CN107011499B - 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
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- CN107011499B CN107011499B CN201710253990.3A CN201710253990A CN107011499B CN 107011499 B CN107011499 B CN 107011499B CN 201710253990 A CN201710253990 A CN 201710253990A CN 107011499 B CN107011499 B CN 107011499B
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- China
- Prior art keywords
- epoxy resin
- flame retardant
- aldehyde radical
- vanilla
- composition epoxy
- Prior art date
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- 235000009499 Vanilla fragrans Nutrition 0.000 title claims abstract description 89
- 235000012036 Vanilla tahitensis Nutrition 0.000 title claims abstract description 89
- 244000263375 Vanilla tahitensis Species 0.000 title claims abstract description 87
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 85
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 85
- 239000003063 flame retardant Substances 0.000 title claims abstract description 80
- 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 67
- 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 26
- 239000000463 material Substances 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 238000007711 solidification Methods 0.000 claims abstract description 10
- 230000008023 solidification Effects 0.000 claims abstract description 10
- 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 44
- 229930185605 Bisphenol Natural products 0.000 claims description 28
- -1 glycidyl ester Chemical class 0.000 claims description 27
- 238000005452 bending Methods 0.000 claims description 21
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 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
- 150000001412 amines Chemical class 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910015900 BF3 Inorganic materials 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 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
- 239000004254 Ammonium phosphate Substances 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 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
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-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
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000004843 novolac epoxy resin Substances 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
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical group 0.000 claims description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 abstract description 21
- 239000004593 Epoxy Substances 0.000 abstract description 15
- 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 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 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 46
- 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
- 235000019441 ethanol Nutrition 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 19
- 238000001723 curing Methods 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- 230000000979 retarding effect Effects 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 239000003208 petroleum Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 150000001875 compounds Chemical class 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
- 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
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 239000004114 Ammonium polyphosphate Substances 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 8
- 229920001276 ammonium polyphosphate Polymers 0.000 description 8
- 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
- 230000000052 comparative effect Effects 0.000 description 7
- 150000002924 oxiranes Chemical class 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
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 238000004821 distillation Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 3
- 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
- 238000006243 chemical reaction 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
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin 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
- 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
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 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
- 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
- 238000013007 heat curing Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 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
- 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
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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 2
- 238000012360 testing method Methods 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
- 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
- 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
- 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
- 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
- 239000012752 auxiliary agent Substances 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
- 238000011161 development Methods 0.000 description 1
- 125000004427 diamine group Chemical group 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
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 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
- 125000005842 heteroatom Chemical group 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
- 238000005259 measurement Methods 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 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
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 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 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 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
- 239000002861 polymer material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- NRTLTGGGUQIRRT-UHFFFAOYSA-N triethylazanium;bromide Chemical compound [Br-].CC[NH+](CC)CC NRTLTGGGUQIRRT-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
-
- 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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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a kind of composition epoxy resins of phosphonium flame retardant of aldehyde radical containing vanilla comprising epoxy resin, curing agent, curing accelerator, main flame retardant and flame retardant etc., the flame retardant are selected from vanilla aldehyde radical phosphonium flame retardant.The invention also discloses the applications of the composition epoxy resin, such as the purposes of the composition epoxy resin or its solidfied material as fire proofing.Composition epoxy resin of the invention is when solidification is as fire proofing application; compared with existing expansion type flame-retarding epoxy systems; not only flame retardant property and mechanical property are more excellent; it is simultaneously raw material because flame retardant therein is using the vanillic aldehyde of sustainability, there are the double effects for economizing on resources and protecting environment.
Description
Technical field
It is the present invention relates to a kind of composition epoxy resin, in particular to a kind of containing the vanilla aldehyde radical phosphonium flame retardant formula
Composition epoxy resin and its application, such as the purposes of fire proofing, belong to technical field of polymer materials.
Background technique
Epoxy resin has excellent mechanical performance, high temperature resistance, 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 molecular materials of epoxy resin,
Fire-retardant in order to achieve the purpose that, 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 electrical equipment " (West Electrical and in terms of fire retardant environment
Electronic Equipment Directive, WEEE) it (in March, 2003 comes into force) and " is 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 require to turn to the pressure for being considered more environmentally friendly fire retardant
Power.Expansion type flame retardant has the advantages that environmental protection, low toxicity, suppression cigarette etc. are indulged more and rapidly developed.However current intumescent
Fire retardant is made of acid source, carbon source and gas source, to reach ideal fire-retardant, additive amount is very big, to can inevitably lead to
The decline of other performances.Therefore, improving the efficiency of expansion type flame retardant and then reducing additive amount is that expansion type flame retardant obtains extensively
One approach of general application.
