CN116606530A - Halogen-free flame-retardant epoxy resin prepreg and preparation method thereof - Google Patents
Halogen-free flame-retardant epoxy resin prepreg and preparation method thereof Download PDFInfo
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- CN116606530A CN116606530A CN202310728104.3A CN202310728104A CN116606530A CN 116606530 A CN116606530 A CN 116606530A CN 202310728104 A CN202310728104 A CN 202310728104A CN 116606530 A CN116606530 A CN 116606530A
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- retardant epoxy
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 70
- 239000003063 flame retardant Substances 0.000 title claims abstract description 70
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 70
- 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 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000004744 fabric Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000003365 glass fiber Substances 0.000 claims abstract description 22
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 12
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- IKURBWJGKCATNH-UHFFFAOYSA-N aniline 1H-imidazole Chemical compound NC1=CC=CC=C1.N1C=NC=C1 IKURBWJGKCATNH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005520 cutting process Methods 0.000 claims abstract description 10
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000009849 vacuum degassing Methods 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- PGFSTEOEDQOZOK-UHFFFAOYSA-N C(C)O.OC1=CC=C(C=O)C=C1 Chemical compound C(C)O.OC1=CC=C(C=O)C=C1 PGFSTEOEDQOZOK-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 150000002462 imidazolines Chemical class 0.000 claims description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 2
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 4
- 239000005696 Diammonium phosphate Substances 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 125000003700 epoxy group Chemical group 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 5
- XDKUKGIJDNUFGK-UHFFFAOYSA-N 4-methylimidazole Chemical group CC1=CN=C[N]1 XDKUKGIJDNUFGK-UHFFFAOYSA-N 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 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 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000012779 reinforcing material 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/02—Polyglycidyl ethers of bis-phenols
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Abstract
The invention relates to the technical field of prepregs, and discloses a halogen-free flame-retardant epoxy resin prepreg and a preparation method thereof, wherein 2, 2-diallyl bisphenol A and epichlorohydrin are mixed to obtain 2,2,1,4-epichlorohydrin diallyl bisphenol A. Adding 2-aminobenzene imidazole and 4-hydroxybenzaldehyde into an ethanol solution containing 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide to obtain the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-BHM composite flame retardant. The modified epoxy resin has more hydroxyl groups, ether bonds and epoxy groups with strong activity, so that chemical bonds are generated between molecules of the epoxy resin and adjacent interfaces, and the viscosity of the prepreg is improved. Cutting glass fiber cloth with the thickness to the required size, mixing modified halogen-free flame-retardant epoxy resin, imidazole accelerator, solvent and ball mill, coating the mixture on the glass fiber cloth, and baking the coated glass fiber cloth to obtain the halogen-free flame-retardant epoxy resin prepreg which has the advantages of high viscosity and higher flame-retardant efficiency.
Description
Technical Field
The invention relates to the technical field of epoxy resin prepregs, in particular to a halogen-free flame-retardant epoxy resin prepreg and a preparation method thereof.
Background
The prepreg is composed of resin and reinforcing materials, and is one of main materials in the production of the multilayer board. As reported in paper research on development and application of halogen-free non-flowing prepreg, a preparation method of the prepreg is reported, rubber elastomer and organic particles are adopted to toughen epoxy resin, and the prepared prepreg reduces the fluidity of an epoxy resin system, does not contain harmful metal, has no halogen, high peel strength and excellent heat resistance. But it does not flow, so that the resulting prepregs have low flowability and low viscosity.
The flame retardant is a functional auxiliary agent for endowing inflammable polymers with flame retardance, and is mainly designed for high polymer flame retardance. For example, the paper "research on the application of halogen-containing flame retardants in plastic products" reports the combustion mechanism of a halogen flame retardant and the application of the halogen flame retardant in three types of resins, and the halogen flame retardant has the advantages of low cost, simple preparation, good thermal stability, processability and high dispersibility. But the generated gas is toxic and can cause harm to human bodies.
Based on the above, developing a high-efficiency environment-friendly phosphorus-containing composite flame retardant and a high-viscosity epoxy resin, which simultaneously satisfies the mechanical property and flame retardant property of the epoxy resin, has become a technical problem to be solved.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides the halogen-free flame-retardant epoxy resin prepreg and the preparation method thereof, and the viscosity and flame-retardant efficiency of the prepreg are improved.
(II) technical scheme
The halogen-free flame-retardant epoxy resin prepreg comprises the following components in parts by weight: 10-20 parts of accelerator, 20-30 parts of solvent, 10-15 parts of curing agent, 40-60 parts of epoxy resin and 30-50 parts of flame retardant.
Further, the curing agent is at least one of imidazoles, imidazolines, trialkyl phosphorus and quaternary ammonium salts.
Further, the flame retardant is at least one of diammonium hydrogen phosphate, melamine cyanurate and sodium triphosphate.
Further, the solvent is at least one of methanol, ethanol, dimethylacetamide, butanone, toluene and cyclohexanone.
