CN114752038A - Halogen-free flame-retardant epoxy resin and preparation method thereof - Google Patents
Halogen-free flame-retardant epoxy resin and preparation method thereof Download PDFInfo
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- CN114752038A CN114752038A CN202210261716.1A CN202210261716A CN114752038A CN 114752038 A CN114752038 A CN 114752038A CN 202210261716 A CN202210261716 A CN 202210261716A CN 114752038 A CN114752038 A CN 114752038A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 30
- 239000003063 flame retardant Substances 0.000 title claims abstract description 30
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 30
- 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 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 67
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000004593 Epoxy Substances 0.000 claims abstract description 22
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 27
- 150000001993 dienes Chemical class 0.000 claims description 18
- 229930185605 Bisphenol Natural products 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 16
- 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 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 12
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 12
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 12
- 229920002866 paraformaldehyde Polymers 0.000 claims description 12
- -1 siloxane chain Chemical group 0.000 claims description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 9
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 claims description 7
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 6
- 238000007792 addition Methods 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 6
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 6
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 6
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 6
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 4
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 claims description 3
- 229940076286 cupric acetate Drugs 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- BXJGUBZTZWCMEX-UHFFFAOYSA-N dimethylhydroquinone Natural products CC1=C(C)C(O)=CC=C1O BXJGUBZTZWCMEX-UHFFFAOYSA-N 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical group C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 238000000034 method Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005821 Claisen rearrangement reaction Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- 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
- C08G59/306—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention relates to a halogen-free flame-retardant epoxy resin and a preparation method thereof, belonging to the technical field of epoxy resin and comprising the following raw materials in parts by weight: 80-100 parts of epoxy monomer, 5-8 parts of curing agent and 10-20 parts of auxiliary agent, and the preparation method comprises the following steps: adding an epoxy monomer, a curing agent and an auxiliary agent into a solvent, removing the solvent after the solvent is clarified, and pouring the solvent into a mold for curing; according to the invention, a self-made epoxy monomer, an auxiliary agent and a curing agent are used for reaction, the epoxy monomer and the auxiliary agent both contain a group with a flame retardant effect, and no flame retardant is required to be additionally added.
Description
Technical Field
The invention belongs to the technical field of epoxy resin, and particularly relates to halogen-free flame-retardant epoxy resin and a preparation method thereof.
Background
The epoxy resin has excellent electrical property, good mechanical property and excellent chemical stability, and is widely applied to the fields of aviation, coating, building, adhesive, electronic copper clad laminate and the like. Because the epoxy resin generates a great amount of black smoke in the combustion process, and the oxygen index is about 20, the epoxy resin has great flame propagation harm, and therefore flame retardant modification is generally carried out. At present, most of flame-retardant epoxy resins are applied by introducing halogen atoms (chlorine, bromine and the like) into the epoxy resins, but the problems of corrosive gas generation, high smoke density and the like generally exist by using halogen compounds as flame retardants, so that the flame-retardant epoxy resins are limited in more and more fields.
Disclosure of Invention
In order to solve the technical problems mentioned in the background technology, the invention provides a halogen-free flame-retardant epoxy resin and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the halogen-free flame-retardant epoxy resin comprises the following raw materials in parts by weight: 80-100 parts of epoxy monomer, 5-8 parts of curing agent and 10-20 parts of auxiliary agent;
the epoxy monomer is prepared by the following steps:
step A11, mixing a bisphenol monomer and absolute ethyl alcohol, adding anhydrous potassium carbonate, heating and refluxing for reaction for 60min, adding allyl bromide, keeping the temperature unchanged, continuing to stir for reaction for 8h, after the reaction is finished, carrying out reduced pressure concentration to remove the solvent, washing with the absolute ethyl alcohol and deionized water, drying, after the drying is finished, heating to 170 ℃ under the protection of nitrogen, keeping the temperature for 2h, heating to 210 ℃, and keeping the temperature for 2h to obtain a diene monomer; the bisphenol monomer and allyl bromide are subjected to substitution reaction, and after the reaction is finished, the reaction is treated and subjected to claisen rearrangement under the condition of nitrogen protection to obtain a diene monomer; the structure of the diene monomer is shown below:
step A12, mixing diene monomer, tetramethyldisiloxane and toluene, adding a Kanster catalyst, heating to 90 ℃, stirring for reacting for 8 hours, filtering with diatomite after the reaction is finished, removing the catalyst, and then concentrating under reduced pressure to remove the solvent to obtain siloxane chain segment monomer; and carrying out hydrosilylation on the diene monomer and the tetramethyldisiloxane to obtain a siloxane chain segment monomer by taking the tetramethyldisiloxane as a center.
