CN108192078A - A kind of preparation method of biology base fire retarding epoxide resin and its biology base fire retarding epoxide resin obtained - Google Patents
A kind of preparation method of biology base fire retarding epoxide resin and its biology base fire retarding epoxide resin obtained Download PDFInfo
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- CN108192078A CN108192078A CN201711211145.6A CN201711211145A CN108192078A CN 108192078 A CN108192078 A CN 108192078A CN 201711211145 A CN201711211145 A CN 201711211145A CN 108192078 A CN108192078 A CN 108192078A
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- biology base
- acetone
- solution
- temperature
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 35
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 32
- 230000000979 retarding effect Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004593 Epoxy Substances 0.000 claims abstract description 32
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 150000001412 amines Chemical class 0.000 claims abstract description 18
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940074391 gallic acid Drugs 0.000 claims abstract description 15
- -1 phospho Chemical class 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 159
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 149
- 239000000047 product Substances 0.000 claims description 89
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 66
- 239000000203 mixture Substances 0.000 claims description 46
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000001914 filtration Methods 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 26
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 239000012074 organic phase Substances 0.000 claims description 22
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 22
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 14
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 13
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 13
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 13
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000012043 crude product Substances 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 11
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 11
- 229940100630 metacresol Drugs 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 235000002639 sodium chloride Nutrition 0.000 claims description 11
- 235000010265 sodium sulphite Nutrition 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 150000002240 furans Chemical class 0.000 claims description 6
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 4
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- OXOWWPXTTOCKKU-UHFFFAOYSA-N 2-propoxybenzoic acid Chemical class CCCOC1=CC=CC=C1C(O)=O OXOWWPXTTOCKKU-UHFFFAOYSA-N 0.000 claims description 3
- ULQQGOGMQRGFFR-UHFFFAOYSA-N 2-chlorobenzenecarboperoxoic acid Chemical compound OOC(=O)C1=CC=CC=C1Cl ULQQGOGMQRGFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229960002668 sodium chloride Drugs 0.000 claims description 2
- DXTLCLWOCYLDHL-UHFFFAOYSA-N 2-ethoxybenzonitrile Chemical compound CCOC1=CC=CC=C1C#N DXTLCLWOCYLDHL-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 abstract description 31
- 239000001301 oxygen Substances 0.000 abstract description 31
- 239000003063 flame retardant Substances 0.000 abstract description 21
- 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 abstract description 18
- 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 abstract description 12
- 238000002485 combustion reaction Methods 0.000 abstract description 10
- 125000003700 epoxy group Chemical group 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 abstract 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 abstract 1
- 125000005842 heteroatom Chemical group 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- 239000002585 base Substances 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000012266 salt solution Substances 0.000 description 10
- 229920006395 saturated elastomer Polymers 0.000 description 10
- 239000003643 water by type Substances 0.000 description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 9
- 239000003610 charcoal Substances 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000002411 thermogravimetry Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000005711 Benzoic acid Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 235000010233 benzoic acid Nutrition 0.000 description 5
- 229940106691 bisphenol a Drugs 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 229920006152 PA1010 Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000005713 exacerbation Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 244000103090 Eucalyptus robusta Species 0.000 description 1
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 240000003152 Rhus chinensis Species 0.000 description 1
- 235000014220 Rhus chinensis Nutrition 0.000 description 1
- 235000005291 Rumex acetosa Nutrition 0.000 description 1
- 240000007001 Rumex acetosella Species 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 244000290333 Vanilla fragrans Species 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical group C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 239000010773 plant oil Substances 0.000 description 1
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000003513 sheep sorrel Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000005221 swamp mahogany Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 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
- C08G59/18—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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- 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
- C08G59/26—Di-epoxy compounds heterocyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy 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
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a kind of full biology base fire retarding epoxide resins, it is to utilize the active group on gallic acid, introduce 9,10 dihydro, 9 oxa-, 10 phospho hetero phenanthrene, 10 oxide (DOPO) and epoxy group, obtain biology base epoxy monomer, substitute the bisphenol A epoxide resin DGEBA used on general industry, and synthesize a kind of higher biology base curing agent of activity --- two chaff amine, it is mixing cured under certain condition with epoxy monomer obtained, the full biology base epoxy resin product with flame retardant property is made.This kind of epoxy resin biological source is extensive, and environmentally protective, reaction process is relatively simple, and flame retardant property is good, and limit oxygen index can reach 34%, and vertical combustion grade can reach 0 grade of V.The invention discloses its preparation methods.
Description
Technical field
The present invention relates to a kind of full biology base fire retarding epoxide resins, introduce P elements in biology base epoxy monomer, make it
Possess good flame retardant property.
Background technology
Petroleum-based plastics can be building, automobile, machine-building, electronic information since it is with various excellent performances
Etc. all trades and professions various raw material and product are provided, played a very important role in modern society's life, still, in face of working as
The problem of increasingly exacerbation of modern world oil energy crisis and environmental pollution, people are begun look for biomass and renewable resource
For raw material, making meets the new material of demand to replace petroleum based material.Most biological materials are nontoxic, and content
It is abundant, the pressure of lack of energy and pollution exacerbation can be alleviated, reduce the dependence that plastic industry supplies petroleum-based chemical product,
Reduce environmental pollution caused by high molecular material production process.At present, the main office of research in relation to biology base high molecular material
It is limited to some natural polymers or the thermoplastic materials such as starch plastic, cellulosic-based material, PHBV, PLA, PBS, biology base PE,
Biological based thermoset applications are studied then relatively fewer.
Epoxy resin is one of most widely used thermosetting resin, the annual yield in the whole world at 2,000,000 tons or so, wherein
Bisphenol A epoxide resin accounts for more than 85%, is mainly prepared by 2 kinds of raw materials of bisphenol-A and epoxychloropropane.Epoxychloropropane can
It is made by biological base glycerol, has been carried out industrialization, the fossil resources but more than 67% bisphenol-A places one's entire reliance upon at present.Together
When bisphenol-A exist to the health of life entity and greatly threaten, the environmentally friendly resin for developing alternative bisphenol A epoxide resin shows
It obtains significant.Meanwhile the oxygen index (OI) of epoxy resin is 19.8, can be burnt in air after igniting, and burning velocity is very fast,
Therefore the flame retardant property of epoxy resin how is improved, expands the big subject that its application range is also applied research.
