CN107011499A - The composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla and its application - Google Patents
The composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla and its application Download PDFInfo
- Publication number
- CN107011499A CN107011499A CN201710253990.3A CN201710253990A CN107011499A CN 107011499 A CN107011499 A CN 107011499A CN 201710253990 A CN201710253990 A CN 201710253990A CN 107011499 A CN107011499 A CN 107011499A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- flame retardant
- aldehyde radical
- vanilla
- composition epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 235000009499 Vanilla fragrans Nutrition 0.000 title claims abstract description 90
- 235000012036 Vanilla tahitensis Nutrition 0.000 title claims abstract description 90
- 244000263375 Vanilla tahitensis Species 0.000 title claims abstract description 88
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 84
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 84
- 239000003063 flame retardant Substances 0.000 title claims abstract description 62
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 title claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000004593 Epoxy Substances 0.000 claims abstract description 16
- 238000004079 fireproofing Methods 0.000 claims abstract description 6
- 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 43
- 229930185605 Bisphenol Natural products 0.000 claims description 29
- -1 glycidyl ester Chemical class 0.000 claims description 26
- 238000001723 curing Methods 0.000 claims description 25
- 238000005452 bending Methods 0.000 claims description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 8
- 150000008065 acid anhydrides Chemical class 0.000 claims description 7
- 125000002723 alicyclic group Chemical group 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- 229910015900 BF3 Inorganic materials 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 238000013007 heat curing Methods 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002383 tung oil Substances 0.000 claims description 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims 1
- 229920003986 novolac Polymers 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 abstract description 21
- 238000007711 solidification Methods 0.000 abstract description 14
- 230000008023 solidification Effects 0.000 abstract description 14
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 38
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000000126 substance Substances 0.000 description 18
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- 230000000979 retarding effect Effects 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 150000002924 oxiranes Chemical class 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 6
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 6
- 229940018564 m-phenylenediamine Drugs 0.000 description 6
- 239000011592 zinc chloride Substances 0.000 description 6
- 235000005074 zinc chloride Nutrition 0.000 description 6
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- BJHJDRPKLAKFSU-UHFFFAOYSA-N C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.[P] Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.[P] BJHJDRPKLAKFSU-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 244000290333 Vanilla fragrans Species 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 125000004427 diamine group Chemical group 0.000 description 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 2
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009267 minimal disease activity Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical group C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- 0 CCC*(C)c(cc1)cc(OC)c1OCC1OC1 Chemical compound CCC*(C)c(cc1)cc(OC)c1OCC1OC1 0.000 description 1
- 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 1
- 241000165940 Houjia Species 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- UPBLAVFWWWKVAJ-UHFFFAOYSA-N [Cl].CCC Chemical compound [Cl].CCC UPBLAVFWWWKVAJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- UUZYBYIOAZTMGC-UHFFFAOYSA-M benzyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CC1=CC=CC=C1 UUZYBYIOAZTMGC-UHFFFAOYSA-M 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- DLQDGVZAEYZNTG-UHFFFAOYSA-N dimethyl hydrogen phosphite Chemical compound COP(O)OC DLQDGVZAEYZNTG-UHFFFAOYSA-N 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000035922 thirst Effects 0.000 description 1
- NRTLTGGGUQIRRT-UHFFFAOYSA-N triethylazanium;bromide Chemical compound [Br-].CC[NH+](CC)CC NRTLTGGGUQIRRT-UHFFFAOYSA-N 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4056—Esters of arylalkanephosphonic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
-
- 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
- C08G59/20—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 epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
- C08G59/304—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing phosphorus
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a kind of composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla, it includes epoxy resin, curing agent, curing accelerator, main flame retardant and flame retardant etc., and the flame retardant is selected from vanilla aldehyde radical phosphonium flame retardant.The invention also discloses the application of the composition epoxy resin, such as described composition epoxy resin or its solidfied material as fire proofing purposes.The composition epoxy resin of the present invention is when solidification is applied as fire proofing; than existing expansion type flame-retarding epoxy systems; not only fire resistance and mechanical property are more excellent; simultaneously because flame retardant therein is to use the vanillic aldehyde of sustainability for raw material, with the double effects economized on resources with environmental protection.
Description
Technical field
The present invention relates to a kind of composition epoxy resin, more particularly to a kind of formula containing the vanilla aldehyde radical phosphonium flame retardant
Composition epoxy resin and its application, such as, as the purposes of fire proofing, belong to technical field of polymer materials.
Background technology
Epoxy resin has excellent mechanical performance, resistance to elevated temperatures, corrosion resistance, cementability and electrical insulating property, extensively
Applied to fields such as automobile, building, electronics, aviations.Inflammable is the common fault of the even most high polymer materials of epoxy resin,
In order to reach fire-retardant purpose, current more common method is that fire retardant is introduced in epoxy-resin systems.With European Union pair
Two big instruction " instruction of waste electronic electric equipment " (West Electrical and in terms of fire retardant environment
Electronic Equipment Directive, WEEE) (in March, 2003 comes into force) and " disabled in electronic and electrical equipment harmful
The promulgation of Substances Directive " (Restriction of Hazardous Substances Directive, RoHS), traditional halogen
The flame-retardant systems such as element are limited by very large.Fire retardant industry faces, which require to turn to, is considered as the pressure of more environmentally friendly fire retardant
Power.There is expansion type flame retardant environmental protection, low toxicity, suppression cigarette etc. to indulge many advantages and be developed rapidly.But current intumescent
Fire retardant is made up of acid source, carbon source and source of the gas, to reach preferably it is fire-retardant, addition is very big, so as to can inevitably lead to
The decline of other performances.Therefore, it is that expansion type flame retardant is obtained extensively to improve the efficiency of expansion type flame retardant and then reduce addition
One approach of general application.