And A13, mixing the siloxane chain segment monomer, epichlorohydrin, benzyltriethylammonium chloride and dioxane, heating to 90 ℃, stirring for reaction for 4 hours, concentrating under reduced pressure to remove the solvent, mixing with toluene, heating to 85 ℃, adding a sodium hydroxide aqueous solution for continuous reaction for 4 hours, adding sodium hydroxide to promote ring-closing reaction, and washing and drying after the reaction is finished to obtain the epoxy monomer. The middle part of each chain link in the generated epoxy resin contains siloxane bonds, so that the prepared polymer uniformly contains a large number of siloxane bonds, the high-temperature resistance of the epoxy resin is improved, and the hydrophobic property of the epoxy resin can be improved by introducing the siloxane bonds. When a fire disaster happens to the material containing the silicon element, a Si-C layer can be rapidly generated outside the material, so that the effects of isolating oxygen and preventing heat transfer are achieved, and melting and dripping can be prevented, and secondary combustion is prevented. Therefore, the phosphorus element and the silicon element are combined together, so that the flame-retardant and char-forming effects of the epoxy resin are improved.
Further, in the step A11, the mass ratio of the bisphenol monomer to the anhydrous potassium carbonate to the allyl bromide is 3.4: 2.7: 2.4;
in the step A12, the dosage mass ratio of the diene monomer to the tetramethyldisiloxane is 6: 1; the addition amount of the Kaster catalyst is 1 percent of the mass of the diene monomer;
in the step A13, the mass fraction of the sodium hydroxide aqueous solution is 35%, and the dosage ratio of the siloxane chain segment monomer, the epichlorohydrin and the benzyltriethylammonium chloride is 5 g: 2 g: 30 mg.
Further, the bisphenol monomer is prepared by the following steps:
mixing diethylene glycol dimethyl ether and hydroquinone, dropwise adding phenylphosphoryl dichloride at the temperature of 0 ℃, heating to 40 ℃ after dropwise adding, stirring for reacting for 2.5 hours, heating to 110 ℃, stirring for reacting for 2 hours, cooling to 20 ℃ after reacting, adding triethylamine to adjust the pH value to be neutral, continuously stirring for 30min, and then decompressing and concentrating to remove the solvent to obtain the bisphenol monomer. The molar ratio of hydroquinone to phenylphosphoryl dichloride is 2: 1. the bisphenol monomer is introduced with a phosphorus-containing group through the reaction of hydroquinone and phenyl phosphoryl dichloride, and a non-volatile polyphosphate film wrapping layer can be generated outside the base material when the phosphorus-containing element is burnt, so that the function of isolating oxygen and heat can be realized.
The auxiliary agent is prepared by the following steps:
step S11, mixing furfural, paraformaldehyde and toluene, reacting for 2 hours at the temperature of 70 ℃, adding p-hydroxybenzaldehyde and paraformaldehyde, keeping the temperature unchanged, continuing stirring for reacting for 12 hours, and after the reaction is finished, carrying out reduced pressure concentration to remove the solvent to obtain an intermediate 1; toluene as a solvent; the structure of the intermediate 1 contains a benzoxazine structure, and the structure of the intermediate retains the aldehyde group of p-hydroxybenzaldehyde, so that the subsequent reaction is facilitated;
step S12, mixing o-phenylenediamine and N, N-dimethylformamide, then adding sodium metabisulfite and magnesium sulfate, stirring uniformly, adding the intermediate 1, heating up and refluxing for 6 hours after the addition is finished, extracting the obtained reaction liquid with dichloromethane and deionized water after the reaction is finished, and then purifying through a column to obtain an intermediate 2; the structure of intermediate 2 is shown below:
and step S13, mixing the intermediate 2 with absolute ethyl alcohol, adding copper acetate, stirring for 30min at the temperature of 20 ℃, heating and refluxing for 24h, filtering the obtained reaction solution after the reaction is finished, washing with absolute ethyl alcohol and deionized water after the filtration is finished, and drying to obtain the auxiliary agent.
