as can be acetone, butanone, DMF, DMAC, ethanol, methanol, ring
Hexanone, 1,4- dioxane, petroleum solvent, toluene, dimethylbenzene, dichloromethane, dimethyl carbonate etc.
Organic solvent, with reach ensure safe and environment-friendly and required performance on the premise of obtain purpose thing.
Preferably, from as each composition such as butanone has, good dissolubility, toxicity is not strong, boiling point is more moderate
Organic solvent；If the material not readily dissolved in epoxy resin ingredient containing crystallinity such as dicyandiamides, it can make
With organic solvents such as part or all of nitrogenous class such as DMF, DMAC.It is understood that in solidification
During solvent be that can improve the speed of volatilization by heating.
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, and the auxiliary agent is defoamer, coupling agent, toughness reinforcing
One kind in agent and levelling agent or at least two.The present invention is not done especially to the species and addition of adding auxiliary agent
Regulation, can be as needed, be 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 aldehyde radical of dielectric properties.
A kind of phosphonitrile epoxy resin with aldehyde radical, it is by non-halogen epoxy resin and the phosphorus with aldehyde radical 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 aldehyde radical,
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 aldehyde radical can be made to be 5~100%
Dosage, more preferably make the phosphonitrile epoxy resin solid content with aldehyde radical 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, epoxy resin more than two functions be phenol aldehyde type epoxy resin, o-cresol formaldehyde epoxy resin,
One kind or at least two combination of bisphenol-A phenolic epoxy resin or acyclic isoprenoid type epoxy resin.
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 aldehyde radical 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 epoxy resin with anti-flammability be phosphorous type epoxy resin, nitrogenous type epoxy resin,
Nitrogenous phosphorous type epoxy resin, silicon-contained type epoxy resin or one kind in sulfur-type epoxy resin or at least two
Combination.
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 be 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
It is not particularly limited." bonding sheet " that " pre-impregnated sheet " is also 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.
Tenth aspect, the present invention provide a kind of plastic packaging material, and it is comprising above-mentioned composition epoxy resin or as above
State fire-retardant combination.Can according to being actually needed, select conventional functional stuffing according to routine dosage add to
Plastic packaging material is configured in above-mentioned composition epoxy resin or above-mentioned fire-retardant combination.
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：
Composition epoxy resin is prepared by the use of the phosphazene compound with aldehyde radical as curing agent in the present invention, profit
The dielectric constant (1GHz) for the copper-clad plate being prepared with said composition is 3.23-3.32, dielectric loss
(1GHz) is 0.005-0.006, Tg can reach 154 DEG C and more than, T- peel strengths can reach 2.0kg/mm2
More than and, interlaminar strength can reach 1.84kg/mm2More than and, saturated water absorption can reach 0.22%
Hereinafter, heat decomposition temperature can reach 410 DEG C and more than, bending strength can reach 12.3kg/mm2More than and,
Flammability (UL-94) reaches V-0 ranks, therefore prepared by the phosphazene compound provided by the invention with aldehyde radical
Obtained copper-clad plate has high heat-resisting, low dielectric and good fire resistance.
Embodiment
Technical scheme is further illustrated with reference to embodiment.
Embodiment 1
The present embodiment phosphazene compound has following structure：
Preparation method is as follows：
The phosphorus cyanogen 1mol of chlordene ring three, acetone are put into three mouthfuls of 2000ml glass reactors with agitating device
200ml, sodium methoxide 5mol, stir, while leading to nitrogen, be warming up to 60 DEG C, instilled with 60min
20% sodium hydroxide solution 621g, 60 DEG C of temperature are kept, 8 hours of stirring reaction, then add adjacent hydroxyl
Benzaldehyde 1mol, continue reaction 5 hours, after reaction, with the method removal system of physics it is inorganic into
Point and moisture, distill solvent in system, obtain the phosphazene compound 1mol with aldehyde radical, by this product
It 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):δppm 10.2(m,1H,-CH), O 6.9-7.5 (m, 4H, benzene
Hydrogen on ring), 3.42 (s, 15H, OCH 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, aldehyde radical absworption peak 2720cm-1。
Using above-mentioned phosphazene compound A 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.Using the composition epoxy resin according to
The standard copper-clad plate sample for meeting the standards such as national standard, UL is made in general copper-clad plate production process, is named as
A copper-clad plates, test the performance of a copper-clad plates, and its result represents in table -1.