Phosphorus-containing compound based on schiff bases have it is extraordinary contain nitrogen simultaneously into carbon effect, gas can be played
Source is acted on, but existing such phosphorus-containing compound is typically to be made using petroleum chemicals as raw material, and often preparation technology is complicated.
With petroleum resources increasingly depleted, it is that polymer industry exists and developed to find sustainable, high-quality, cheap oil substitute
It is crucial.Bio-based materials while reduction is consumed to petrochemicals, are also reduced using renewable resource as primary raw material
It is the important development direction of current high polymer material to the pollution of environment in petroleum-based feedstock production process.And also the one of industry
It is straight to thirst for developing the functional organic material with excellent fire-retardancy etc. and easily prepared bio-based.
The content of the invention
It is a primary object of the present invention to provide a kind of phosphonium flame retardant of aldehyde radical containing vanilla composition epoxy resin and its
Using to overcome deficiency of the prior art.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
The embodiments of the invention provide a kind of composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla, its include according to
The following component that parts by weight are calculated：100 parts of epoxy resin, 5~150 parts of curing agent, 0~6 part of curing accelerator, main flame retardant
3~15 parts and 0.5~10 part of flame retardant；Wherein, the flame retardant uses vanilla aldehyde radical phosphonium flame retardant.
Further, the vanilla aldehyde radical phosphor-containing flame-proof auxiliary agent has the structure shown in any one in formula (1)~formula (4)：
Wherein R1For
R2For linear paraffin or aromatic hydrocarbon or alicyclic ring alkane structure with 2-20 carbon atom, 0≤n≤10.
The embodiment of the present invention additionally provides the solidfied material of the composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla.
It is preferred that, the fire resistance of the solidfied material is not less than UL-94V0, and bending strength is in more than 90MPa, vitrifying temperature
Degree is more than 100 DEG C.
The embodiment of the present invention additionally provides the preparation method of the solidfied material, including：The composition aldehyde radical containing vanilla is contained
The each component of the composition epoxy resin of phosphorus fire retardant is uniformly mixed, and carries out heat cure, so as to form the solidfied material.
The embodiment of the present invention additionally provides composition epoxy resin or its solidification of the phosphonium flame retardant of aldehyde radical containing vanilla
Thing is in preparing the purposes in fire proofing.
Compared with prior art, advantages of the present invention at least includes：
1) the vanilla aldehyde radical phosphonium flame retardant that the present invention is provided is with the platform of second largest natural reproducible resource lignin
Compound vanillic aldehyde is prepared for raw material, with extraordinary into charcoal effect, be can simultaneously serve as source of the gas and is played swollen well
The effect of swollen layer of charcoal, with expansion type flame retardant commonly use acid source act synergistically, reach effectively it is fire-retardant on the premise of, can be significantly
The addition of fire retardant is reduced, is alleviating oil crisis and reduction CO2Discharge in terms of all have certain positive role；And its
Preparation method technique is simple, and raw material is easy to get, easy to implement, is conducive to reducing cost in actual production, practical；
2) present invention is with vanilla aldehyde radical phosphorus-containing compound, then coordinates the conventional acid source of expansion type flame retardant, and ring is modified jointly
Oxygen tree fat, obtains composition epoxy resin compared with traditional expansion type flame-retarding epoxy systems, mechanical property and fire resistance are more
Plus it is excellent, while the vanillic aldehyde for having used sustainability is raw material, with the double effects economized on resources with environmental protection；It is consolidated
Compound is formulated by epoxy silicones hybrid, epoxy resin, lignin and curing agent and curing accelerator are compound, respectively
There is synergy between individual component, particularly between epoxy silicones hybrid, epoxy resin, lignin, with very strong
Synergy, good flame resistance, simultaneously because fire retardant addition is few, heat, mechanical property are also excellent.
Embodiment
In view of deficiency of the prior art, inventor is able to propose the present invention's through studying for a long period of time and largely putting into practice
Technical scheme, will be further explained to the technical scheme, its implementation process and principle etc. as follows.
The one side of the embodiment of the present invention provides a kind of vanilla aldehyde radical phosphonium flame retardant, and it has following formula (1)~formula
(4) structure shown in any one in：
Wherein, R1IncludingIn structure shown in any one,
R2Including linear paraffin or aromatic hydrocarbon or alicyclic ring alkane structure with 2~20 carbon atoms, 0≤n≤10.
Vanilla aldehyde radical phosphonium flame retardant described in present invention can be prepared by mode known to industry.