Phosphorus-containing compound based on schiff bases contains nitrogen at carbon effect with extraordinary simultaneously, can play gas
Source effect, but existing such phosphorus-containing compound is usually to be made using petroleum chemicals as raw material, and often preparation process is complicated.
As petroleum resources are increasingly depleted, finding sustainable, high-quality, cheap petroleum substitute is that polymer industry exists and develops
It is crucial.Bio-based materials while reducing to petrochemicals consumption, are also reduced using renewable resource as primary raw material
It is the important development direction of current high molecular material to the pollution of environment in petroleum-based feedstock production process.And also the one of industry
Straight serious hope is developed with excellent fire-retardancy etc. and the functional organic material of easily prepared biology base.
Summary of the invention
The main purpose of the present invention is to provide a kind of composition epoxy resin of phosphonium flame retardant of aldehyde radical containing vanilla and its
Using to overcome deficiency in the prior art.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
The embodiment of the invention provides a kind of composition epoxy resin of phosphonium flame retardant of aldehyde radical containing vanilla, it includes according to
The following component that parts by weight calculate: 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 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 invention also provides the solidfied materials of the composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla.
Preferably, the flame retardant property of the solidfied material is not less than UL-94V0, and bending strength is in 90MPa or more, vitrifying temperature
Degree is at 100 DEG C or more.
The embodiment of the invention also provides the preparation methods of the solidfied material, comprising: will form the aldehyde radical containing vanilla and contains
The each component of the composition epoxy resin of phosphorus fire retardant uniformly mixes, and carries out heat cure, to form the solidfied material.
The embodiment of the invention also provides the composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla or its solidifications
Object is in preparing the purposes in fire proofing.
Compared with prior art, advantages of the present invention includes at least:
1) vanilla aldehyde radical phosphonium flame retardant provided by the invention is with the platform of the second largest natural reproducible resource lignin
Compound vanillic aldehyde is raw material and prepares, have it is extraordinary at charcoal effect, can simultaneously serve as gas source play it is swollen well
The effect of swollen layer of charcoal acts synergistically with the common acid source of expansion type flame retardant, can be significantly under the premise of reaching effectively fire-retardant
The additive amount for reducing fire retardant is alleviating oil crisis and is reducing CO2Discharge in terms of all have certain positive effect；And its
Preparation method simple process, raw material are easy to get, easy to implement, are conducive to reduce cost in actual production, practical；
2) present invention is with vanilla aldehyde radical phosphorus-containing compound, then cooperates the common acid source of expansion type flame retardant, is modified ring jointly
Oxygen resin, obtained composition epoxy resin is compared with traditional expansion type flame-retarding epoxy systems, and mechanical property and flame retardant property are more
Add excellent, while having used the vanillic aldehyde of sustainability is raw material, has and economizes on resources and protect the double effects of environment；It is solid
Compound is formulated by epoxy silicones hybrid, epoxy resin, lignin and curing agent and curing accelerator are compound, respectively
There are synergistic effect, especially epoxy silicones hybrid, epoxy resin between a component, between lignin, has very strong
Synergistic effect, good flame resistance, simultaneously because fire retardant additive amount is few, heat, mechanical property are also excellent.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention
Technical solution as follows will be further explained the technical solution, its implementation process and principle etc..
The one aspect of the embodiment of the present invention provides a kind of vanilla aldehyde radical phosphonium flame retardant, with following formula (1)~formula
(4) structure shown in any one in:
Wherein, R1IncludingIn structure shown in any one,
R2Including having the linear paraffin of 2~20 carbon atoms or aromatic hydrocarbon or alicyclic ring alkane structure, 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: will be fragrant
Oxalaldehyde, diamine compound, phosphorus-containing compound, catalyst and organic solvent uniformly mix, later in 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
R2Linear paraffin or aromatic hydrocarbon or alicyclic ring alkane structure including 2~20 carbon atoms.
Further, the preparation method may also include that the phosphorous bis-phenol of the vanilla aldehyde radical, epoxychloropropane and alkalinity
Substance uniformly mixes, and later in 20~120 DEG C of 0.2~48h of reaction, obtains 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 the 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'- diaminodiphenylmethane, 4,4'- diamino-dicyclohexyl methane, ethylenediamine, 1,6- hexamethylene diamine and 1,3- propane diamine
Any one or two or more combinations, but not limited to this.