It is flame-retardant modified to epoxy resin progress, the chemical element with flame retardant property can be introduced epoxy resin solidifying system
In.By ignition-proof element introduce curing system method it is general there are two types of：Response type and non-reactive.Non-reactive is to use physics
Mode handles base material, and fire retardant is added directly by ignition resistant substrate, and this anti-method is simple and practicable, but due to fire retardant with
The incompatible mechanical performance for causing material of base material declines；Response type is then that ignition-proof element is introduced into epoxy molecule skeleton, altogether
Valency is connected on polymer molecular chain, can improve flame retarding efficiency to avoid the migration of fire retardant.
Gallic acid (GA) is the Hydrolysis of compound of natural plants polyphenol, and content of the plant polyphenol in plant is rich
Richness derives from a wealth of sources, and can synthesize more phenol-type epoxy resins, aromatic structure also can containing 1 carboxyl and 3 hydroxyls in structure
Assign the good thermomechanical property of epoxy resin.102276788 A of Chinese patent CN disclose a kind of ring based on gallic acid
Oxygen resin and preparation method thereof, by gallic acid, epoxy halogenopropane and catalyst mix after, 100~120 DEG C react 2~
5h, is then cooled to 20~40 DEG C, adds in alkali compounds and water, the reaction was continued 2~5h, wash, go solvent, it is dry after obtain
Epoxy resin based on gallic acid, preparation process is simple, controllability is good, is easy to industrializing implementation.But excessive epoxy
Halogenopropane tends not to react with gallic acid completely, and easily generates epoxy oligomer rather than epoxy monomer with acid.Specially
Sharp CN106519712A discloses a kind of full biology base epoxidised soybean oil resin of high-performance, by epoxidised soybean oil and polyamide
1010 prepolymers are prepared by curing in the presence of a catalyst, and drawing Zhong Qiangdu is 5-38.5MPa, fracture enlongation rate 55%-
356%, there is excellent mechanical performance.It is used to prepare the monomer of polyamide 1010 prepolymer, i.e., decanedioic acid and decamethylene diamine be also all
From renewable resource, the curing agent as epoxidized soybean oil.But since plant oil base contains longer aliphatic chain, and containing virtue
The epoxy resin of perfume base group is compared, and thermal stability is poor.US patents WO2016172353A1 discloses one kind and comes from vanilla
The preparation method of the epoxy resin of aldehyde.Vanillic aldehyde base epoxy is made first with schiff base reaction, then by glycidyl.
Obtained epoxy monomer activity is high, can be used as resinous coat.But the epoxide group quantity in its epoxy monomer is less, leads to it
The crosslink density of final solidfied material is relatively low.、
The present invention provides a kind of preparation method of full biology base fire retarding epoxide resin, since raw material sources are in nutgall
Acid, it is a kind of polyphenol compound existing for nature, is widely present in the plants such as sorrel, eucalyptus robusta, Fructus Corni,
Therefore meet the standard of environmental protection and energy saving.P elements in epoxy monomer, aromatic structure, the presence of multiple epoxy groups so that final
The thermal stability of the epoxy resin of preparation improves a lot compared with industrial epoxy resin, and limit oxygen index can reach
More than 30%
Invention content
Traditional synthetic resin anti-flammability is poor and raw material are toxic it is an object of the invention to solving, and non-renewable asks
Topic, provides a kind of preparation method of full biology base fire retarding epoxide resin.This method raw material is cheap and easy to get, and reaction process is more simple
It is single, too harsh reaction condition is not needed to, epoxy monomer epoxy group is more, improves the crosslink density of epoxy resin, fragrance
Structure also contributes to the raising of material thermal stability, as curing agent furans diamines curing activity with it is industrial general solid
Agent activity is quite.The introduction of P elements effectively increases its flame retardant property.In order to realize more than goal of the invention, skill of the invention
Art scheme is as follows：
A kind of preparation method of full biology base fire retarding epoxide resin, which is characterized in that gallic acid is as initial feed, by alkene
Propylated, addition reaction occurs for -10- phosphas -10- oxides (DOPO) miscellaneous with 9,10- dihydro-9-oxies, using oxidation reaction
Epoxy group is introduced, it is mixing cured in a heated condition with the two chaff amine as made from chaff amine, obtain final product, the biology
Base epoxy monomer and curing agent, synthesis include the following steps：
Step 1, toward adding in solvent, potassium carbonate and gallic acid in flask, 5~20min of strong stirring, then, 20~
The solution of allyl bromide, bromoallylene is slowly added in 60min, mixture is heated to 50~80 DEG C, keeps 20~48h, mistake at this temperature
Filter, obtained solution is rotated, most crude product is dissolved in dichloromethane at last, with saturated common salt water washing, dichloromethane layer
Revolving evaporation obtains smart product, and 7~15h of vacuum drying obtains 1: 3,4,5- triolefin propoxy benzoic acid of product at 50~80 DEG C
Ester；The molar ratio of gallic acid and potassium carbonate is 1: 5~11, and the molar ratio of gallic acid and allyl bromide, bromoallylene is 1: 6~12；It chooses
Solvent be one kind in tetrahydrofuran, acetone, dichloromethane or ether；
Its reaction is as follows：
Added in step 2, the round-bottomed flask with condenser pipe the miscellaneous -10- phosphas -10- oxides of 9,10- dihydro-9-oxies and
Solvent, flask are heated to 60~100 DEG C under argon atmosphere, and the miscellaneous -10- phosphas -10- oxides of 9,10- dihydro-9-oxies are completely molten
Xie Hou adds in product 1 in 30~80min, and reaction mixture keeps 10~40h at this temperature, after being cooled to room temperature, mistake
Filter obtains product, is cleaned 2~5 times with mixed solvent, 3~8h is then dried in vacuo at 80~140 DEG C, obtains product 2：DOPO
Base 3,4,5- triolefin propoxy benzoic acid esters；The molar ratio of product 1 and the miscellaneous -10- phosphas -10- oxides of 9,10- dihydro-9-oxy
It is 1: 1~2.2；The mixed solvent is two kinds of solvents in dimethylbenzene or tetrahydrofuran and dichloromethane or acetone with volume