For example, a kind of method for preparing the vanilla aldehyde radical phosphonium flame retardant provided in an embodiment of the present invention includes：By perfume (or spice)
Oxalaldehyde, diamine compound, phosphorus-containing compound, catalyst and organic solvent are uniformly mixed, after 20~120 DEG C react 0.5~
48h, obtains the phosphorous bis-phenol of vanilla aldehyde radical, and the phosphorous bis-phenol of vanilla aldehyde radical has structure shown in formula (1) or formula (2)；
Wherein, R1Including
R2Include the linear paraffin or aromatic hydrocarbon or alicyclic ring alkane structure of 2~20 carbon atoms.
Further, the preparation method may also include：By the phosphorous bis-phenol of vanilla aldehyde radical, epoxychloropropane and alkalescence
Material is uniformly mixed, after 20~120 DEG C react 0.2~48h, obtain the phosphorous epoxide of vanilla aldehyde radical, the vanilla
The phosphorous epoxide of aldehyde radical has structure shown in formula (3) or formula (4)；
Wherein, R1Including
R2Including linear paraffins or aromatic hydrocarbon or alicyclic ring alkane structure more than 2~20 carbon atoms, 0≤n≤10.
One of preferably, the vanillic aldehyde, diamine compound, phosphorus-containing compound, catalyst and organic molten
The mass ratio of agent is 100：(15~100)：(20~300)：(0~15)：(50~500).
One of preferably, the quality of the phosphorous bis-phenol of vanilla aldehyde radical, epoxychloropropane and alkaline matter
Than for 100：(20~500)：(30~300).
One of preferably, the diamine compound include p-phenylenediamine, m-phenylene diamine (MPD), to cyclohexanediamine,
In 4,4'- MDAs, 4,4'- diamino-dicyclohexyl methanes, ethylenediamine, 1,6- hexamethylene diamines and 1,3- propane diamine
Any one or two or more combinations, but not limited to this.
It is preferred that, the phosphorus-containing compound includes diethyl phosphite, dimethylphosphite, phosphorous acid dipropyl, phosphorous
Any one in diphenyl phthalate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or two or more combinations, but
Not limited to this.
It is preferred that, the catalyst includes aluminium chloride, zinc chloride, iron chloride, boron trifluoride, columbium pentachloride and antimony pentafluoride
In any one or two or more combinations, but not limited to this.
It is preferred that, the organic solvent includes dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), alcohols, ethers
With any one in aromatic hydrocarbon solvent or two or more combinations；It is preferred that, the alcohols solvent includes ethanol；It is preferred that
, the ether solvent includes tetrahydrofuran and/or dioxane；It is preferred that, the aromatic hydrocarbon solvent includes toluene, but
Not limited to this.
It is preferred that, the alkaline matter includes tetramethyl ammonium chloride, TBAB, benzyltrimethylammonium bromide, benzyl
Base triethylammonium bromide, cetyl trimethylammonium bromide, DTAB, octadecyl trimethyl bromination
At least one of ammonium, hexamethylenetetramine, sodium hydroxide, sodium carbonate, lithium hydroxide, potassium hydroxide and potassium carbonate or at least one
The aqueous solution planted, but not limited to this.
The embodiment of the present invention another aspect provides a kind of epoxy composite of the phosphonium flame retardant of aldehyde radical containing vanilla
Thing, it includes following component according to the number of parts by weight：100 parts of epoxy resin, 5~150 parts of curing agent, curing accelerator 0
0.5~10 part of~6 parts, 3~15 parts of main flame retardant and flame retardant；Wherein, the flame retardant is using foregoing any
Vanilla aldehyde radical phosphonium flame retardant.
Further, the epoxy resin includes bisphenol A type epoxy resin, bisphenol f type epoxy resin, glycidyl ester type
Any one in epoxy resin, glycidyl amine type epoxy resin and novolac epoxy resin or two or more combinations, but not
It is limited to this.
Further, the curing agent can be selected from all kinds of Suitable epoxy curing agent known to industry, and epoxy hardener
Consumption can depending on the type according to the epoxy hardener used, its be it is known to those skilled in the art know, for example may be used
To refer to《Epoxy hardener and additive》(Chemical Industry Press, 2011-09-01 is published, ISBN：9787122110275).
For example, the curing agent can selected from any one in amine curing agent, acid anhydride type curing agent and phenolic resin or two kinds with
On combination, but not limited to this.For example, the amine curing agent can preferably be selected from diethylenetriamine, 4,4 '-diaminourea hexichol first
Any one in alkane, amido amine, polyamide, polyetheramine and dicyandiamide or two or more combinations, but not limited to this.Example
Such as, the acid anhydride type curing agent can preferably be selected from any one in methyl hexahydrophthalic anhydride, itaconic anhydride and tung oil acid anhydride or two
Plant the combination of the above, but not limited to this.
Further, the curing accelerator can also be selected from all kinds known to industry.For example, the solidification promotes
Agent can be selected from any one in tertiary amine, quaternary amine, organic base and lewis acid or two or more combinations, but are not limited to
This.For example, the curing accelerator can preferably be selected from 2-methylimidazole, TBAB, 2,4,6- tri- (dimethylamino first
Base) phenol, any one or two or more combinations in boron trifluoride, but not limited to this.
Further, the main flame retardant includes APP, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, pyrophosphoric acid
Any one in ammonium or two or more combinations, but not limited to this.