Preferably, 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
It is without being limited thereto.
Preferably, 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.
Preferably, the organic solvent includes dimethylformamide, dimethyl acetamide, dimethyl sulfoxide, alcohols, ethers
With any one or the two or more combinations in aromatic hydrocarbon solvent；Preferably, the alcohols solvent includes ethyl alcohol；It is preferred that
, the ether solvent includes tetrahydrofuran and/or dioxane；Preferably, the aromatic hydrocarbon solvent includes toluene, but
It is without being limited thereto.
Preferably, the alkaline matter includes tetramethyl ammonium chloride, tetrabutylammonium bromide, benzyltrimethylammonium bromide, benzyl
Base triethylammonium bromide, cetyl trimethylammonium bromide, dodecyl trimethyl ammonium bromide, 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 of kind, but not limited to this.
The embodiment of the present invention another aspect provides a kind of epoxy composites of phosphonium flame retardant of aldehyde radical containing vanilla
Object, it includes following components according to the number of parts by weight: 100 parts of epoxy resin, 5~150 parts of curing agent, curing accelerator 0
~6 parts, 3~15 parts of main flame retardant and 0.5~10 part of flame retardant；Wherein, the flame retardant is using above-mentioned 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 all kinds of Suitable epoxy curing agent known to the industry, and epoxy hardener
Dosage can be known to those skilled in the art to know depending on the type according to used epoxy hardener, such as can
With reference to " epoxy hardener and additive " (Chemical Industry Press, 2011-09-01 are 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 '-diamino 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
Kind or more combination, but not limited to this.
Further, the curing accelerator can also be selected from various types 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, tetrabutylammonium bromide, 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 ammonium polyphosphate, 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
Close the solidfied material of object.The solidfied material not only has excellent flame retardant property, while having excellent comprehensive performance includes height
Glass transition temperature and bending strength etc..For example, the flame retardant property of the solidfied material is not less than UL-94V0, bending strength
In 90MPa or more, glass transition temperature is at 100 DEG C or more.
The other side of the embodiment of the present invention additionally provides the preparation method of the solidfied material, comprising: will be described in composition
The each component of the composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla uniformly mixes, and carries out heat cure, to form institute
State solidfied material.
One of preferably, the preparation method specifically includes: 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 uniformly mixed, it
Solidify 0.5~10 hour in 50~90 DEG C afterwards, solidifies 0.5~10 hour in 90~150 DEG C, solidifies 0~10 in 150~200 DEG C
Hour, obtain the solidfied material.
The embodiment of the invention also provides the composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla or its solidifications
Object is in preparing the purposes in fire proofing.
Below in conjunction with the technical solution of the present invention is further explained explanation, but the implementation of the invention of several embodiments
Mode is without being limited thereto.
Embodiment 1:
(1) vanillic aldehyde 100g, p-phenylenediamine 36g, ethyl alcohol 500mL are reacted 1 hour at 40 DEG C, zinc chloride is then added
2.5g and dimethylphosphite 72g is warming up to 80 DEG C and reacts 3 hours, obtains after petroleum ether precipitation, ethanol washing such as following formula (5)
Shown in the phosphorous bis-phenol of vanilla aldehyde radical.According to the hydrogen nuclear magnetic resonance spectrogram of the phosphorous bis-phenol of vanilla aldehyde radical it is found that1H nuclear-magnetism is total
There is 6.7-7.1ppm to represent the proton peak on vanilla aldehyde structure phenyl ring in vibration (d6-DMSO is solvent), 6.5ppm is represented to benzene two
Proton peak on amine structure phenyl ring, 3.8ppm are the proton peak on vanilla aldehyde structure methyl.
(2) the vanilla aldehyde radical synthesized in bisphenol A type epoxy resin (E-51) 100g, ammonium polyphosphate 15g and step (1) is contained
Phosphorus bis-phenol 0.5g is uniformly mixed using ball mill, is added 4,4 '-diaminodiphenylmethane 25g, is uniformly mixed, first 90
Solidify at DEG C 2 hours, then solidify at 150 DEG C 2 hours, finally solidifies 2 hours, i.e. acquisition flame retardant epoxy tree at 180 DEG C
Rouge solidfied material.