Further, the molar ratio of the furfural to the p-hydroxybenzaldehyde to the paraformaldehyde in the step S11 is 1: 1: 2; the dosage of the paraformaldehyde added in the two times is equal; in the step S12, the mass ratio of the dosage of o-phenylenediamine to the dosage of the intermediate 1 to the dosage of sodium metabisulfite to the dosage of magnesium sulfate is 9: 20: 16: 10; in the step S13, the dosage ratio of the intermediate 2 to the cupric acetate to the absolute ethyl alcohol is 2 g: 50mL of: 1g of the total weight of the composition.
Further, the curing agent is one of diaminodiphenylmethane and 1, 3-diaminomethylcyclohexane.
A preparation method of halogen-free flame-retardant epoxy resin comprises the following steps:
adding 80-100 parts of epoxy monomer, 5-10 parts of curing agent and 10-20 parts of auxiliary agent into a solvent, removing the solvent after the solvent is clarified, pouring the solvent into a mold, sequentially curing at 100 ℃, 1h, 160 ℃, 1h, 200 ℃ and 1h, and naturally cooling to room temperature after curing is finished to prevent the sample from cracking. The mass ratio of dimethylbenzene to n-butanol selected as a solvent is 3: 1 in a solvent mixture.
The invention has the beneficial effects that:
according to the invention, the self-made epoxy monomer, the auxiliary agent and the curing agent are used for reaction, the epoxy monomer and the auxiliary agent both contain groups with a flame-retardant effect, no additional flame retardant is needed, no toxic or harmful substances are released in the combustion process, and the problems of low melting point, easy precipitation, poor compatibility and the like of the additive flame retardant are solved. In addition, the auxiliary agent is an imidazole-containing copper complex, benzoxazine in the structure of the auxiliary agent has good char formation, a stable char layer is formed after combustion, and metal oxide plays a role in improving flame retardance, and an oxazine ring generates a ring-opening reaction in a curing process to form phenolic hydroxyl, and the phenolic hydroxyl generates a cross-linking reaction with an epoxy group, so that the high-temperature resistance of the cured epoxy resin is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing a bisphenol monomer:
mixing diethylene glycol dimethyl ether and hydroquinone, dropwise adding phenylphosphoryl dichloride at the temperature of 0 ℃, heating to 40 ℃ after dropwise adding, stirring for reacting for 2.5 hours, heating to 110 ℃, stirring for reacting for 2 hours, cooling to 20 ℃ after reacting, adding triethylamine to adjust the pH value to be neutral, continuously stirring for 30min, and then decompressing and concentrating to remove the solvent to obtain the bisphenol monomer. The molar ratio of hydroquinone to phenylphosphoryl dichloride is 2: 1.