The other side of the embodiment of the present invention additionally provides the epoxy resin group of the phosphonium flame retardant of aldehyde radical containing vanilla
The solidfied material of compound.Described solidfied material not only has excellent fire resistance, while having excellent combination property to include height
Glass transition temperature and bending strength etc..For example, the fire resistance of the solidfied material is not less than UL-94V0, bending strength
In more than 90MPa, glass transition temperature is more than 100 DEG C.
The other side of the embodiment of the present invention additionally provides the preparation method of the solidfied material, including：It will constitute described
The each component of the composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla is uniformly mixed, and carries out heat cure, so as to form institute
State solidfied material.
One of preferably, the preparation method is specifically included：100 parts of epoxy resin, 5~150 parts are consolidated
Agent, 0~6 part of curing accelerator, 3~15 parts of main flame retardants, 0.5~10 part of vanilla aldehyde radical phosphonium flame retardant are well mixed, it
Solidify 0.5~10 hour after 50~90 DEG C, solidify 0.5~10 hour in 90~150 DEG C, solidify 0~10 in 150~200 DEG C
Hour, obtain the solidfied material.
The embodiment of the present invention additionally provides composition epoxy resin or its solidification of the phosphonium flame retardant of aldehyde radical containing vanilla
Thing is in preparing the purposes in fire proofing.
Below in conjunction with some embodiments the technical solution of the present invention is further explained explanation, but the present invention implementation
Mode not limited to this.
Embodiment 1：
(1) vanillic aldehyde 100g, p-phenylenediamine 36g, ethanol 500mL are reacted 1 hour at 40 DEG C, then adds zinc chloride
2.5g and dimethylphosphite 72g, is warming up to 80 DEG C and reacts 3 hours, is obtained after petroleum ether precipitation, ethanol washing such as following formula (5)
The shown phosphorous bis-phenol of vanilla aldehyde radical.It can be seen from the hydrogen nuclear magnetic resonance spectrogram of the phosphorous bis-phenol of vanilla aldehyde radical,1H nuclear-magnetisms are total to
Shaking in (d6-DMSO is solvent) has 6.7-7.1ppm to represent the proton peak on vanilla aldehyde structure phenyl ring, and 6.5ppm is represented to benzene two
Proton peak on amine structure phenyl ring, 3.8ppm is the proton peak on vanilla aldehyde structure methyl.
(2) the vanilla aldehyde radical by synthesis in bisphenol A type epoxy resin (E-51) 100g, APP 15g and step (1) contains
Phosphorus bis-phenol 0.5g is well mixed using ball mill, adds 4,4 '-MDA 25g, is uniformly mixed, first 90
Solidify at DEG C 2 hours, then solidify at 150 DEG C 2 hours, finally solidify at 180 DEG C 2 hours, that is, obtain flame retardant epoxy tree
Fat solidfied material.
After testing, the present embodiment obtains the fire resistance of fire retarding epoxide resin solidfied material and reaches UL-94V0 (by standard ASTM
D3801-00 is measured, similarly hereinafter), bending strength is that (by determining, sample is rectangular to bending strength universal testing machine to 140MPa
Body, size is 60 × 10 × 3.5mm3, span is 48mm, and test speed is 2mm/min, similarly hereinafter), glass transition temperature (Tg)
For 165 DEG C (sample solidification after, smash, tested with differential scanning calorimeter, N2Atmosphere, heating rate is 20 DEG C/min, under
Together).
Comparative example 1：The step of with embodiment 1 (2), is essentially identical, but without synthesizing in APP and embodiment 1
The phosphorous bis-phenol of vanilla aldehyde radical, but by bisphenol A type epoxy resin (E-51) 100g, 4,4 '-MDA 25g, stir
It is well mixed, first solidification 2 hours at 90 DEG C, then solidification 2 hours at 150 DEG C, finally solidification 2 hours at 180 DEG C, i.e.,
Obtain epoxy resin cured product.The fire resistance of the epoxy resin cured product reaches UL-94 without rank, and bending strength is 142MPa,
Tg is 162 DEG C.
Comparative example 2：The step of with embodiment 1 (2), is essentially identical, but without APP, but by bisphenol type epoxy
The phosphorous bis-phenol 15.5g of vanilla aldehyde radical that resin (E-51) 100g, embodiment 1 are synthesized, it is well mixed using ball mill；Add 4,
4 '-MDA 25g, is uniformly mixed, and first solidifies at 90 DEG C 2 hours, then solidifies 2 hours at 150 DEG C,
Finally solidify 2 hours at 180 DEG C, produce epoxy resin cured product.The fire resistance of the epoxy resin cured product reaches UL-94
Without rank, bending strength is 145MPa, and Tg is 168 DEG C.
Comparative example 3：The step of with embodiment 1 (2), is essentially identical, but the vanilla aldehyde radical synthesized without embodiment 1 is phosphorous
Bis-phenol, but by bisphenol A type epoxy resin (E-51) 100g, APP 15.5g, be well mixed using ball mill；Add
4,4 '-MDA 25g, are uniformly mixed, and first solidify at 90 DEG C 2 hours, then solidification 2 is small at 150 DEG C
When, finally solidify 2 hours at 180 DEG C, produce epoxy resin cured product.The fire resistance of the epoxy resin cured product reaches
UL-94 is without rank, and bending strength is 138MPa, and Tg is 163 DEG C.
Embodiment 1 is compared with comparative example 1-3 and understood, fire retarding epoxide resin solidification is obtained using technical scheme
The fire resistance of thing is greatly improved, and bending strength and glass transition temperature are maintained.