Than 1: 1 mixing；；
Its reaction is as follows：
Solution, the metachloroperbenzoic acid and 4 of product 2,4 '-thiobis (first between 6- tertiary butyls are added in step 3, flask
Phenol reacts 40~60h at 20~50 DEG C, is subsequently cooled to 0~-10 DEG C, keeps 3~10h at this temperature, is filtered to remove filter
Slag, filtrate are washed successively with 10% sodium sulfite solution, 5% sodium carbonate liquor and saturated sodium-chloride water solution, anhydrous sulphur
Sour magnesium removes water remaining in organic phase and is then rotated, and obtained solid is dissolved in 5ml dichloromethane, pours 10 times into
Cold methanol in, the precipitation that is obtained by filtration is dried in vacuo 40~60h at 20~50 DEG C, obtains 3,4,5- tricyclic ethoxy of DOPO bases
The molar ratio of yl benzoic acid ester, product 2 and metachloroperbenzoic acid is 1: 9~12, product 2 and 4,4 '-thiobis (6- tertiary butyls
Metacresol) molar ratio be 3~6: 1；The solvent of the solution for the product 2 chosen is tetrahydrofuran, acetone, dichloromethane
Or one kind in ether；
Its reaction is as follows：
Step 4 adds in chaff amine in the round-bottomed flask with reflux condensing tube, is cooled to -5~5 DEG C, it is added dropwise 10~
The hydrochloric acid of 20w%, then temperature rise to 20~35 DEG C, stir 10~30min, acetone added in into mixture, temperature is improved to 30
~60 DEG C, a certain amount of acetone is added, reaction is completed after 5~10 days, adds acetone, and mixture is cooled to 20~30 DEG C,
100~200ml deionized waters are added in, adjust pH to 8~13 with 15wt%NaOH solution, mixture extracts 2~5 with ethyl acetate
Secondary, organic phase is washed with sodium-chloride water solution, is dried with anhydrous magnesium sulfate, and revolving removes ethyl acetate, obtains biology base curing agent
The molar ratio of furans dimethylamine, chaff amine and hydrochloric acid is 1: 2~4, and chaff amine and the molar ratio of acetone added in three times are 1: 2~4:
0.1~0.4: 0.1~0.4；
The structure of the product of gained is as follows：
Step 5, the phosphorous epoxy monomer for obtaining step 3 stir 8~30min at 30~80 DEG C, add in step 4 and obtain
Biology base curing agent furans dimethylamine, the mass ratio of phosphorous epoxy monomer and biology base curing agent furans dimethylamine for 1: 2~
4,3~8min is stirred, the mold of preheating is poured into, cures 4h at 80 DEG C, cure 10h at 150 DEG C, full biology base flame retardant epoxy is made
Resin.
One kind full biology base fire retarding epoxide resin product as made from above-mentioned preparation method.
Compared with prior art, beneficial effects of the present invention are as follows：
(1) epoxy resin for preparing of the present invention, raw material are all derived from renewable resource, cheap environmental protection and energy saving, entirely
Reaction process is simply less toxic；
(2) by the use of gallic acid as the raw material for preparing epoxy monomer, aromatic structure helps to improve the heat of material
Stability, multiple functional groups also contribute to introduce epoxy group, improve the crosslink density of epoxy resin；
(3) addition reaction occurs using the P-H keys of DOPO and double bond and introduces P elements, improve the anti-flammability of epoxy resin
Energy；
Specific embodiment
A kind of preparation method of full biology base fire retarding epoxide resin of the present invention is illustrated using embodiment below.Implement
Example is that the present invention is described in further detail, but they do not form the present invention and limit.
Embodiment 1：
(1) 20ml tetrahydrofurans, 0.088mol potassium carbonate are packed into sealed flask, 0.0176mol gallic acids strongly stir
Mix 5min.Then, the solution of allyl bromide, bromoallylene is slowly added in 20min.Mixture is heated to 50 DEG C, keeps at this temperature
20h.Obtained product is filtered to remove the impurity in solution, revolving.Most crude product is dissolved in dichloromethane at last, uses saturated salt solution
Washing.Dichloromethane layer revolving evaporation obtains smart product, and vacuum drying 7h obtains product 1 at 50 DEG C.
(2) 0.0176molDOPO, 30ml tetrahydrofurans, in argon atmosphere are added in the round-bottomed flask with condenser pipe
Under be heated to 60 DEG C.After DOPO is completely dissolved, 0.0176mol products 1 add in 30min, and reaction mixture is at this temperature
Keep 10h.After being cooled to room temperature, product is obtained by filtration, is washed 2 times with tetrahydrofuran/dimethylbenzene (1: 1), then at 80 DEG C
3h is dried in vacuo, obtains product 2.
(3) tetrahydrofuran solution (30ml) of product 2 (0.0176mol), the m-chloro peroxide of 0.1584mol are added in flask
Benzoic acid and 0.00587mol 4,4 '-thiobis (6- tertiary butyls metacresol) react 40h at 20 DEG C, are subsequently cooled to 0 DEG C,
3h is kept at a temperature of this, is filtered to remove filter residue, 10% sodium sulfite solution of filtrate, 5% sodium carbonate liquor and saturation food
Brine washs successively, and anhydrous magnesium sulfate removes water remaining in organic phase, is then rotated, obtained solid is dissolved in 5ml
It in dichloromethane, pours into and precipitation is obtained by filtration in 10 times of cold methanol, 40h is dried in vacuo at 20 DEG C, phosphorous epoxy monomer is made
(4) 0.1mol chaffs amine is added in the round-bottomed flask with reflux condensing tube, is cooled to -5 DEG C.10w% is added dropwise
Hydrochloric acid (0.2mol).Then temperature rises to 20 DEG C, stirs 10min.0.2mol acetone is added in into mixture.Temperature is heated to 30
℃.Add 0.01mol acetone.Reaction is completed after 5 days, adds 0.01mol acetone.Mixture is cooled to 20 DEG C, adds in
100ml deionized waters.PH to 8 is adjusted with 15wt%NaOH solution, mixture is extracted 2 times with ethyl acetate.Organic phase salt
Water washing is dried with anhydrous magnesium sulfate, and revolving removes ethyl acetate, and biology base curing agent is made.
(5) phosphorous epoxy monomer at 30 DEG C is finally stirred into 8min, adds in biology base curing agent (ratio 1: 2w/w),
3min is stirred, pours into the mold of preheating, 4h at 80 DEG C, 10h at 150 DEG C.
Thermogravimetric analysis is carried out to sample, heating rate is 10 DEG C/min, residual when initial decomposition temperature is 305 DEG C, 800 DEG C
Charcoal rate is 32%.
According to GB/T2046.2-2009, its limit oxygen index is levied with limit oxygen index instrument, limit oxygen index is
27.3%.