example 2
Preparing an epoxy monomer:
step A11, mixing the bisphenol monomer prepared in the embodiment 1 with absolute ethyl alcohol, then adding anhydrous potassium carbonate, heating and refluxing for reaction for 60min, then adding allyl bromide, keeping the temperature unchanged, continuing to stir for reaction for 8h, after the reaction is finished, decompressing and concentrating to remove the solvent, washing with absolute ethyl alcohol and deionized water, drying, heating to 170 ℃ under the protection of nitrogen after the drying is finished, keeping the temperature for 2h, heating to 210 ℃, and keeping the temperature for 2h to obtain a diene monomer; the mass ratio of the bisphenol monomer to the anhydrous potassium carbonate to the allyl bromide is 3.4: 2.7: 2.4;
step A12, mixing diene monomer, tetramethyldisiloxane and toluene, adding a Kanster catalyst, heating to 90 ℃, stirring for reacting for 8 hours, filtering with diatomite after the reaction is finished, removing the catalyst, and then concentrating under reduced pressure to remove the solvent to obtain siloxane chain segment monomer; the dosage mass ratio of the diene monomer to the tetramethyldisiloxane is 6: 1; the addition amount of the Kaster catalyst is 1 percent of the mass of the diene monomer;
and A13, mixing the siloxane chain segment monomer, epoxy chloropropane, benzyltriethylammonium chloride and dioxane, heating to 90 ℃, stirring for reaction for 4 hours, concentrating under reduced pressure to remove the solvent, mixing with toluene, heating to 85 ℃, adding a sodium hydroxide aqueous solution for continuous reaction for 4 hours, and washing and drying after the reaction is finished to obtain the epoxy monomer. The mass fraction of the sodium hydroxide aqueous solution is 35%, and the dosage ratio of the siloxane chain segment monomer, the epichlorohydrin and the benzyltriethylammonium chloride is 5 g: 2 g: 30 mg.
Example 3
Preparing an auxiliary agent:
step S11, mixing furfural, paraformaldehyde and toluene, reacting for 2 hours at the temperature of 70 ℃, adding p-hydroxybenzaldehyde and paraformaldehyde, keeping the temperature unchanged, continuing stirring for reacting for 12 hours, and after the reaction is finished, carrying out reduced pressure concentration to remove the solvent to obtain an intermediate 1;
step S12, mixing o-phenylenediamine and N, N-dimethylformamide, then adding sodium metabisulfite and magnesium sulfate, stirring uniformly, adding the intermediate 1, heating up and refluxing for 6 hours after the addition is finished, extracting the obtained reaction liquid with dichloromethane and deionized water after the reaction is finished, and then purifying through a column to obtain an intermediate 2;
and step S13, mixing the intermediate 2 with absolute ethyl alcohol, adding copper acetate, stirring for 30min at the temperature of 20 ℃, heating and refluxing for 24h, filtering the obtained reaction solution after the reaction is finished, washing with absolute ethyl alcohol and deionized water after the filtration is finished, and drying to obtain the auxiliary agent.
Wherein, in the step S11, the molar ratio of the furfural to the p-hydroxybenzaldehyde to the paraformaldehyde is 1: 1: 2; the dosage of the paraformaldehyde added in the two times is equal; in the step S12, the using amount mass ratio of the o-phenylenediamine to the intermediate 1 to the sodium metabisulfite to the magnesium sulfate is 9: 20: 16: 10; in the step S13, the dosage ratio of the intermediate 2 to the cupric acetate to the absolute ethyl alcohol is 2 g: 50mL of: 1g of the total weight of the composition.
Example 4
A preparation method of halogen-free flame-retardant epoxy resin comprises the following steps:
adding 80 parts of the epoxy monomer prepared in example 2, 5 parts of the curing agent and 10 parts of the auxiliary agent prepared in example 3 into a solvent, removing the solvent after the solvent is clarified, pouring into a mold, curing at 100 ℃, 1h, 160 ℃, 1h, 200 ℃ and 1h in sequence, and naturally cooling to room temperature after curing. The curing agent is diaminodiphenylmethane.
Example 5
A preparation method of halogen-free flame-retardant epoxy resin comprises the following steps:
adding 90 parts of the epoxy monomer prepared in example 2, 8 parts of the curing agent and 15 parts of the auxiliary agent prepared in example 3 into a solvent, removing the solvent after the solvent is clarified, pouring into a mold, curing at 100 ℃, 1h, 160 ℃, 1h, 200 ℃ and 1h in sequence, and naturally cooling to room temperature after curing. The curing agent is diaminodiphenylmethane.