Through detecting, the flame retardant property of the obtained fire retarding epoxide resin solidfied material of the present embodiment reaches UL-94V0 (by standard ASTM
D3801-00 is measured, similarly hereinafter), bending strength is that (for bending strength universal testing machine by measurement, sample is rectangular to 140MPa
Body, having a size of 60 × 10 × 3.5mm3, span 48mm, test speed 2mm/min, similarly hereinafter), glass transition temperature (Tg)
For 165 DEG C (sample solidification after, be ground into a powder, tested with differential scanning calorimeter, N2Atmosphere, heating rate are 20 DEG C/min, under
Together).
Comparative example 1: it is essentially identical with (2) the step of embodiment 1, but do not add and synthesize in ammonium polyphosphate and embodiment 1
The phosphorous bis-phenol of vanilla aldehyde radical, but by bisphenol A type epoxy resin (E-51) 100g, 4,4 '-diaminodiphenylmethane 25g, it stirs
It is uniformly mixed, first solidifies at 90 DEG C 2 hours, then solidify at 150 DEG C 2 hours, finally solidify 2 hours at 180 DEG C, i.e.,
Obtain epoxy resin cured product.The flame retardant property of the epoxy resin cured product reaches UL-94 without rank, bending strength 142MPa,
Tg is 162 DEG C.
Comparative example 2: it is essentially identical with (2) the step of embodiment 1, but do not add ammonium polyphosphate, but by bisphenol type epoxy
The phosphorous bis-phenol 15.5g of vanilla aldehyde radical that resin (E-51) 100g, embodiment 1 synthesize, is uniformly mixed using ball mill；Add 4,
4 '-diaminodiphenylmethane 25g, are uniformly mixed, and first solidify 2 hours at 90 DEG C, then solidify 2 hours at 150 DEG C,
Solidify 2 hours at 180 DEG C finally to get epoxy resin cured product.The flame retardant property of the epoxy resin cured product reaches UL-94
Without rank, bending strength 145MPa, Tg are 168 DEG C.
Comparative example 3: it is essentially identical with (2) the step of embodiment 1, but the vanilla aldehyde radical for not adding the synthesis of embodiment 1 is phosphorous
Bis-phenol, but by bisphenol A type epoxy resin (E-51) 100g, ammonium polyphosphate 15.5g, it is uniformly mixed using ball mill；It adds
4,4 '-diaminodiphenylmethane 25g, are uniformly mixed, and first solidify at 90 DEG C 2 hours, then solidification 2 is small at 150 DEG C
When, solidify 2 hours at 180 DEG C finally to get epoxy resin cured product.The flame retardant property of the epoxy resin cured product reaches
For UL-94 without rank, bending strength 138MPa, Tg are 163 DEG C.
By embodiment 1 it is found that being solidified using the obtained fire retarding epoxide resin of technical solution of the present invention compared with comparative example 1-3
The flame retardant property of object is greatly improved, and bending strength and glass transition temperature are maintained.
Embodiment 2:
(1) it is reacted 1 hour by vanillic aldehyde 100g, to cyclohexanediamine 36g, ethyl alcohol 500mL at 40 DEG C, zinc chloride is then added
2.5g and diphenyl phosphite 154g is warming up to 90 DEG C and reacts 2 hours, obtains after petroleum ether precipitation, ethanol washing such as following formula (6)
Shown in the phosphorous bis-phenol of vanilla aldehyde radical.According to the hydrogen nuclear magnetic resonance spectrogram of the phosphorous bis-phenol of vanilla aldehyde radical it is found that1H nuclear-magnetism is total
There is 6.6-7.4ppm to represent the proton peak on diphenyl phosphite and vanilla aldehyde structure phenyl ring in vibration (d6-DMSO is solvent),
2.6ppm represents the proton peak being connected on carbon on alicyclic ring with imido grpup, and 1.2~1.8ppm is Isosorbide-5-Nitrae-cyclohexanediamine structure methylene
The chemical shift of upper proton, 3.7ppm are the proton peak on vanilla aldehyde structure methyl.
(2) it will be closed in glycidyl amine type epoxy resin (AG80) 100g, ammonium phosphate 10g, ammonium polyphosphate 3g and step (1)
At the phosphorous bis-phenol 1g of vanilla aldehyde radical, using ball mill be uniformly mixed；Polyetheramine (D230, Aladdin provide) 70g is added, is stirred
It mixes uniformly mixed, first solidify at 70 DEG C 4 hours, then solidify 3 hours at 150 DEG C, that is, obtain fire retarding epoxide resin and solidify
Object.Through detecting, the anti-flammability of the obtained fire retarding epoxide resin solidfied material of the present embodiment reaches UL-94V0, bending strength 125MPa,
Tg is 115 DEG C.