Using CZF-3 type horizontal vertical combustion appliances, sample strip specification is：Length × width x thickness=130.0mm × 12.7mm
× 3.2mm, it is V-1 grades to obtain the sample flame retardant property grade.
Embodiment 2：
(1) 20ml dichloromethane, 0.088mol potassium carbonate and 0.0176mol gallic acids, strength are packed into sealed flask
Stir 20min.Then, the dichloromethane solution of allyl bromide, bromoallylene is slowly added in 60min.Mixture is heated to 80 DEG C, at this
At a temperature of keep 48h.Obtained product filtering, revolving.Most crude product is dissolved in dichloromethane at last, is cleaned with saturated salt solution.
Dichloromethane layer revolving evaporation obtains smart product, and vacuum drying 15h obtains product 1 at 80 DEG C.
(2) 0.0176molDOPO is added in the round-bottomed flask with condenser pipe, 80ml dichloromethane, flask is in argon atmospher
100 DEG C are heated under enclosing.After DOPO is completely dissolved, 0.0176mol products 1 add in 80min, and reaction mixture is in this temperature
Lower holding 40h.After being cooled to room temperature, product is obtained by filtration, cleans 5 times with dimethylbenzene/tetrahydrofuran mixed solution (1: 1), so
8h is dried in vacuo at 140 DEG C afterwards, obtains product 2.
(3) dichloromethane solution (80ml) of product 2 (0.0176mol), 0.01584mol m-chloro peroxides are added in flask
Benzoic acid, 0.00587mol4,4 '-thiobis (6- tertiary butyls metacresol).60h is reacted at 50 DEG C, is subsequently cooled to -10 DEG C,
10h is kept at a temperature of this, is filtered to remove filter residue, 10% sodium sulfite solution of filtrate, 5% sodium carbonate liquor, saturation food
Brine cleans, and anhydrous magnesium sulfate removes water remaining in organic phase and then rotated.Obtained solid is dissolved in 5ml dichloromethanes
In alkane, pour into and precipitation is obtained by filtration in 10 times of cold methanol.Finally, 60h is dried in vacuo at 50 DEG C.
(4) chaff amine (0.1mol) is added in the round-bottomed flask with reflux condensing tube, is cooled to 5 DEG C.The hydrochloric acid of 20w%
(0.2mol) is added dropwise.Then temperature rises to 35 DEG C, stirs 30min.0.2mol acetone adds in mixture.Temperature is improved to 60
℃.Add 0.01mol acetone.Reaction is completed after 10 days, adds 0.01mol acetone.Mixture is cooled to 30 DEG C, adds in
200ml deionized waters.PH to 13 is adjusted with 15wt%NaOH solution, mixture is extracted 5 times with ethyl acetate.Organic phase salt
Water cleans, and is dried with anhydrous magnesium sulfate, and revolving removes ethyl acetate.
Phosphorous epoxy monomer at 80 DEG C is finally stirred into 30min, adds in biology base curing agent (ratio 1：4w/w), it stirs
8min is mixed, pours into the mold of preheating, 4h at 80 DEG C, 10h at 150 DEG C.
Thermogravimetric analysis is carried out to sample, heating rate is 10 DEG C/min, residual when initial decomposition temperature is 308 DEG C, 800 DEG C
Charcoal rate is 33.2%.
According to GB/T2046.2-2009, its limit oxygen index is levied with limit oxygen index instrument, limit oxygen index is
27.5%.
Using CZF-3 type horizontal vertical combustion appliances, sample strip specification is：Length × width x thickness=130.0mm × 12.7mm
× 3.2mm, it is V-1 grades to obtain the sample flame retardant property grade.
Embodiment 3：
(1) 30ml acetone, 0.088mol potassium carbonate and 0.0176mol gallic acids, strong stirring are packed into sealed flask
15min.Then, the acetone soln of allyl bromide, bromoallylene is slowly added in 40min.Mixture is heated to 60 DEG C, protects at this temperature
Hold 30h.Obtained product filtering, revolving.Most crude product is dissolved in dichloromethane at last, is cleaned with saturated salt solution.Dichloromethane
Layer revolving evaporation obtains smart product, and vacuum drying 10h obtains product 1 at 70 DEG C.
(2) 0.0176molDOPO is added in the round-bottomed flask with condenser pipe, 50ml acetone, flask is under argon atmosphere
It is heated to 80 DEG C.After DOPO is completely dissolved, 0.0176mol products 1 add in 50min, and reaction mixture is protected at this temperature
Hold 30h.After being cooled to room temperature, product is obtained by filtration, is cleaned 3 times with dimethylbenzene/tetrahydrofuran (1: 1), it is then true at 100 DEG C
The dry 5h of sky, obtains product 2.
(3) acetone soln (50ml) of product 2 (0.0176mol), 0.1584mol m-chloro peroxide benzene first are added in flask
Acid, 0.00587mol4,4 '-thiobis (6- tertiary butyls metacresol).50h is reacted at 30 DEG C, is subsequently cooled to -5 DEG C, it is warm herein
Degree is lower to keep 7h, is filtered to remove filter residue, 10% sodium sulfite solution of filtrate, 5% sodium carbonate liquor, and saturated salt solution is clear
It washes, anhydrous magnesium sulfate removes water remaining in organic phase and then rotated.Obtained solid is dissolved in 5ml dichloromethane,
It pours into and precipitation is obtained by filtration in 10 times of cold methanol.Finally, 50h, product 2 are dried in vacuo at 30 DEG C.
(4) chaff amine (0.1mol) is added in the round-bottomed flask with reflux condensing tube, is cooled to 0 DEG C.The hydrochloric acid of 15w%
(0.2mol) is added dropwise.Then temperature rises to 30 DEG C, stirs 20min.0.2mol acetone adds in mixture.Temperature is improved to 40
℃.Add 0.01mol acetone.Reaction is completed after 7 days, adds 0.01mol acetone.Mixture is cooled to 25 DEG C, adds in
150ml deionized waters.PH to 10 is adjusted with 15wt%NaOH solution, mixture is extracted 3 times with ethyl acetate.Organic phase salt
Water cleans, and is dried with anhydrous magnesium sulfate, and revolving removes ethyl acetate.
Phosphorous epoxy monomer at 60 DEG C is finally stirred into 20min, adds in biology base curing agent (ratio 1: 3), stirring
5min, pours into the mold of preheating, 4h at 80 DEG C, 10h at 150 DEG C.