Example 6
A preparation method of halogen-free flame-retardant epoxy resin comprises the following steps:
adding 100 parts of the epoxy monomer prepared in the example 2, 10 parts of the curing agent and 20 parts of the auxiliary agent prepared in the example 3 into a solvent, removing the solvent after the solvent is clarified, pouring the solvent into a mold, curing the solvent at 100 ℃, 1h, 160 ℃, 1h, 200 ℃ and 1h in sequence, and naturally cooling the mixture to room temperature after the curing is finished. The curing agent is 1, 3-bisaminomethylcyclohexane.
Comparative example 1
Mixing the bisphenol monomer prepared in the example 1 with absolute ethyl alcohol, adding anhydrous potassium carbonate, carrying out heating reflux reaction for 60min, adding allyl bromide, keeping the temperature unchanged, continuing to stir for reaction for 8h, after the reaction is finished, carrying out reduced pressure concentration to remove the solvent, washing with absolute ethyl alcohol and deionized water, drying, heating to 170 ℃ under the protection of nitrogen after the drying is finished, keeping the temperature for 2h, heating to 210 ℃, and keeping the temperature for 2h to obtain a diene monomer; the mass ratio of the bisphenol monomer to the anhydrous potassium carbonate to the allyl bromide is 3.4: 2.7: 2.4;
mixing a diene monomer, epoxy chloropropane, benzyltriethylammonium chloride and dioxane, heating to 90 ℃, stirring for reacting for 4 hours, concentrating under reduced pressure to remove a solvent, mixing with toluene, heating to 85 ℃, adding a sodium hydroxide aqueous solution, continuing to react for 4 hours, washing and drying after the reaction is finished to obtain the epoxy monomer. The mass fraction of the sodium hydroxide aqueous solution is 35 percent, and the dosage ratio of the diene monomer, the epichlorohydrin and the benzyltriethylammonium chloride is 4 g: 2 g: 30 mg.
Comparative example 2
The epoxy monomer of example 5 was replaced with the epoxy monomer of comparative example 1, and the remaining raw materials and preparation process were maintained.
Comparative example 3
Compared with the example 5, no auxiliary agent is added, and the rest raw materials and the preparation process are kept unchanged.
The samples prepared in examples 4 to 6 and comparative examples 2 to 3 were tested, and the glass transition temperature Tg and flame retardant rating test results of the test samples are shown in Table 1 below: the flame retardant rating is determined according to the UL94 vertical burning method;
TABLE 1
| Example 4 | Example 5 | Example 6 | Comparative example 2 | Comparative example 3 | |
| Flame retardant rating | V-0 | V-0 | V-0 | V-1 | V-1 |
| Tg/℃ | 171 | 171 | 172 | 165 | 143 |
| Water contact angle-O | 108.1 | 108.4 | 108.5 | 72 | 89 |
In comparative example 3, no auxiliary agent is added, so that the crosslinking process of phenolic hydroxyl and epoxy groups after ring opening is lacked, the glass transition temperature Tg of the benzoxazine is lower than that of the added examples 4-6 and comparative example 1, the benzoxazine has the promotion effect of improving the heat resistance and the flame retardance of the sample, and siloxane bonds are introduced, so that the samples prepared in examples 4-6 have good hydrophobicity and the resistance to moisture penetration is improved.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (7)
1. The halogen-free flame-retardant epoxy resin is characterized by comprising the following raw materials in parts by weight: 80-100 parts of epoxy monomer, 5-8 parts of curing agent and 10-20 parts of auxiliary agent;
the epoxy monomer is prepared by the following steps:
mixing siloxane chain segment monomers, epoxy chloropropane, benzyltriethylammonium chloride and dioxane, heating to 90 ℃, stirring for reacting for 4 hours, concentrating under reduced pressure to remove a solvent, mixing with toluene, heating to 85 ℃, adding a sodium hydroxide aqueous solution, and continuing to react for 4 hours to obtain the epoxy monomers, wherein the mass fraction of the sodium hydroxide aqueous solution is 35%, and the dosage ratio of the siloxane chain segment monomers, the epoxy chloropropane and the benzyltriethylammonium chloride is 5 g: 2 g: 30 mg.