Embodiment 3:
(1) by vanillic aldehyde 100g, 4,4'- diaminodiphenylmethane 65g, ethyl alcohol 500mL 40 DEG C react 1 hour, then
Diethyl phosphite 45g is added, is warming up to 90 DEG C and reacts 2 hours, obtain after petroleum ether precipitation, ethanol washing such as following formula (7) institute
The phosphorous bis-phenol of vanilla aldehyde radical shown.According to the hydrogen nuclear magnetic resonance spectrogram of the phosphorous bis-phenol of vanilla aldehyde radical it is found that1H nuclear magnetic resonance
There is 6.7-7.3ppm to represent the matter on 4,4 '-diaminodiphenyl-methanes and vanilla aldehyde structure phenyl ring in (d6-DMSO is solvent)
Sub- peak, 1.3ppm are the proton peak on diethyl phosphite structure methyl, 4,4 '-diaminodiphenyl-methane structure of 3.5ppm
The chemical shift of proton on methylene, 3.7ppm are the proton peak on vanilla aldehyde structure methyl.
(2) by bisphenol A type epoxy resin (E-54, Lanxing Chemical New Material Co., Ltd. provide) 80g, bisphenol A-type
It is synthesized in epoxy resin (E-20, Lanxing Chemical New Material Co., Ltd. provide) 20g, diammonium hydrogen phosphate 11g and step (1)
The phosphorous bis-phenol 2g of vanilla aldehyde radical, using ball mill be uniformly mixed；Dicyandiamide 50g and boron trifluoride (BF3) 1g are added, is stirred
It is uniformly mixed, first solidifies 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.Through detecting, the flame retardant property of the obtained fire retarding epoxide resin solidfied material of the present embodiment reaches
UL-94V0, bending strength 129MPa, Tg are 155 DEG C.
Comparative example 4: it is essentially identical with (2) the step of embodiment 3, but the vanilla aldehyde radical for not adding the synthesis of embodiment 3 is phosphorous
Bis-phenol.For the flame retardant property UL-94-V0 of obtained epoxy resin cured product without rank, bending strength 126MPa, Tg are 150 DEG C.
Comparative example 5: it is essentially identical with (2) the step of embodiment 3, but do not add diammonium hydrogen phosphate.Obtained epoxy resin is solid
For the flame retardant property UL-94-V0 of compound without rank, bending strength 130MPa, Tg are 165 DEG C.
Embodiment 4:
(1) vanillic aldehyde 100g, 4,4'- diamino-dicyclohexyl methane 65g, ethyl alcohol 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, is warming up to 90 DEG C of reactions 2
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 bromide react 2 hours in 80 DEG C, 40% NaOH aqueous solution 100g are added, 50
DEG C reaction 2 hours, washing, distillation obtain the phosphorous epoxide of vanilla aldehyde radical, epoxide number 0.195 as shown in following formula (9).
According to the hydrogen nuclear magnetic resonance spectrogram of the phosphorous epoxide of vanilla aldehyde radical it is found that1H 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 represent the proton peak being connected on the characteristic chemical shifts and alicyclic ring of proton with imido grpup in epoxy group,
1.1~1.8ppm is its in addition to proton on the methylene being connected with imido grpup of 4,4 '-diamino-dicyclohexyl methane structures
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 synthesized in step (1) is uniformly mixed using ball mill；Add diethylenetriamine
20g, tung oil acid anhydride 5g and tetrabutylammonium bromide 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, i.e. acquisition fire retarding epoxide resin solidfied material at 160 DEG C.Through detecting, the present embodiment obtains resistance
The UL-94V0 of epoxy resin cured product is fired, bending strength 130MPa, Tg are 170 DEG C.