Thermogravimetric analysis is carried out to sample, heating rate is 10 DEG C/min, residual when initial decomposition temperature is 302 DEG C, 800 DEG C
Charcoal rate is 31.2%.
According to GB/T2046.2-2009, its limit oxygen index is levied with limit oxygen index instrument, limit oxygen index is
27.1%.
Using CZF-3 type horizontal vertical combustion appliances, sample strip specification is：Length × width x thickness=130.0mm × 12.7mm
× 3.2mm, it is V-1 grades to obtain the sample flame retardant property grade.
Embodiment 4：
(1) 20ml tetrahydrofurans, 0.1936mol potassium carbonate, 0.0176mol gallic acids, strength are packed into sealed flask
Stir 5min.Then, the tetrahydrofuran solution of allyl bromide, bromoallylene (0.2112mol) is slowly added in 20min.Mixture is heated to 50
DEG C, 20h is kept at this temperature.Obtained product filtering, revolving.Most crude product is dissolved in dichloromethane at last, is eaten with saturation
Brine cleans.Dichloromethane layer revolving evaporation obtains smart product, and vacuum drying 7h obtains product 1 at 50 DEG C.
(2) 0.03872molDOPO is added in the round-bottomed flask with condenser pipe, 30ml tetrahydrofurans, flask is in argon atmospher
60 DEG C are heated under enclosing.After DOPO is completely dissolved, 0.0176mol products 1 add in 30min, and reaction mixture is in this temperature
Lower holding 10h.After being cooled to room temperature, product is obtained by filtration, is cleaned 2 times with tetrahydrofuran/dimethylbenzene (1: 1), then at 80 DEG C
Lower vacuum drying 3h, obtains product 2.
(3) tetrahydrofuran solution (30ml) of product 2 (0.0176mol), the m-chloro peroxide of 0.2112mol are added in flask
Benzoic acid, 0.002933mol4,4 '-thiobis (6- tertiary butyls metacresol).40h is reacted at 20 DEG C, is subsequently cooled to 0 DEG C,
3h is kept at a temperature of this, is filtered to remove filter residue, filtrate is with 10% sodium sulfite solution, 5% sodium carbonate liquor, saturated common salt
Water cleans, and anhydrous magnesium sulfate removes water remaining in organic phase and then rotated.Obtained solid is dissolved in 5ml dichloromethane
In, it pours into and precipitation is obtained by filtration in 10 times of cold methanol.Finally, 40h is dried in vacuo at 20 DEG C.
(4) 0.1mol chaffs amine is added in the round-bottomed flask with reflux condensing tube, is cooled to -5 DEG C.The hydrochloric acid of 10w%
(0.4mol) is added dropwise.Then temperature rises to 20 DEG C, stirs 10min.0.4mol acetone adds in mixture.Temperature is improved to 30
℃.Add 0.04mol acetone.Reaction is completed after 5 days, adds 0.04mol acetone.Mixture is cooled to 20 DEG C, adds in
100ml deionized waters.PH to 8 is adjusted with 15wt%NaOH solution, mixture is extracted 2 times with ethyl acetate.Organic phase salt
Water cleans, and is dried with anhydrous magnesium sulfate, and revolving removes ethyl acetate.
Phosphorous epoxy monomer at 30 DEG C is finally stirred into 8min, adds in biology base curing agent (ratio 1: 2), stirring
3min, pours into the mold of preheating, 4h at 80 DEG C, 10h at 150 DEG C.
Thermogravimetric analysis is carried out to sample, heating rate is 10 DEG C/min, residual when initial decomposition temperature is 312 DEG C, 800 DEG C
Charcoal rate is 35.3%.
According to GB/T2046.2-2009, its limit oxygen index is levied with limit oxygen index instrument, limit oxygen index is
28.2%.
Using CZF-3 type horizontal vertical combustion appliances, sample strip specification is：Length × width x thickness=130.0mm × 12.7mm
× 3.2mm, it is V-O grades to obtain the sample flame retardant property grade.
Embodiment 5：
(1) 20ml dichloromethane, 0.1936mol potassium carbonate and 0.0176mol gallic acids, strength are packed into sealed flask
Stir 20min.Then, the dichloromethane solution of allyl bromide, bromoallylene (0.2112mol) is slowly added in 60min.Mixture is heated to
80 DEG C, 48h is kept at this temperature.Obtained product filtering, revolving.Most crude product is dissolved in dichloromethane at last, uses saturation
Saline solution cleans.Dichloromethane layer revolving evaporation obtains smart product, and vacuum drying 15h obtains product 1 at 80 DEG C.
(2) 0.03872molDOPO is added in the round-bottomed flask with condenser pipe, 80ml dichloromethane, flask is in argon atmospher
100 DEG C are heated under enclosing.After DOPO is completely dissolved, 0.0176mol products 1 add in 80min, and reaction mixture is in this temperature
Lower holding 40h.After being cooled to room temperature, product is obtained by filtration, cleans 5 times with dimethylbenzene/tetrahydrofuran mixed solution (1: 1), so
8h is dried in vacuo at 140 DEG C afterwards, obtains product 2.
(3) dichloromethane solution (80ml) of product 2 (0.0176mol), 0.2112mol m-chloro peroxide benzene are added in flask
Formic acid, 0.002933mol4,4 '-thiobis (6- tertiary butyls metacresol).60h is reacted at 50 DEG C, is subsequently cooled to -10 DEG C,
10h is kept at a temperature of this, is filtered to remove filter residue, 10% sodium sulfite solution of filtrate, 5% sodium carbonate liquor, saturation food
Brine cleans, and anhydrous magnesium sulfate removes water remaining in organic phase and then rotated.Obtained solid is dissolved in 5ml dichloromethanes
In alkane, pour into and precipitation is obtained by filtration in 10 times of cold methanol.Finally, 60h is dried in vacuo at 50 DEG C.
(4) chaff amine (0.1mol) is added in the round-bottomed flask with reflux condensing tube, is cooled to 5 DEG C.The hydrochloric acid of 20w%
(0.4mol) is added dropwise.Then temperature rises to 35 DEG C, stirs 30min.0.4mol acetone adds in mixture.Temperature is improved to 60
℃.Add 0.04mol acetone.Reaction is completed after 10 days, adds 0.04mol acetone.Mixture is cooled to 30 DEG C, adds in
200ml deionized waters.PH to 13 is adjusted with 15wt%NaOH solution, mixture is extracted 5 times with ethyl acetate.Organic phase salt
Water cleans, and is dried with anhydrous magnesium sulfate, and revolving removes ethyl acetate.