Embodiment 2
The present embodiment phosphazene compound has following structure：
Preparation method is as follows：
The phosphorus cyanogen 1mol of chlordene ring three, acetone are put into three mouthfuls of 2000ml glass reactors with agitating device
200ml, sodium methoxide 3mol, stir, while leading to nitrogen, be warming up to 60 DEG C, instilled with 60min
20% sodium hydroxide solution 621g, 60 DEG C of temperature are kept, 5 hours of stirring reaction, are then added to hydroxyl
Base phenylacetaldehyde 3mol, continue reaction 8 hours, after reaction, with the method removal system of physics it is inorganic into
Point and moisture, distill solvent in system, obtain the phosphazene compound 1mol with aldehyde radical, by this product
It 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):δppm 9.7(m,3H,-CHO),6.6-6.9(m,12H,
Hydrogen on phenyl ring), 3.66 (m, 6H ,-CH 2CHO),3.40(s,9H,OCH 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,
Aldehyde radical 2720cm-1, contraposition substituted benzene ring 827cm-1, aldehyde radical absworption peak 2720cm-1。
Using above-mentioned phosphazene compound B 211g as curing agent, the adjacent first that epoxide equivalent is 200g/eq is added
Novolac epoxy resin 200g, curing accelerator 2-methylimidazole 0.2g, prepares composition epoxy resin.So
It is made afterwards using the composition epoxy resin according to general copper-clad plate production process and meets the mark such as national standard, UL
Accurate standard copper-clad plate sample, b copper-clad plates are named as, test the performance of b copper-clad plates, its result is in table -1
Middle expression.
Embodiment 3
The present embodiment phosphazene compound has following structure：
Preparation method is as follows：
The phosphorus cyanogen 1mol of chlordene ring three, acetone are put into three mouthfuls of 2000ml glass reactors with agitating device
200ml, sodium methoxide 1mol, stir, while leading to nitrogen, be warming up to 60 DEG C, instilled with 60min
20% sodium hydroxide solution 621g, 60 DEG C of temperature are kept, 5 hours of stirring reaction, are then added to ammonia
Base phenylacetaldehyde 5mol, continue reaction 8 hours, after reaction, with the method removal system of physics it is inorganic into
Point and moisture, distill solvent in system, obtain the phosphazene compound 1mol with aldehyde radical, by this product
It 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):δppm 9.7(m,1H,-CH), O 6.3-6.8 (m, 4H, benzene
Hydrogen on ring), 4.0 (m, 1H ,-PNH-),3.66(m,2H,-CH 2CHO),3.48(m,2H,-CH 2CONH2),
3.40(s,15H,OCH 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,
Aldehyde radical 2720cm-1, contraposition substituted benzene ring 827cm-1, aldehyde radical absworption peak 2720cm-1。
Using above-mentioned phosphazene compound C 170g as curing agent, the adjacent first that epoxide equivalent is 200g/eq is added
Novolac epoxy resin 200g, curing accelerator 2-methylimidazole 0.2g, prepares composition epoxy resin.So
It is made afterwards using the composition epoxy resin according to general copper-clad plate production process and meets the mark such as national standard, UL
Accurate standard copper-clad plate sample, c copper-clad plates are named as, test the performance of c copper-clad plates, its result is in table -1
Middle expression.
Embodiment 4
The present embodiment phosphazene compound has following structure：
Preparation method is as follows：
The phosphorus cyanogen 1mol of chlordene ring three, acetone are put into three mouthfuls of 2000ml glass reactors with agitating device
200ml, sodium methoxide 3mol, stir, while leading to nitrogen, be warming up to 60 DEG C, instilled with 60min
20% sodium hydroxide solution 621g, 60 DEG C of temperature are kept, 8 hours of stirring reaction, are then added to hydroxyl
Base benzenpropanal 3mol, continue reaction 5 hours, after reaction, with the method removal system of physics it is inorganic into
Point and moisture, distill solvent in system, obtain the phosphazene compound 1mol with aldehyde radical, by this product
It 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):δppm 9.7(m,1H,-CHO),6.7-6.9(m,4H,
Hydrogen on phenyl ring), 3.40 (s, 15H, OCH 3)2.88(m,2H,-CH 2CH2CHO),2.74(m,2H,-
CH 2CHO)。
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,
Aldehyde radical 2720cm-1, contraposition substituted benzene ring 827cm-1, aldehyde radical absworption peak 2720cm-1。
Using above-mentioned phosphazene compound E 224g as curing agent, the orthoresol that epoxide equivalent is 200g/eq is added
Formaldehyde epoxy resin 200g, curing accelerator 2-methylimidazole 0.2g, prepares composition epoxy resin.Then
It is made using the composition epoxy resin according to general copper-clad plate production process and meets the standards such as national standard, UL
Standard copper-clad plate sample, be named as d copper-clad plates, test the performance of d copper-clad plates, its result is in table -1
Represent.