A preparation method of halogen-free flame-retardant epoxy resin, which comprises the following steps:
(1) Mixing 2, 2-diallyl bisphenol A and epichlorohydrin, stirring for 10-15min, adding a benzyl triethyl ammonium chloride catalyst, reacting for 1-4h under the protection of nitrogen, dropwise adding 20-40% sodium hydroxide solution, reacting for 16-18h, filtering, extracting with ethyl acetate and distilled water, washing and drying to obtain 2,2,1,4-epichlorohydrin-diallyl bisphenol A;
(2) Adding 2-aminobenzene imidazole and 4-hydroxybenzaldehyde into a reaction kettle, stirring for 15-20min, reacting for 4-6h, dripping an ethanol solution containing 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide into the reaction kettle at 60-80 ℃ for stirring for 4-6h, filtering, washing with ethanol, and drying to obtain 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide-BHM;
(3) Mixing EDPA and 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide-BHM at 100-120 ℃, stirring, vacuumizing, cooling, adding ethanol, dissolving completely, vacuum degassing, and curing at 60-80 ℃ for 2-4h to obtain modified epoxy resin;
(4) Cutting glass fiber cloth to the required size, taking 10-15 parts by weight of modified halogen-free flame-retardant epoxy resin, 20-30 parts by weight of imidazole accelerator, 20-40 parts by weight of solvent, ball-milling and mixing for 40-70min, coating the mixture on the glass fiber cloth, and baking the mixture for 3-6min at 160-180 ℃ to obtain the halogen-free flame-retardant epoxy resin prepreg.
Further, in the step (1), the mass ratio of the 2, 2-diallyl bisphenol A to the epichlorohydrin is 1:1.2-1.5.
Further, in the step (2), the mass ratio of the 2-aminoimidazole to the 4-hydroxybenzaldehyde ethanol to the ethanol is 1:1.1-1.5:1.2-1.6.
Further, the glass fiber cloth in the step (4) is cut to be 1-2mm in required size.
(III) beneficial technical effects
Mixing 2, 2-diallyl bisphenol A and epichlorohydrin, adding a benzyl triethyl ammonium chloride catalyst, dropwise adding a sodium hydroxide solution under the protection of nitrogen, filtering, extracting with ethyl acetate and distilled water, washing and drying to obtain 2,2,1,4-epichlorohydrin diallyl bisphenol A; adding 2-aminobenzene imidazole and 4-hydroxybenzaldehyde into a reaction kettle, dripping an ethanol solution containing 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide into the reaction kettle, filtering, washing with ethanol, and drying to obtain 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide-BHM; mixing EDPA and 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide-BHM, vacuumizing, cooling, adding ethanol, completely dissolving, vacuum degassing, and solidifying to obtain modified epoxy resin; cutting glass fiber cloth to the required size, mixing the halogen-free flame-retardant epoxy resin, the imidazole accelerator, the solvent and the ball mill according to weight, coating the mixture on the glass fiber cloth, and baking the mixture to obtain the halogen-free flame-retardant epoxy resin prepreg.
Drawings
FIG. 1 shows the effect of gel content on water absorption.
Detailed Description
Example 1
(1) The halogen-free flame-retardant epoxy resin prepreg consists of the following components in parts by weight: 100g of accelerator, 200g of solvent, 100g of curing agent, 250g of epoxy resin and 150g of flame retardant.
(2) 10g of 2, 2-diallyl bisphenol A and 12g of epichlorohydrin are mixed, stirred for 10min, added with benzyl triethyl ammonium chloride catalyst, reacted for 1h under the protection of nitrogen, dropwise added with 20% sodium hydroxide solution, reacted for 16h, filtered, extracted with ethyl acetate and distilled water, washed and dried to obtain 2,2,1,4-epichlorohydrin-diallyl bisphenol A;
(3) Adding 10g of 2-aminobenzene imidazole and 11g of 4-hydroxybenzaldehyde into a reaction kettle, stirring for 15min, reacting for 4h, dripping 12g of ethanol solution containing 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide into the reaction kettle at 60 ℃ for stirring for 4h, filtering, washing with ethanol, and drying to obtain 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide-BHM;
(4) Mixing and stirring EDPA and 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide-BHM at 100 ℃, vacuumizing, cooling, adding ethanol, completely dissolving, vacuum degassing, and curing at 60 ℃ for 2 hours to obtain modified epoxy resin;
(5) Cutting glass fiber cloth to a required size, taking 10 parts by weight of modified halogen-free flame-retardant epoxy resin, 20 parts by weight of 2-methylimidazole or 4-methyl or 2-ethylimidazole, 20 parts by weight of methanol or ethanol or acetone, ball-milling and mixing for 40min, coating the mixture on the glass fiber cloth, and baking at 160 ℃ for 3min to obtain the halogen-free flame-retardant epoxy resin prepreg.
Example 2
(1) The halogen-free flame-retardant epoxy resin prepreg consists of the following components in parts by weight: 150g of accelerator, 250g of solvent, 150g of curing agent, 300g of epoxy resin and 200g of flame retardant.