Embodiment 5:
(1) vanillic aldehyde 100g, m-phenylene diamine (MPD) 36g, ethyl alcohol 500mL are reacted 1 hour at 40 DEG C, zinc chloride is then added
2.5g and diphenyl phosphite 154g is warming up to 90 DEG C and reacts 2 hours, obtains 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 bromide
It answers 2 hours, adds 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 0.036.It is total according to the nuclear-magnetism of the phosphorous epoxide of vanilla aldehyde radical
Shake hydrogen spectrogram it is found that1There 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 phenyl ring on two imino group ortho position protons
Displacement study, tri- peaks 2.3~3.5ppm represent the characteristic chemical shifts of proton in epoxy 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, Ba Ling Huaxing provide) 70g, Bisphenol F
It is synthesized in type epoxy resin (EPICLON 830LVP, big Japanese ink company provide) 30g, ammonium pyrophosphate 7g and step (1)
The phosphorous epoxide 4g of vanilla aldehyde radical is uniformly 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, i.e. acquisition fire retarding epoxide resin at 200 DEG C
Solidfied material.Through detecting, the UL-94V0 of the obtained fire retarding epoxide resin solidfied material of the present embodiment, bending strength 135MPa, Tg are
120℃。
Embodiment 6:
(1) vanillic aldehyde 100g, 1,6- hexamethylene diamine 38g, ethyl alcohol 500mL are reacted 1 hour at 40 DEG C, phosphorous acid is then added
Dimethyl ester 72g is warming up to 90 DEG C and reacts 2 hours, obtains the vanillic aldehyde as shown in following formula (12) after petroleum ether precipitation, ethanol washing
The phosphorous bis-phenol of base, then reacted 2 hours with 20g epoxychloropropane and 10g cetyl trimethylammonium bromide in 80 DEG C, it adds
40% NaOH aqueous solution 60g reacts 2 hours at 50 DEG C, and washing, distillation are obtained as vanilla aldehyde radical shown in following formula (13) is phosphorous
Epoxide, epoxide number 0.027.According to the hydrogen nuclear magnetic resonance spectrogram of the phosphorous epoxide of vanilla aldehyde radical it is found that1There 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 in epoxy group on the characteristic chemical shifts of proton and the methylene being connected with imido grpup, 1.1~
1.8ppm is the chemical shift of other protons of 1, the 6- hexamethylene diamine 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 provides) 100g, pfpe acid ammonium 5g and step
(1) the phosphorous epoxide 8g of vanilla aldehyde radical synthesized in is uniformly mixed using ball mill；Add itaconic anhydride 55g and 2-
Methylimidazole 5g, is uniformly mixed, and solidifies 3 hours, i.e. acquisition flame retardant epoxy tree at solidifying 7 hours, 190 DEG C at 120 DEG C
Rouge solidfied material.Through detecting, the UL-94V0 of the obtained fire retarding epoxide resin solidfied material of the present embodiment, bending strength 125MPa, Tg are
145℃。
Embodiment 7:
(1) vanillic aldehyde 100g, 1,3- propane diamine 24g, ethyl alcohol 500mL are reacted 1 hour at 40 DEG C, zinc chloride is then added
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 cetyl
Trimethylammonium bromide reacts 2 hours in 80 DEG C, adds 40% NaOH aqueous solution 60g, reacts 2 hours at 50 DEG C, and washing is steamed
Evaporate to obtain the phosphorous epoxide of vanilla aldehyde radical, epoxide number 0.029 as shown in following formula (15).It is phosphorous according to the vanilla aldehyde radical
The hydrogen nuclear magnetic resonance spectrogram of epoxide it is found that1There is 6.7-8.3ppm representative 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 generation
Proton peak in table epoxy group on the characteristic chemical shifts of proton and the methylene being connected with imido grpup, 1.6ppm 1,3- third
Proton peak on diamine structures mid methylenes, 3.8ppm are the proton peak on vanilla aldehyde structure methyl.
(2) by novolac epoxy resin (NPPN-631, South Asia plastics industry limited liability company provide) 100g, ammonium pyrophosphate
The 3g and middle phosphorous epoxide 10g of vanilla aldehyde radical synthesized of step (1), is uniformly 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 solidifies 5 hours at 130 DEG C, then solidify 5 hours at 170 DEG C, that is, obtain fire-retardant ring
Oxygen resin cured matter.Through detecting, UL-94V0, the bending strength 90MPa of the obtained fire retarding epoxide resin solidfied material of the present embodiment,
Tg is 100 DEG C.
Embodiment 8:
(1) vanillic aldehyde 100g, ethylenediamine 15g, ethyl alcohol 500mL are reacted 1 hour at 40 DEG C, zinc chloride 2.5g is then added
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, ethyl alcohol
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 three
Base ammonium bromide reacts 2 hours in 80 DEG C, adds 40% NaOH aqueous solution 60g, reacts 2 hours at 50 DEG C, washes, distills
To the phosphorous epoxide of vanilla aldehyde radical, epoxide number 0.029 as shown in following formula (17).According to the phosphorous epoxy of vanilla aldehyde radical
The hydrogen nuclear magnetic resonance spectrogram of compound it is found that1There 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 phenanthrene -10- oxide of dihydro-9-oxy and vanilla aldehyde structure phenyl ring, 2.3~3.9ppm represent epoxy
The characteristic chemical shifts of proton and the proton peak on the methylene being connected with nitrogen and the proton on vanilla aldehyde structure methyl on group
Peak.