Embodiment 5
The present embodiment phosphazene compound has following structure：
The phosphorus cyanogen 1mol of chlordene ring three, acetone are put into three mouthfuls of 2000ml glass reactors with agitating device
200ml, sodium methoxide 1mol, stir, while leading to nitrogen, be warming up to 60 DEG C, instilled with 60min
20% sodium hydroxide solution 621g, 60 DEG C of temperature are kept, 8 hours of stirring reaction, then add 3- hydroxyls
Base propionic aldehyde 5mol, continue reaction 5 hours, after reaction, with inorganic constituents in the method removal system of physics
And moisture, solvent in system is distilled, the phosphazene compound 1mol with aldehyde radical is obtained, this product is ordered
Entitled E.
Proton nmr spectra sign is carried out to obtained compound E, it is as a result as follows：
1H NMR(CDCl3,500MHz):δppm 9.7(m,1H,-CHO),3.86(m,2H,
-OCH 2CH2CHO),3.40(s,15H,OCH 3)2.59(m,2H,-OCH2CH 2CHO))。
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,
Aldehyde radical 2720cm-1, contraposition substituted benzene ring 827cm-1,CH2- O absworption peak 2983cm-1, aldehyde radical absorption
Peak 2720cm-1。
Using above-mentioned phosphazene compound E 106g as curing agent, the orthoresol that epoxide equivalent is 200g/eq is added
Formaldehyde epoxy resin 200g, curing accelerator 2-methylimidazole 0.2g, prepares composition epoxy resin.Then
It is made using the composition epoxy resin according to general copper-clad plate production process and meets the standards such as national standard, UL
Standard copper-clad plate sample, be named as e copper-clad plates, test the performance of e copper-clad plates, its result is in table -1
Represent.
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 f for meeting the standards such as national standard, UL is made according to general copper-clad plate production process, covers copper
F 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 g for meeting the standards such as national standard, UL is made in general copper-clad plate production process, covers copper g
Properties represented in table -1.
Table -1
The test data of above table, show that the phosphazene compound of the present invention and its derivative work as use in epoxy
When in resin curing system and other systems, there is good anti-flammability, its solidfied material has well heat-resisting
Property, water resistance, cohesiveness and mechanical performance, electrical property.The present invention fire-retardant compound belong to low cost,
The environment-friendly type flame-retardant of the novel environmental friendly for the energy-saving and emission-reducing that raw material sources are abundant, properties are good
Material.
Applicant state, the present invention by above-described embodiment come illustrate the present invention phosphazene compound, curing agent,
Phosphonitrile epoxy resin and its application, but the invention is not limited in above-described embodiment, that is, do not mean that the present invention
Having to rely on above-described embodiment could implement.Person of ordinary skill in the field is it will be clearly understood that to the present invention
Any improvement, the addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, concrete mode
Selection etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of phosphazene compound with aldehyde radical, it is characterised in that it has the molecule knot as shown in formula I
Structure：
In formula I, R is any organic group for meeting its chemical environment；X is In any one；Y is to meet its chemical environment
Any inertia nucleophilic group；M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2, non-annularity polyphosphazene
Base M3In one kind and its any combination；A is the integer more than or equal to 1, and b is the integer more than or equal to zero,
And 2 times of number of phosphorus atoms on a+b=M groups.
2. the phosphazene compound according to claim 1 with aldehyde radical, it is characterised in that R is substitution
Or unsubstituted straight-chain alkyl-sub, substituted or unsubstituted branched alkylidene, substituted or unsubstituted sub- virtue
Base, substituted or unsubstituted inferior heteroaryl, substituted or unsubstituted alkylenearylene, substitution or
Unsubstituted arylidene alkylene, substituted or unsubstituted alkylidene inferior heteroaryl or substituted or unsubstituted
Inferior heteroaryl alkylidene in any one；
Preferably, Y be substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substitution or
Unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy,
Substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group, substituted or unsubstituted sulphonic acid ester
Any one in base or substituted or unsubstituted phosphonate group；The alkoxy, cycloalkyloxy, aryloxy group,
Alkoxy aryl, heteroarylalkoxy, carbonate group, sulfonate group or phosphonate group substituent independently
For straight or branched alkyl, alkoxy, cycloalkyloxy, aryl, aryloxy group, alkoxy aryl, heteroaryl,
In carboxylic acid ester groups, carbonate group, sulfonate group or phosphonate group any one or at least two combination,
The substituent does 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 30wt%M2And at most 45wt%M3。
3. the phosphazene compound according to claim 1 or 2 with aldehyde radical, it is characterised in that described
Phosphazene compound with aldehyde radical 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 curing agent of epoxy resin, it is characterised in that the curing agent includes such as claim 1-3
Any one of the phosphazene compound with aldehyde radical；
Preferably, the reactive group equivalents reacted using same epoxy resin is counts, the phosphonitrile chemical combination with aldehyde radical
Thing accounts for curing agent more than 30%；
It is further preferred that the reactive group equivalents reacted using same epoxy resin is counts, the phosphorus with aldehyde radical
Nitrile compound accounts for the 55%~100% of curing agent；
Preferably, the curing agent is also free of nitrogen polyphenol comprising curing agent B, the curing agent B to be not phosphorous
Based compound, nitrogenous not phosphorous polyphenol based compound, phosphorous not nitrogenous polyphenol based compound or nitrogenous phosphorous more
In phenol-based compounds any one or at least two combination；
Preferably, the curing agent B is amine compound, benzoxazine colophony, acid anhydrides, polyacid and three
One kind or at least two combination in boron fluoride and its complex compound；
Preferably, the amine compound is dicyandiamide, diethyl triamine, MDA or diamino
In base diphenyl sulphone (DPS) any one or at least two combination；
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.