Embodiment 2：
(1) reacted 1 hour at 40 DEG C by vanillic aldehyde 100g, to cyclohexanediamine 36g, ethanol 500mL, then add zinc chloride
2.5g and diphenyl phosphite 154g, is warming up to 90 DEG C and reacts 2 hours, is obtained after petroleum ether precipitation, ethanol washing such as following formula (6)
The shown phosphorous bis-phenol of vanilla aldehyde radical.It can be seen from the hydrogen nuclear magnetic resonance spectrogram of the phosphorous bis-phenol of vanilla aldehyde radical,1H nuclear-magnetisms are total to
Shaking in (d6-DMSO is solvent) has 6.6-7.4ppm to represent the proton peak on diphenyl phosphite and vanilla aldehyde structure phenyl ring,
2.6ppm represents the proton peak being connected on alicyclic ring with imido grpup on carbon, and 1.2~1.8ppm is Isosorbide-5-Nitrae-cyclohexanediamine structure methylene
The chemical shift of upper proton, 3.7ppm is the proton peak on vanilla aldehyde structure methyl.
(2) it will be closed in glycidyl amine type epoxy resin (AG80) 100g, ammonium phosphate 10g, APP 3g and step (1)
Into the phosphorous bis-phenol 1g of vanilla aldehyde radical, it is well mixed using ball mill；Polyetheramine (D230, Aladdin is provided) 70g is added, is stirred
Mix well mixed, first solidify at 70 DEG C 4 hours, then solidify at 150 DEG C 3 hours, that is, obtain fire retarding epoxide resin solidification
Thing.After testing, the present embodiment obtains the anti-flammability of fire retarding epoxide resin solidfied material and reaches UL-94V0, and bending strength is 125MPa,
Tg is 115 DEG C.
Embodiment 3：
(1) by vanillic aldehyde 100g, 4,4'- MDAs 65g, ethanol 500mL 40 DEG C react 1 hour, then
Diethyl phosphite 45g is added, 90 DEG C is warming up to and reacts 2 hours, is obtained after petroleum ether precipitation, ethanol washing such as following formula (7) institute
The phosphorous bis-phenol of vanilla aldehyde radical shown.It can be seen from the hydrogen nuclear magnetic resonance spectrogram of the phosphorous bis-phenol of vanilla aldehyde radical,1H nuclear magnetic resonance
There is 6.7-7.3ppm to represent the matter on 4,4 '-diaminodiphenyl-methane and vanilla aldehyde structure phenyl ring in (d6-DMSO is solvent)
Sub- peak, 1.3ppm is the proton peak on diethyl phosphite structure methyl, and 3.5ppm is 4,4 '-diaminodiphenyl-methane structure
The chemical shift of proton on methylene, 3.7ppm is the proton peak on vanilla aldehyde structure methyl.
(2) by bisphenol A type epoxy resin (E-54, Lanxing Chemical New Material Co., Ltd. provides) 80g, bisphenol A-type
Synthesized in epoxy resin (E-20, Lanxing Chemical New Material Co., Ltd. provides) 20g, diammonium hydrogen phosphate 11g and step (1)
The phosphorous bis-phenol 2g of vanilla aldehyde radical, it is well mixed using ball mill；Dicyandiamide 50g and boron trifluoride (BF3) 1g are added, is stirred
It is well mixed, first solidify at 60 DEG C 8 hours, then solidify at 100 DEG C 4 hours, finally solidify 10 hours at 150 DEG C,
Obtain fire retarding epoxide resin solidfied material.After testing, the present embodiment obtains the fire resistance of fire retarding epoxide resin solidfied material and reached
UL-94V0, bending strength is 129MPa, and Tg is 155 DEG C.
Comparative example 4：The step of with embodiment 3 (2), is essentially identical, but the vanilla aldehyde radical synthesized without embodiment 3 is phosphorous
Bis-phenol.The fire resistance UL-94-V0 of obtained epoxy resin cured product is without rank, and bending strength is 126MPa, and Tg is 150 DEG C.
Comparative example 5：The step of with embodiment 3 (2), is essentially identical, but without diammonium hydrogen phosphate.Obtained epoxy resin is consolidated
The fire resistance UL-94-V0 of compound is without rank, and bending strength is 130MPa, and Tg is 165 DEG C.
Embodiment 4：
(1) vanillic aldehyde 100g, 4,4'- diamino-dicyclohexyl methanes 65g, ethanol 500mL are reacted 1 hour at 40 DEG C,
Then aluminium chloride 2.5g and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 142g is added, 90 DEG C of reactions 2 are warming up to
Hour, obtain the phosphorous bis-phenol of vanilla aldehyde radical as shown in following formula (8) after petroleum ether precipitation, ethanol washing, then with 300g epoxy chlorine
Propane and 10g cetyl trimethylammonium bromides react 2 hours in 80 DEG C, 40% NaOH aqueous solution 100g are added, 50
DEG C reaction 2 hours, washing, distillation obtains the phosphorous epoxide of vanilla aldehyde radical as shown in following formula (9), and epoxide number is 0.195.