2. The halogen-free flame-retardant epoxy resin according to claim 1, wherein the siloxane chain segment monomer is prepared by the following steps:
mixing a bisphenol monomer and absolute ethyl alcohol, then adding anhydrous potassium carbonate, heating, refluxing and reacting for 60min, then adding allyl bromide, keeping the temperature unchanged, continuing stirring and reacting for 8h, after the reaction is finished, concentrating under reduced pressure to remove the solvent, washing with absolute ethyl alcohol and deionized water, drying, after the drying is finished, under the condition of nitrogen protection, heating to 170 ℃, keeping for 2h, then heating to 210 ℃, and keeping for 2h to obtain a diene monomer; the mass ratio of the bisphenol monomer to the anhydrous potassium carbonate to the allyl bromide is 3.4: 2.7: 2.4;
mixing a diene monomer, tetramethyldisiloxane and toluene, adding a Kanster catalyst, heating to 90 ℃, and stirring for reacting for 8 hours to obtain a siloxane chain segment monomer; the dosage mass ratio of the diene monomer to the tetramethyldisiloxane is 6: 1; the amount of the Kaster catalyst added is 1% of the mass of the diene monomer.
3. The halogen-free flame-retardant epoxy resin according to claim 2, wherein the bisphenol monomer is prepared by the following steps:
mixing diethylene glycol dimethyl ether and hydroquinone, dropwise adding phenylphosphoryl dichloride at the temperature of 0 ℃, heating to 40 ℃ after dropwise adding, stirring for reacting for 2.5 hours, then heating to 110 ℃, stirring for reacting for 2 hours, cooling to 20 ℃ after reacting, adding triethylamine to adjust the pH value to be neutral, continuously stirring for 30min, and then decompressing and concentrating to remove the solvent to obtain a bisphenol monomer; the molar ratio of hydroquinone to phenylphosphoryl dichloride is 2: 1.
4. the halogen-free flame-retardant epoxy resin as claimed in claim 1, wherein the auxiliary is prepared by the steps of:
s11, mixing furfural, paraformaldehyde and toluene, reacting for 2 hours at the temperature of 70 ℃, adding p-hydroxybenzaldehyde and paraformaldehyde, keeping the temperature unchanged, and continuously stirring for reacting for 12 hours to obtain an intermediate 1;
step S12, mixing o-phenylenediamine and N, N-dimethylformamide, then adding sodium metabisulfite and magnesium sulfate, stirring uniformly, adding the intermediate 1, and heating up and carrying out reflux reaction for 6 hours after the addition to obtain an intermediate 2;
and step S13, mixing the intermediate 2 with absolute ethyl alcohol, then adding copper acetate, stirring for 30min at the temperature of 20 ℃, and then heating and refluxing for reaction for 24h to obtain the auxiliary agent.
5. The halogen-free flame retardant epoxy resin as claimed in claim 4, wherein the molar ratio of the furfural, the p-hydroxybenzaldehyde and the paraformaldehyde in step S11 is 1: 1: 2; the dosage of the paraformaldehyde added in the two times is equal; in the step S12, the using amount mass ratio of the o-phenylenediamine to the intermediate 1 to the sodium metabisulfite to the magnesium sulfate is 9: 20: 16: 10; in the step S13, the dosage ratio of the intermediate 2 to the cupric acetate to the absolute ethyl alcohol is 2 g: 50mL of: 1g of the total weight of the composition.
6. The halogen-free flame-retardant epoxy resin as claimed in claim 1, wherein the curing agent is one of diaminodiphenylmethane and 1, 3-diaminomethylcyclohexane.
7. The preparation method of the halogen-free flame retardant epoxy resin according to claim 1, characterized by comprising the following steps:
adding epoxy monomer, curing agent and auxiliary agent into solvent, removing solvent after the solvent is clarified, pouring into a mould, and sequentially curing at 100 deg.C for 1h, 160 deg.C for 1h, 200 deg.C for 1 h.
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