Phosphorous epoxy monomer at 80 DEG C is finally stirred into 30min, adds in biology base curing agent (ratio 1: 4), stirring
8min, pours into the mold of preheating, 4h at 80 DEG C, 10h at 150 DEG C.
Thermogravimetric analysis is carried out to sample, heating rate is 10 DEG C/min, residual when initial decomposition temperature is 305 DEG C, 800 DEG C
Charcoal rate is 31.2%.
According to GB/T2046.2-2009, its limit oxygen index is levied with limit oxygen index instrument, limit oxygen index is
27.2%.
Using CZF-3 type horizontal vertical combustion appliances, sample strip specification is：Length × width x thickness=130.0mm × 12.7mm
× 3.2mm, it is V-1 grades to obtain the sample flame retardant property grade.
Embodiment 6：
(1) 30ml acetone, 0.1936mol potassium carbonate and 0.0176mol gallic acids, strong stirring are packed into sealed flask
15min.Then, the acetone soln of allyl bromide, bromoallylene (0.2112mol) is slowly added in 40min.Mixture is heated to 60 DEG C, at this
30h is kept at a temperature.Obtained product filtering, revolving.Most crude product is dissolved in dichloromethane at last, clear with saturated salt solution
It washes.Dichloromethane layer revolving evaporation obtains smart product, and vacuum drying 10h obtains product 1 at 70 DEG C.
(2) 0.03872molDOPO is added in the round-bottomed flask with condenser pipe, 50ml acetone, flask is under argon atmosphere
It is heated to 80 DEG C.After DOPO is completely dissolved, 0.0176mol products 1 add in 50min, and reaction mixture is protected at this temperature
Hold 30h.After being cooled to room temperature, product is obtained by filtration, is cleaned 3 times with dimethylbenzene/tetrahydrofuran (1: 1), it is then true at 100 DEG C
The dry 5h of sky, obtains product 2.
(3) acetone soln (50ml) of product 2 (0.0176mol), 0.2112mol m-chloro peroxide benzene first are added in flask
Acid, 0.002933mol4,4 '-thiobis (6- tertiary butyls metacresol).50h is reacted at 30 DEG C, is subsequently cooled to -5 DEG C, it is warm herein
Degree is lower to keep 7h, is filtered to remove filter residue, 10% sodium sulfite solution of filtrate, 5% sodium carbonate liquor, and saturated salt solution is clear
It washes, anhydrous magnesium sulfate removes water remaining in organic phase and then rotated.Obtained solid is dissolved in 5ml dichloromethane,
It pours into and precipitation is obtained by filtration in 10 times of cold methanol.Finally, 50h, product 2 are dried in vacuo at 30 DEG C.
(4) chaff amine (0.1mol) is added in the round-bottomed flask with reflux condensing tube, is cooled to 0 DEG C.The hydrochloric acid of 15w%
(0.4mol) is added dropwise.Then temperature rises to 30 DEG C, stirs 20min.0.4mol acetone adds in mixture.Temperature is improved to 40
℃.Add 0.04mol acetone.Reaction is completed after 7 days, adds 0.04mol acetone.Mixture is cooled to 25 DEG C, adds in
150ml deionized waters.PH to 10 is adjusted with 15wt%NaOH solution, mixture is extracted 3 times with ethyl acetate.Organic phase salt
Water cleans, and is dried with anhydrous magnesium sulfate, and revolving removes ethyl acetate.
Phosphorous epoxy monomer at 60 DEG C is finally stirred into 20min, adds in biology base curing agent (ratio 1: 3), stirring
5min, pours into the mold of preheating, 4h at 80 DEG C, 10h at 150 DEG C.
Thermogravimetric analysis is carried out to sample, heating rate is 10 DEG C/min, residual when initial decomposition temperature is 315 DEG C, 800 DEG C
Charcoal rate is 34%.
According to GB/T2046.2-2009, its limit oxygen index is levied with limit oxygen index instrument, limit oxygen index is
27.8%.
Using CZF-3 type horizontal vertical combustion appliances, sample strip specification is：Length × width x thickness=130.0mm × 12.7mm
× 3.2mm, it is V-0 grades to obtain the sample flame retardant property grade.
Embodiment 7：
(1) 20ml tetrahydrofurans, 0.1408mol potassium carbonate, 0.0176mol gallic acids, strength are packed into sealed flask
Stir 5min.Then, the solution of allyl bromide, bromoallylene (0.176mol) is slowly added in 20min.Mixture is heated to 50 DEG C, at this
At a temperature of keep 20h.Obtained product filtering, revolving.Most crude product is dissolved in dichloromethane at last, is cleaned with saturated salt solution.
Dichloromethane layer revolving evaporation obtains smart product, and vacuum drying 7h obtains product 1 at 50 DEG C.
(2) 0.0264molDOPO is added in the round-bottomed flask with condenser pipe, 30ml tetrahydrofurans, flask is in argon atmospher
60 DEG C are heated under enclosing.After DOPO is completely dissolved, 0.0176mol products 1 add in 30min, and reaction mixture is in this temperature
Lower holding 10h.After being cooled to room temperature, product is obtained by filtration, is cleaned 2 times with tetrahydrofuran/dimethylbenzene (1: 1), then at 80 DEG C
Lower vacuum drying 3h, obtains product 2.
(3) tetrahydrofuran solution (30ml) of product 2 (0.0176mol), the m-chloro peroxide of 0.1936mol are added in flask
Benzoic acid, 0.00352mol4,4 '-thiobis (6- tertiary butyls metacresol).40h is reacted at 20 DEG C, is subsequently cooled to 0 DEG C, herein
At a temperature of keep 3h, be filtered to remove filter residue, filtrate is with 10% sodium sulfite solution, 5% sodium carbonate liquor, saturated salt solution
Cleaning, anhydrous magnesium sulfate remove water remaining in organic phase and are then rotated.Obtained solid is dissolved in 5ml dichloromethane
In, it pours into and precipitation is obtained by filtration in 10 times of cold methanol.Finally, 40h is dried in vacuo at 20 DEG C.