It can be seen from the hydrogen nuclear magnetic resonance spectrogram of the phosphorous epoxide of vanilla aldehyde radical,1H nuclear magnetic resonance (d6-DMSO is solvent)
In there is 6.7-8.3ppm to represent the matter on 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and vanilla aldehyde structure phenyl ring
Sub- peak, 2.3~3.5ppm represents the proton peak being connected on epoxide group on the characteristic chemical shifts and alicyclic ring of proton with imido grpup,
1.1~1.8ppm is its in addition to proton on the methylene being connected with imido grpup of 4,4 '-diamino-dicyclohexyl methane structure
The chemical shift 3.7ppm of his proton is the proton peak on vanilla aldehyde structure methyl.
(2) by glycidyl ester type epoxy resin (o-phthalic acid diglycidyl ester) 100g, ammonium dihydrogen phosphate 9g and
The phosphorous epoxide 6g of vanilla aldehyde radical of synthesis in step (1), it is well mixed using ball mill；Add diethylenetriamine
20g, tung oil acid anhydride 5g and TBAB 2g, are uniformly mixed, and first solidify 10 hours at 50 DEG C, then at 90 DEG C
Solidification 1 hour, then solidify 1 hour at 160 DEG C, that is, obtain fire retarding epoxide resin solidfied material.After testing, the present embodiment obtains resistance
The UL-94V0 of epoxy resin cured product is fired, bending strength is 130MPa, and Tg is 170 DEG C.
Embodiment 5：
(1) vanillic aldehyde 100g, m-phenylene diamine (MPD) 36g, ethanol 500mL are reacted 1 hour at 40 DEG C, then adds zinc chloride
2.5g and diphenyl phosphite 154g, is warming up to 90 DEG C and reacts 2 hours, is obtained after petroleum ether precipitation, ethanol washing such as following formula
(10) the phosphorous bis-phenol of vanilla aldehyde radical shown in, then it is anti-in 80 DEG C with 40g epoxychloropropane and 10g cetyl trimethylammonium bromides
Answer 2 hours, add 40% NaOH aqueous solution 100g, reacted 2 hours at 50 DEG C, washing, distillation are obtained such as following formula (11) institute
The phosphorous epoxide of vanilla aldehyde radical shown, epoxide number is 0.036.It is common according to the nuclear-magnetism of the phosphorous epoxide of vanilla aldehyde radical
Knowable to the hydrogen spectrogram that shakes,1There is 6.6-7.4ppm to represent m-phenylene diamine (MPD), phosphorous acid hexichol in H nuclear magnetic resonance (d6-DMSO is solvent)
Proton peak on ester and vanilla aldehyde structure phenyl ring, 5.9ppm and 6.1ppm are the characterization on two imino group ortho position protons on phenyl ring
Displacement study, 2.3~3.5ppm, tri- peaks represent the characteristic chemical shifts of proton on epoxide group, and 3.75ppm is vanilla aldehyde structure
Proton peak on methyl.
(2) by bisphenol A type epoxy resin (CYD-014U, Yueyang petrochemical industry Co., Ltd of Ba Ling Huaxing provides) 70g, Bisphenol F
Synthesis in type epoxy resin (EPICLON 830LVP, big Japanese ink company provides) 30g, ammonium pyrophosphate 7g and step (1)
The phosphorous epoxide 4g of vanilla aldehyde radical, it is well mixed using ball mill；Phenolic resin 10g and 2-methylimidazole 4g are added,
It is uniformly mixed, first solidifies at 140 DEG C 10 hours, then solidify 1 hour at 200 DEG C, that is, obtain fire retarding epoxide resin
Solidfied material.After testing, the present embodiment obtains the UL-94V0 of fire retarding epoxide resin solidfied material, and bending strength is 135MPa, and Tg is
120℃。
Embodiment 6：
(1) vanillic aldehyde 100g, 1,6- hexamethylene diamines 38g, ethanol 500mL are reacted 1 hour at 40 DEG C, then adds phosphorous acid
Dimethyl ester 72g, is warming up to 90 DEG C and reacts 2 hours, and the vanillic aldehyde as shown in following formula (12) is obtained after petroleum ether precipitation, ethanol washing
The phosphorous bis-phenol of base, then reacted 2 hours in 80 DEG C with 20g epoxychloropropane and 10g cetyl trimethylammonium bromides, add
40% NaOH aqueous solution 60g, react 2 hours at 50 DEG C, and the vanilla aldehyde radical that washing, distillation are obtained as shown in following formula (13) is phosphorous
Epoxide, epoxide number is 0.027.It can be seen from the hydrogen nuclear magnetic resonance spectrogram of the phosphorous epoxide of vanilla aldehyde radical,1There is 6.7-7.1ppm to represent the proton peak on vanilla aldehyde structure phenyl ring in H nuclear magnetic resonance (d6-DMSO is solvent), 2.3~
3.5ppm represents the proton peak on the characteristic chemical shifts of proton and the methylene being connected with imido grpup on epoxide group, 1.1~
1.8ppm is the chemical shift of other protons of 1, the 6- hexamethylene diamines structure in addition to proton on the methylene being connected with imido grpup,
3.7ppm is the proton peak on vanilla aldehyde structure methyl.