(2) the vanilla aldehyde radical synthesized in bisphenol A type epoxy resin (E-44) 100g, ammonium polyphosphate 9g and step (1) is contained
Phosphorus bis-phenol 1g is uniformly mixed using ball mill；It adds diaminodiphenylsulfone 20g to be uniformly mixed, first then at 100 DEG C
Lower solidification 4 hours finally solidifies 4 hours, i.e. acquisition fire retarding epoxide resin solidfied material at 200 DEG C.Through detecting, the present embodiment institute
The flame retardant property for obtaining fire retarding epoxide resin solidfied material reaches UL-94V0, and bending strength 160MPa, Tg are 170 DEG C.
Embodiment 9:
(1) by vanillic aldehyde 100g, 1,20- eicosane diamine 50g, ethyl alcohol 500mL 40 DEG C react 1 hour, then plus
Enter diphenyl phosphite 72g, is warming up to 120 DEG C and reacts 0.5 hour, obtain after petroleum ether precipitation, ethanol washing such as following formula (18)
Shown in the phosphorous bis-phenol of vanilla aldehyde radical, then reacted 1 hour with 20g epoxychloropropane and 1g tetrabutylammonium bromide in 100 DEG C, then plus
The NaOH aqueous solution 60g for entering 40% reacts 2 hours at 50 DEG C, and washing, distillation obtain the vanilla aldehyde radical as shown in following formula (19) and contain
Phosphorus epoxide, epoxide number 0.021.According to the hydrogen nuclear magnetic resonance spectrogram of the phosphorous epoxide of vanilla aldehyde radical it is found that
?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 are represented in epoxy group on the characteristic chemical shifts of proton and the methylene being connected with imido grpup
Proton peak, 0.8-1.8ppm 1, other in addition to proton on the methylene that is connected with imido grpup of 20- eicosane diamine structures
The chemical shift of proton, 3.7ppm are the proton peak on vanilla aldehyde structure methyl.
(2) by bisphenol f type epoxy resin (D.E.R.TM354, DOW Chemical provides) 100g, ammonium polyphosphate 5g and step
(1) the phosphorous epoxide 5g of vanilla aldehyde radical synthesized in is uniformly mixed using ball mill；Add phenolic resin 50g and 2-
Methylimidazole 1g, is uniformly mixed, and first solidifies 10 hours at 140 DEG C, then solidifies 1 hour at 200 DEG C, that is, hindered
Fire epoxy resin cured product.Through detecting, the UL-94V0 of the obtained fire retarding epoxide resin solidfied material of the present embodiment, bending strength is
100MPa, Tg are 110 DEG C.
Pass through the comparison of embodiment 1-9 and comparative example 1-5, it can be seen that, it is obtained by above-mentioned technical proposal of the invention
Fire retarded epoxy resin composition solidification after, not only there is excellent flame retardant property, while there is high glass transition temperature
The excellent comprehensive performance with intensity etc..
In addition, inventor also refers to the mode of embodiment 1- embodiment 9, with the other raw materials listed in this specification
It is 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 those of ordinary skill in the art
For, under the premise of not departing from concept of the invention, other modification and improvement can also be made, these belong to this hair
Bright protection scope.
Claims (9)
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, and has formula (1)~formula
(4) structure shown in any one in:
Wherein R1For
R2For linear paraffin or aromatic hydrocarbon or alicyclic ring alkane structure with 2-20 carbon atom, 0≤n≤10；
The epoxy resin is selected from bisphenol A type epoxy resin, bisphenol f type epoxy resin, glycidyl ester type epoxy resin, shrink
Any one in glyceramine type epoxy resin and novolac epoxy resin or two or more combinations；The main flame retardant is selected from poly-
Ammonium phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, any one or two or more combinations in ammonium pyrophosphate；It is described
The flame retardant property of the solidfied material of the composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla is not less than UL-94 V0, bending strength
In 90MPa or more, glass transition temperature is at 100 DEG C or more.