5. a kind of composition epoxy resin, it is characterised in that comprising epoxy resin, and such as claim 4
Described curing agent；
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 aldehyde radical
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 epoxy resin with anti-flammability be phosphorous type epoxy resin, nitrogenous type epoxy resin,
Nitrogenous phosphorous type epoxy resin or silicon-contained type epoxy resin and one kind in sulfur-type epoxy resin or at least two
The combination of kind；
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 and levelling agent or at least two.
6. a kind of phosphonitrile epoxy resin, it is characterised in that be by non-halogen epoxy resin and as right will
The phosphazene compound with aldehyde radical any one of 1-3 is sought under conditions of the epoxy radicals surplus of epoxy resin,
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 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 aldehyde radical,
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 aldehyde radical can be made to be 5~100%
Dosage, more preferably make the phosphonitrile epoxy resin solid content with aldehyde radical 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 and bisphenol S type ring
One kind or at least two combination in oxygen tree fat or biphenyl type epoxy resin；
Preferably, epoxy resin more than two functions be phenol aldehyde type epoxy resin, o-cresol formaldehyde epoxy resin,
One kind or at least two combination of bisphenol-A phenolic epoxy resin or acyclic isoprenoid type epoxy resin.
7. a kind of fire-retardant combination, it is characterised in that include phosphonitrile asphalt mixtures modified by epoxy resin 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 epoxy resin with anti-flammability be phosphorous type epoxy resin, nitrogenous type epoxy resin,
Nitrogenous phosphorous type epoxy resin, silicon-contained type epoxy resin or one kind in sulfur-type epoxy resin or at least two
Combination；
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 at least one as claimed in claim 8
Pre-impregnated sheet, by carrying 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.
A kind of 10. plastic packaging material, it is characterised in that comprising composition epoxy resin as claimed in claim 5 or
Person's fire-retardant combination as claimed in claim 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610290670.0A CN107337696A (en) | 2016-05-03 | 2016-05-03 | Phosphazene compound, curing agent, phosphonitrile epoxy resin and composite metal substrate and plastic packaging material with aldehyde radical |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610290670.0A CN107337696A (en) | 2016-05-03 | 2016-05-03 | Phosphazene compound, curing agent, phosphonitrile epoxy resin and composite metal substrate and plastic packaging material with aldehyde radical |
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| Publication Number | Publication Date |
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| CN107337696A true CN107337696A (en) | 2017-11-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610290670.0A Pending CN107337696A (en) | 2016-05-03 | 2016-05-03 | Phosphazene compound, curing agent, phosphonitrile epoxy resin and composite metal substrate and plastic packaging material with aldehyde radical |
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| Country | Link |
|---|---|
| CN (1) | CN107337696A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110615928A (en) * | 2019-09-30 | 2019-12-27 | 北京工业大学 | Modified coal gangue powder filled polyolefin flame-retardant composite material and preparation process thereof |
| CN111560156A (en) * | 2019-02-13 | 2020-08-21 | 味之素株式会社 | Resin composition |
| CN112442065A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing flame retardant with aldehyde group and preparation method and application thereof |
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| CN102757579A (en) * | 2012-07-19 | 2012-10-31 | 三峡大学 | Oxa-phosphaphenanthrene flame retardant containing cyclotriphosphonitrile structure, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102757579A (en) * | 2012-07-19 | 2012-10-31 | 三峡大学 | Oxa-phosphaphenanthrene flame retardant containing cyclotriphosphonitrile structure, and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111560156A (en) * | 2019-02-13 | 2020-08-21 | 味之素株式会社 | Resin composition |
| CN112442065A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing flame retardant with aldehyde group and preparation method and application thereof |
| CN110615928A (en) * | 2019-09-30 | 2019-12-27 | 北京工业大学 | Modified coal gangue powder filled polyolefin flame-retardant composite material and preparation process thereof |
| CN110615928B (en) * | 2019-09-30 | 2022-03-08 | 北京工业大学 | Modified coal gangue powder filled polyolefin flame-retardant composite material and preparation process thereof |
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