(2) by bisphenol f type epoxy resin (D.E.R.TM354, DOW Chemical is provided) 100g, pfpe acid ammonium 5g and step
(1) the phosphorous epoxide 8g of vanilla aldehyde radical of synthesis in, it is well mixed using ball mill；Add itaconic anhydride 55g and 2-
Methylimidazole 5g, is uniformly mixed, and solidifies at solidifying 7 hours, 190 DEG C at 120 DEG C 3 hours, that is, obtains flame retardant epoxy tree
Fat solidfied material.After testing, the present embodiment obtains the UL-94V0 of fire retarding epoxide resin solidfied material, and bending strength is 125MPa, and Tg is
145℃。
Embodiment 7：
(1) vanillic aldehyde 100g, 1,3- propane diamine 24g, ethanol 500mL are reacted 1 hour at 40 DEG C, then adds zinc chloride
2.5g and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 71g, is warming up to 90 DEG C and reacts 2 hours, petroleum ether precipitation,
Obtain the phosphorous bis-phenol of vanilla aldehyde radical as shown in following formula (14) after ethanol washing, then with 20g epoxychloropropane and 10g cetyls
Trimethylammonium bromide reacts 2 hours in 80 DEG C, adds 40% NaOH aqueous solution 60g, is reacted 2 hours at 50 DEG C, washing, steaming
The phosphorous epoxide of vanilla aldehyde radical obtained as shown in following formula (15) is evaporated, epoxide number is 0.029.It is phosphorous according to the vanilla aldehyde radical
Knowable to the hydrogen nuclear magnetic resonance spectrogram of epoxide,1There are 6.7-8.3ppm representatives in H nuclear magnetic resonance (d6-DMSO is solvent)
Proton peak on 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and vanilla aldehyde structure phenyl ring, 2.3~3.6ppm generations
Proton peak on table epoxide group on the characteristic chemical shifts of proton and the methylene being connected with imido grpup, 1.6ppm is 1,3- third
Proton peak on diamine structures mid methylenes, 3.8ppm is the proton peak on vanilla aldehyde structure methyl.
(2) by novolac epoxy resin (NPPN-631, South Asia plastics industry limited company provides) 100g, ammonium pyrophosphate
The 3g and phosphorous epoxide 10g of vanilla aldehyde radical of the middle synthesis of step (1), it is well mixed using ball mill；Add polyamide
(Xuzhou Chinaresearch Science＆Technology Industry Co., Ltd.'s offer) 80g and 2,4,6- tri- (dimethylamino methyl) phenol 6g, are uniformly mixed,
First solidify at 80 DEG C 6 hours, then solidify 5 hours at 130 DEG C, then solidify 5 hours at 170 DEG C, that is, obtain fire-retardant ring
Oxygen resin cured matter.After testing, the present embodiment obtains the UL-94V0 of fire retarding epoxide resin solidfied material, and bending strength is 90MPa,
Tg is 100 DEG C.
Embodiment 8：
(1) vanillic aldehyde 100g, ethylenediamine 15g, ethanol 500mL are reacted 1 hour at 40 DEG C, then adds zinc chloride 2.5g
With 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 71g, it is warming up to 90 DEG C and reacts 2 hours, petroleum ether precipitation, ethanol
Obtain the phosphorous bis-phenol of vanilla aldehyde radical as shown in following formula (16) after washing, then with 20g epoxychloropropane and 10g cetyl front threes
Base ammonium bromide reacts 2 hours in 80 DEG C, adds 40% NaOH aqueous solution 60g, is reacted 2 hours at 50 DEG C, washes, distills
To the phosphorous epoxide of vanilla aldehyde radical as shown in following formula (17), epoxide number is 0.029.According to the phosphorous epoxy of vanilla aldehyde radical
Knowable to the hydrogen nuclear magnetic resonance spectrogram of compound,1There is 6.7-8.3ppm to represent 9,10- in H nuclear magnetic resonance (d6-DMSO is solvent)
Proton peak on the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of dihydro-9-oxy and vanilla aldehyde structure phenyl ring, 2.3~3.9ppm represents epoxy
Proton on group in the characteristic chemical shifts of proton and proton peak and vanilla aldehyde structure methyl on the methylene being connected with nitrogen
Peak.
(2) the vanilla aldehyde radical by synthesis in bisphenol A type epoxy resin (E-44) 100g, APP 9g and step (1) contains
Phosphorus bis-phenol 1g, it is well mixed using ball mill；Add diaminodiphenylsulfone 20g to be uniformly mixed, first then at 100 DEG C
Lower solidification 4 hours, finally solidifies 4 hours at 200 DEG C, that is, obtains fire retarding epoxide resin solidfied material.After testing, the present embodiment institute
The fire resistance for obtaining fire retarding epoxide resin solidfied material reaches UL-94V0, and bending strength is 160MPa, and Tg is 170 DEG C.