2. composition epoxy resin according to claim 1, it is characterised in that: the curing agent be selected from amine curing agent,
Any one in acid anhydride type curing agent and phenolic resin or two or more combinations.
3. composition epoxy resin according to claim 2, it is characterised in that: the amine curing agent is selected from divinyl three
In amine, 4,4 '-diaminodiphenylmethane, amido amine, polyamide, polyetheramine and dicyandiamide any one or it is two or more
Combination.
4. composition epoxy resin according to claim 2, it is characterised in that: the acid anhydride type curing agent is selected from methyl six
Any one in hydrogen phthalic anhydride, itaconic anhydride and tung oil acid anhydride or two or more combinations.
5. composition epoxy resin according to claim 1, it is characterised in that: the curing accelerator is selected from tertiary amine, season
Any one in amine salt, organic base and lewis acid or two or more combinations.
6. composition epoxy resin according to claim 5, it is characterised in that: the curing accelerator is selected from 2- methyl miaow
Azoles, tetrabutylammonium bromide, 2,4,6- tri- (dimethylamino methyl) phenol, any one or two or more groups in boron trifluoride
It closes.
7. the solidfied material of the composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla as described in any one of claim 1-6,
Its flame retardant property is not less than UL-94 V0, and bending strength is in 90MPa or more, and glass transition temperature is at 100 DEG C or more.
8. the preparation method of solidfied material as claimed in claim 7, characterized by comprising: will be any in composition claim 1-6
The each component of the composition epoxy resin of the phosphonium flame retardant of aldehyde radical containing vanilla described in uniformly mixes, and solidifies later in 50~90 DEG C
0.5~10 hour, in 90~150 DEG C solidify 0.5~10 hour, in 150~200 DEG C solidify 0~10 hour, obtain the solidification
Object.
9. the composition epoxy resin or claim of the phosphonium flame retardant of aldehyde radical containing vanilla as described in any one of claim 1-6
Solidfied material described in 7 is in preparing the purposes in fire proofing.
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| US10266771B2 (en) | 2017-05-02 | 2019-04-23 | International Business Machines Corporation | Bondable flame-retardant vanillin-derived molecules |
| US10167427B2 (en) | 2017-05-02 | 2019-01-01 | International Business Machines Corporation | Flame-retardant vanillin-derived cross-linkers |
| US10214693B2 (en) | 2017-05-02 | 2019-02-26 | International Business Machines Corporation | Flame-retardant vanillin-derived small molecules |
| US10266772B2 (en) | 2017-05-02 | 2019-04-23 | International Business Machines Corporation | Flame-retardant vanillin-derived monomers |
| CN108148095B (en) * | 2017-12-29 | 2019-10-18 | 福建师范大学 | A kind of tertiary amine-type flame retardant curing agent and preparation method thereof for epoxy resin |
| CN110386907B (en) * | 2019-06-18 | 2023-04-25 | 东华大学 | Epoxy resin monomer containing imine bond, and preparation method and application thereof |
| CN110746646B (en) * | 2019-09-16 | 2021-05-18 | 皖西学院 | Biomass-based flame retardant and preparation method thereof |
| CN111875593B (en) * | 2020-08-10 | 2021-09-28 | 中国科学院宁波材料技术与工程研究所 | Low-viscosity bio-based flame-retardant epoxy resin precursor and preparation method and application thereof |
| CN112521660B (en) * | 2020-11-11 | 2021-08-06 | 厦门大学 | Titanium dioxide hybrid nano particle flame retardant containing phosphorus, nitrogen and silicon and preparation method and application thereof |
| CN112961321A (en) * | 2021-02-19 | 2021-06-15 | 江南大学 | Heat-conducting intrinsic flame-retardant lignin derivative-based epoxy resin composite material and preparation method thereof |
| CN113698575B (en) * | 2021-09-02 | 2022-04-26 | 四川大学 | Siloxane Schiff base structure-based high-impact-resistance remodelable flame-retardant epoxy resin and preparation method thereof |
| CN114409873B (en) * | 2022-02-21 | 2024-04-16 | 中国民用航空飞行学院 | Vanillin basic sign flame-retardant epoxy resin containing fatty amine and preparation method thereof |
| CN115028965A (en) * | 2022-06-24 | 2022-09-09 | 福建师范大学 | Modified epoxy resin and preparation method thereof |
| CN114874266A (en) * | 2022-06-24 | 2022-08-09 | 福建师范大学 | Biomass flame retardant applied to epoxy resin and preparation method thereof |
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