(4) 0.1mol chaffs amine is added in the round-bottomed flask with reflux condensing tube, is cooled to -5 DEG C.The hydrochloric acid of 10w%
(0.3mol) is added dropwise.Then temperature rises to 20 DEG C, stirs 10min.0.3mol acetone adds in mixture.Temperature is improved to 30
℃.Add 0.03mol acetone.Reaction is completed after 5 days, adds 0.03mol acetone.Mixture is cooled to 20 DEG C, adds in
100ml deionized waters.PH to 8 is adjusted with 15wt%NaOH solution, mixture is extracted 2 times with ethyl acetate.Organic phase salt
Water cleans, and is dried with anhydrous magnesium sulfate, and revolving removes ethyl acetate.
Phosphorous epoxy monomer at 30 DEG C is finally stirred into 8min, adds in biology base curing agent (ratio 1: 2), stirring
3min, pours into the mold of preheating, 4h at 80 DEG C, 10h at 150 DEG C.
Thermogravimetric analysis is carried out to sample, heating rate is 10 DEG C/min, residual when initial decomposition temperature is 301 DEG C, 800 DEG C
Charcoal rate is 33%.
According to GB/T2046.2-2009, its limit oxygen index is levied with limit oxygen index instrument, limit oxygen index is
27.5%.
Using CZF-3 type horizontal vertical combustion appliances, sample strip specification is：Length × width x thickness=130.0mm × 12.7mm
× 3.2mm, it is V-1 grades to obtain the sample flame retardant property grade.
Embodiment 8：
(1) loading 20ml dichloromethane in sealed flask, 0.：1408mol potassium carbonate and 0.0176mol gallic acids, by force
Power stirs 20min.Then, the dichloromethane solution of allyl bromide, bromoallylene (0.176mol) is slowly added in 60min.Mixture is heated to
80 DEG C, 48h is kept at this temperature.Obtained product filtering, revolving.Most crude product is dissolved in dichloromethane at last, uses saturation
Saline solution cleans.Dichloromethane layer revolving evaporation obtains smart product, and vacuum drying 15h obtains product 1 at 80 DEG C.
(2) 0.0264molDOPO is added in the round-bottomed flask with condenser pipe, 80ml dichloromethane, flask is in argon atmospher
100 DEG C are heated under enclosing.After DOPO is completely dissolved, 0.0176mol products 1 add in 80min, and reaction mixture is in this temperature
Lower holding 40h.After being cooled to room temperature, product is obtained by filtration, cleans 5 times with dimethylbenzene/tetrahydrofuran mixed solution (1: 1), so
8h is dried in vacuo at 140 DEG C afterwards, obtains product 2.
(3) dichloromethane solution (80ml) of product 2 (0.0176mol), 0.1936mol m-chloro peroxide benzene are added in flask
Formic acid, 0.00352mol4,4 '-thiobis (6- tertiary butyls metacresol).60h is reacted at 50 DEG C, is subsequently cooled to -10 DEG C, herein
At a temperature of keep 10h, be filtered to remove filter residue, filtrate is with 10% sodium sulfite solution, 5% sodium carbonate liquor, saturated common salt
Water cleans, and anhydrous magnesium sulfate removes water remaining in organic phase and then rotated.Obtained solid is dissolved in 5ml dichloromethane
In, it pours into and precipitation is obtained by filtration in 10 times of cold methanol.Finally, 60h is dried in vacuo at 50 DEG C.
(4) chaff amine (0.1mol) is added in the round-bottomed flask with reflux condensing tube, is cooled to 5 DEG C.The hydrochloric acid of 20w%
(0.3mol) is added dropwise.Then temperature rises to 35 DEG C, stirs 30min.0.3mol acetone adds in mixture.Temperature is improved to 60
℃.Add 0.03mol acetone.Reaction is completed after 10 days, adds 0.03mol acetone.Mixture is cooled to 30 DEG C, adds in
200ml deionized waters.PH to 13 is adjusted with 15wt%NaOH solution, mixture is extracted 5 times with ethyl acetate.Organic phase salt
Water cleans, and is dried with anhydrous magnesium sulfate, and revolving removes ethyl acetate.
Phosphorous epoxy monomer at 80 DEG C is finally stirred into 30min, adds in biology base curing agent (ratio 1: 4), stirring
8min, pours into the mold of preheating, 4h at 80 DEG C, 10h at 150 DEG C.
Thermogravimetric analysis is carried out to sample, heating rate is 10 DEG C/min, residual when initial decomposition temperature is 311 DEG C, 800 DEG C
Charcoal rate is 35.2%.
According to GB/T2046.2-2009, its limit oxygen index is levied with limit oxygen index instrument, limit oxygen index is
28.1%.
Using CZF-3 type horizontal vertical combustion appliances, sample strip specification is：Length × width x thickness=130.0mm × 12.7mm
× 3.2mm, it is V-0 grades to obtain the sample flame retardant property grade.
Embodiment 9：
(1) 30ml acetone, 0.1408mol potassium carbonate and 0.0176mol gallic acids, strong stirring are packed into sealed flask
15min.Then, the acetone soln of allyl bromide, bromoallylene (0.176mol) is slowly added in 40min.Mixture is heated to 60 DEG C, at this
30h is kept at a temperature.Obtained product filtering, revolving.Most crude product is dissolved in dichloromethane at last, clear with saturated salt solution
It washes.Dichloromethane layer revolving evaporation obtains smart product, and vacuum drying 10h obtains product 1 at 70 DEG C.
(2) 0.0264molDOPO is added in the round-bottomed flask with condenser pipe, 50ml acetone, flask is under argon atmosphere
It is heated to 80 DEG C.After DOPO is completely dissolved, 0.0176mol products 1 add in 50min, and reaction mixture is protected at this temperature
Hold 30h.After being cooled to room temperature, product is obtained by filtration, is cleaned 3 times with dimethylbenzene/tetrahydrofuran (1: 1), it is then true at 100 DEG C
The dry 5h of sky, obtains product 2.
(3) acetone soln (50ml) of product 2 (0.0176mol), 0.1936mol m-chloro peroxide benzene first are added in flask
Acid, 0.00352mol4,4 '-thiobis (6- tertiary butyls metacresol).50h is reacted at 30 DEG C, is subsequently cooled to -5 DEG C, it is warm herein
Degree is lower to keep 7h, is filtered to remove filter residue, 10% sodium sulfite solution of filtrate, 5% sodium carbonate liquor, and saturated salt solution is clear
It washes, anhydrous magnesium sulfate removes water remaining in organic phase and then rotated.Obtained solid is dissolved in 5ml dichloromethane,
It pours into and precipitation is obtained by filtration in 10 times of cold methanol.Finally, 50h, product 2 are dried in vacuo at 30 DEG C.