Embodiment 9：
(1) vanillic aldehyde 100g, 1,20- eicosane diamines 50g, ethanol 500mL are reacted 1 hour at 40 DEG C, Ran Houjia
Enter diphenyl phosphite 72g, be warming up to 120 DEG C and react 0.5 hour, obtained after petroleum ether precipitation, ethanol washing such as following formula (18)
The shown phosphorous bis-phenol of vanilla aldehyde radical, then reacted 1 hour in 100 DEG C with 20g epoxychloropropane and 1g TBABs, then add
Enter 40% NaOH aqueous solution 60g, reacted 2 hours at 50 DEG C, washing, the vanilla aldehyde radical that obtains as shown in following formula (19) of distillation contain
Phosphorus epoxide, epoxide number is 0.021.It can be seen from the hydrogen nuclear magnetic resonance spectrogram of the phosphorous epoxide of vanilla aldehyde radical,
1There is 6.6-7.4ppm to represent on diphenyl phosphite and vanilla aldehyde structure phenyl ring in H nuclear magnetic resonance (d6-DMSO is solvent)
Proton peak, 2.3~3.5ppm is represented on epoxide group on the characteristic chemical shifts of proton and the methylene being connected with imido grpup
Proton peak, 0.8-1.8ppm is other in addition to proton on the methylene that is connected with imido grpup of 1,20- eicosanes diamine structures
The chemical shift of proton, 3.7ppm is the proton peak on vanilla aldehyde structure methyl.
(2) by bisphenol f type epoxy resin (D.E.R.TM354, DOW Chemical is provided) 100g, APP 5g and step
(1) the phosphorous epoxide 5g of vanilla aldehyde radical of synthesis in, it is well mixed using ball mill；Add phenolic resin 50g and 2-
Methylimidazole 1g, is uniformly mixed, and first solidifies at 140 DEG C 10 hours, then solidifies 1 hour at 200 DEG C, that is, hindered
Fire epoxy resin cured product.After testing, the present embodiment obtains the UL-94V0 of fire retarding epoxide resin solidfied material, and bending strength is
100MPa, Tg are 110 DEG C.
Pass through embodiment 1-9 and comparative example 1-5 contrast, it can be seen that, obtained by the above-mentioned technical proposal of the present invention
Fire retarded epoxy resin composition solidification after, not only with excellent fire resistance, while having high glass transition temperature
The excellent combination property with intensity etc..
In addition, mode of the inventor referring also to embodiment 1- embodiments 9, with the other raw materials listed in this specification
Tested with condition etc., and highly effective flame-retardant composition epoxy resin and its consolidating with Good All-around Property has equally been made
Compound.
It should be pointed out that above-described is only some embodiments of the present invention, for one of ordinary skill in the art
For, on the premise of the creation design of the present invention is not departed from, other modification and improvement can also be made, these belong to this hair
Bright protection domain.
Claims (10)
1. a kind of composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla, it is characterised in that comprising according to the number of parts by weight
Following component：100 parts of epoxy resin, 5~150 parts of curing agent, 0~6 part of curing accelerator, 3~15 parts of main flame retardant and
0.5~10 part of flame retardant；Wherein, the flame retardant uses vanilla aldehyde radical phosphonium flame retardant.
2. composition epoxy resin according to claim 1, it is characterised in that the vanilla aldehyde radical phosphor-containing flame-proof auxiliary agent tool
There is the structure shown in any one in formula (1)~formula (4)：
Wherein R1For
R2For linear paraffin or aromatic hydrocarbon or alicyclic ring alkane structure with 2-20 carbon atom, 0≤n≤10.
3. composition epoxy resin according to claim 1, it is characterised in that：The epoxy resin includes bisphenol A-type ring
Oxygen tree fat, bisphenol f type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin and epoxy novolac tree
Any one in fat or two or more combinations.
4. composition epoxy resin according to claim 1, it is characterised in that：The curing agent include amine curing agent,
Any one in acid anhydride type curing agent and phenolic resin or two or more combinations；It is preferred that, the amine curing agent includes
Any one in diethylenetriamine, 4,4 '-MDA, amido amine, polyamide, polyetheramine and dicyandiamide or two
Plant the combination of the above；It is preferred that, the acid anhydride type curing agent includes appointing in methyl hexahydrophthalic anhydride, itaconic anhydride and tung oil acid anhydride
The combinations for one or more of anticipating.
5. composition epoxy resin according to claim 1, it is characterised in that：The curing accelerator includes tertiary amine, season
Any one in amine salt, organic base and lewis acid or two or more combinations；It is preferred that, the curing accelerator includes 2-
Any one or two kinds in methylimidazole, TBAB, 2,4,6- tri- (dimethylamino methyl) phenol, boron trifluoride with
On combination.
6. composition epoxy resin according to claim 1, it is characterised in that：The main flame retardant include APP,
Any one in ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium pyrophosphate or two or more combinations.
7. the solidfied material of the composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla as any one of claim 1-6；
It is preferred that, the fire resistance of the solidfied material is not less than UL-94V0, and bending strength is in more than 90MPa, and glass transition temperature is 100
More than DEG C.
8. the preparation method of solidfied material as claimed in claim 7, it is characterised in that including：It will constitute any in claim 1-6
The each component of the composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla is uniformly mixed described in, and carries out heat cure, so that
Form the solidfied material.
9. preparation method according to claim 8, it is characterised in that including：Will the composition phosphor-containing flame-proof of aldehyde radical containing vanilla
The each component of the composition epoxy resin of agent is uniformly mixed, after 50~90 DEG C solidify 0.5~10 hour, in 90~150 DEG C
Solidify 0.5~10 hour, solidify 0~10 hour in 150~200 DEG C, obtain the solidfied material.
10. the composition epoxy resin or right of the phosphonium flame retardant of aldehyde radical containing vanilla will as any one of claim 1-6
Solidfied material described in 7 is sought in preparing the purposes in fire proofing.
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