(4) chaff amine (0.1mol) is added in the round-bottomed flask with reflux condensing tube, is cooled to 0 DEG C.The hydrochloric acid of 15w%
(0.3mol) is added dropwise.Then temperature rises to 30 DEG C, stirs 20min.0.3mol acetone adds in mixture.Temperature is improved to 40
℃.Add 0.03mol acetone.Reaction is completed after 7 days, adds 0.03mol acetone.Mixture is cooled to 25 DEG C, adds in
150ml deionized waters.PH to 10 is adjusted with 15wt%NaOH solution, mixture is extracted 3 times with ethyl acetate.Organic phase salt
Water cleans, and is dried with anhydrous magnesium sulfate, and revolving removes ethyl acetate.
Phosphorous epoxy monomer at 60 DEG C is finally stirred into 20min, adds in biology base curing agent (ratio 1: 3), stirring
5min, pours into the mold of preheating, 4h at 80 DEG C, 10h at 150 DEG C.
Thermogravimetric analysis is carried out to sample, heating rate is 10 DEG C/min, residual when initial decomposition temperature is 312 DEG C, 800 DEG C
Charcoal rate is 34.8%.
According to GB/T2046.2-2009, its limit oxygen index, limit oxygen index 28% are levied with limit oxygen index instrument.
Using CZF-3 type horizontal vertical combustion appliances, sample strip specification is：Length × width x thickness=130.0mm × 12.7mm
× 3.2mm, it is V-O grades to obtain the sample flame retardant property grade.
Change the proportioning of each raw material, a series of full biology base fire retarding epoxide resins, indices such as 1 institute of table is prepared
Show：
Table 1：
Claims (2)
1. a kind of preparation method of full biology base fire retarding epoxide resin, which is characterized in that it includes the following steps：
Step 1, toward adding in solvent, potassium carbonate and gallic acid, 5~20min of strong stirring, then, in 20~60min in flask
The solution of allyl bromide, bromoallylene is slowly added to, mixture is heated to 50~80 DEG C, keeps 20~48h, obtained production at this temperature
Object is filtered to remove impurity, and solution revolving removes solvent and obtains crude product, crude product is dissolved in dichloromethane, with saturated sodium-chloride water
Solution washs, and dichloromethane layer revolving evaporation obtains smart product, and 7~15h of vacuum drying obtains product 1: 3,4 at 50~80 DEG C,
5- triolefin propoxy benzoic acid esters；The molar ratio of gallic acid and potassium carbonate is 1: 5~11, and gallic acid and allyl bromide, bromoallylene rub
You are than being 1: 6~12；The solvent is one kind in tetrahydrofuran, acetone, dichloromethane or ether；
Step 2 adds in miscellaneous -10- phosphas -10- oxides of 9,10- dihydro-9-oxies and molten in the round-bottomed flask with condenser pipe
Agent, flask are heated to 60~100 DEG C under argon atmosphere, and the miscellaneous -10- phosphas -10- oxides of 9,10- dihydro-9-oxies are completely dissolved
Afterwards, product 1 being added in 30~80min, reaction mixture keeps 10~40h at this temperature, after being cooled to room temperature, filtering
Product is obtained, is cleaned with mixed solvent, 3~8h is then dried in vacuo at 80~140 DEG C, obtains product 2：DOPO bases 3,4,5-
Triolefin propoxy benzoic acid ester；The molar ratio of product 1 and the miscellaneous -10- phosphas -10- oxides of 9,10- dihydro-9-oxy for 1: 1~
2.2；The mixed solvent is mixed with volume ratio 1: 1 for dimethylbenzene or tetrahydrofuran and two kinds of solvents in dichloromethane or acetone
It closes；
Solution, the metachloroperbenzoic acid and 4 of addition product 2 in step 3, flask, and 4 '-thiobis (6- tertiary butyl metacresols, 20
40~60h is reacted at~50 DEG C, is subsequently cooled to 0~-10 DEG C, 3~10h is kept at this temperature, is filtered to remove filter residue, filtrate
It is washed successively with 10% sodium sulfite solution, 5% sodium carbonate liquor and saturated sodium-chloride water solution, anhydrous magnesium sulfate removes
In organic phase then remaining water is rotated, and by the dissolving of obtained solid in methylene chloride, pours the cold first of 10 times of volumes into
In alcohol, the precipitation that is obtained by filtration, vacuum drying obtains phosphorous 3,4,5- tricyclic ethoxy benzonitrile acid esters of epoxy monomer DOPO bases, produces
The molar ratio of object 2 and metachloroperbenzoic acid is 1: 9~12, product 2 and 4, mole of 4 '-thiobis (6- tertiary butyls metacresol)
Than being 3~6: 1；The solvent of 2 solution of product is one kind in tetrahydrofuran, acetone, dichloromethane or ether；
Step 4 adds in chaff amine in the round-bottomed flask with reflux condensing tube, is cooled to -5~5 DEG C, 10~20w% is added dropwise
Hydrochloric acid, then temperature rise to 20~35 DEG C, stir 10~30min, acetone added in into mixture, temperature is improved to 30~60
DEG C, add acetone, reaction is completed after 5~10 days, and third time adds in acetone, and mixture is cooled to 20~30 DEG C, addition go from
Sub- water adjusts pH to 8~13 with 15wt%NaOH solution, and mixture is extracted with ethyl acetate, organic phase sodium-chloride water solution
Washing, is dried with anhydrous magnesium sulfate, and revolving removes ethyl acetate, obtains biology base curing agent furans dimethylamine, chaff amine and hydrochloric acid
Molar ratio is 1: 2~4, and chaff amine and the molar ratio of acetone added in three times are 1: 2~4: 0.1~0.4: 0.1~0.4；
Step 5, the phosphorous epoxy monomer for obtaining step 3 stir 8~30min at 30~80 DEG C, add in the life that step 4 obtains
Object base curing agent furans dimethylamine, the mass ratio of phosphorous epoxy monomer and biology base curing agent furans dimethylamine is 1: 2~4, is stirred
3~8min is mixed, pours into the mold of preheating, cures 4h at 80 DEG C, cures 10h at 150 DEG C, full biology base fire retarding epoxide resin is made
Product.
2. a kind of biology base fire retarding epoxide resin complete as made from preparation method described in claim 1.
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