(2) Mixing 12g of 2, 2-diallyl bisphenol A and 18g of epichlorohydrin, stirring for 15min, adding a benzyl triethyl ammonium chloride catalyst, reacting for 4h under the protection of nitrogen, dropwise adding 40% sodium hydroxide solution, reacting for 18h, filtering, extracting with ethyl acetate and distilled water, washing and drying to obtain 2,2,1,4-epichlorohydrin-diallyl bisphenol A;
(3) Adding 12g of 2-aminobenzene imidazole and 18g of 4-hydroxybenzaldehyde into a reaction kettle, stirring for 20min, reacting for 6h, dripping 19.2g of ethanol solution containing 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide into the reaction kettle at 80 ℃ for stirring for 6h, filtering, washing with ethanol, and drying to obtain 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide-BHM;
(4) Mixing and stirring EDPA and 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide-BHM at 120 ℃, vacuumizing, cooling, adding ethanol, completely dissolving, vacuum degassing, and curing at 80 ℃ for 4 hours to obtain modified epoxy resin;
(5) Cutting glass fiber cloth to a required size, taking 15 parts of modified halogen-free flame-retardant epoxy resin, 30 parts of 2-methylimidazole or 4-methyl or 2-ethylimidazole, 40 parts of methanol or ethanol or acetone according to weight, ball-milling and mixing for 70min, coating the glass fiber cloth, and baking at 180 ℃ for 6min to obtain the halogen-free flame-retardant epoxy resin prepreg.
Example 3
(1) The halogen-free flame-retardant epoxy resin prepreg consists of the following components in parts by weight: 125g accelerator, 225g solvent, 125g curing agent, 275g epoxy resin, 175g flame retardant.
(2) Mixing 11g of 2, 2-diallyl bisphenol A and 15g of epichlorohydrin, stirring for 12.5min, adding a benzyl triethyl ammonium chloride catalyst, reacting for 2.5h under the protection of nitrogen, dropwise adding 30% sodium hydroxide solution, reacting for 17h, filtering, extracting with ethyl acetate and distilled water, washing and drying to obtain 2,2,1,4-epichlorohydrin-diallyl bisphenol A;
(3) Adding 11g of 2-aminobenzene imidazole and 14.5g of 4-hydroxybenzaldehyde into a reaction kettle, stirring for 17.5min, reacting for 5h, dripping 15.6g of ethanol solution containing 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide into the reaction kettle at 70 ℃ for stirring for 5h, filtering, washing with ethanol, and drying to obtain 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide-BHM;
(4) Mixing and stirring EDPA and 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide-BHM at 110 ℃, vacuumizing, cooling, adding ethanol, completely dissolving, vacuum degassing, and curing at 70 ℃ for 3 hours to obtain modified epoxy resin;
(5) Cutting glass fiber cloth to a required size, taking 12.5 parts of modified halogen-free flame-retardant epoxy resin, 25 parts of 2-methylimidazole or 4-methyl or 2-ethylimidazole, 30 parts of methanol or ethanol or acetone according to weight, ball-milling and mixing for 55min, coating the glass fiber cloth, and baking at 170 ℃ for 4.5min to obtain the halogen-free flame-retardant epoxy resin prepreg.
Comparative example 1
(1) The halogen-free flame-retardant epoxy resin prepreg consists of the following components in parts by weight: 125g accelerator, 225g solvent, 125g curing agent, 275g epoxy resin, 175g flame retardant.
(2) 10g of 2, 2-diallyl bisphenol A and 12g of epichlorohydrin are mixed, stirred for 10min, added with benzyl triethyl ammonium chloride catalyst, reacted for 1h under the protection of nitrogen, dropwise added with 20% sodium hydroxide solution, reacted for 16h, filtered, extracted with ethyl acetate and distilled water, washed and dried to obtain 2,2,1,4-epichlorohydrin-diallyl bisphenol A;
(3) Adding 12g of 2-aminobenzene imidazole and 18g of 4-hydroxybenzaldehyde into a reaction kettle, stirring for 20min, reacting for 6h, dripping 19.2g of ethanol solution containing 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide into the reaction kettle at 80 ℃ for stirring for 6h, filtering, washing with ethanol, and drying to obtain 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide-BHM;
(4) Mixing and stirring EDPA and 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide-BHM at 110 ℃, vacuumizing, cooling, adding ethanol, completely dissolving, vacuum degassing, and curing at 70 ℃ for 3 hours to obtain modified epoxy resin;
(5) Cutting glass fiber cloth to a required size, taking 12.5 parts of modified halogen-free flame-retardant epoxy resin, 25 parts of 2-methylimidazole or 4-methyl or 2-ethylimidazole, 30 parts of methanol or ethanol or acetone according to weight, ball-milling and mixing for 55min, coating the glass fiber cloth, and baking at 170 ℃ for 4.5min to obtain the halogen-free flame-retardant epoxy resin prepreg.
Comparative example 2
(1) The halogen-free flame-retardant epoxy resin prepreg consists of the following components in parts by weight: 150g of accelerator, 250g of solvent, 150g of curing agent, 300g of epoxy resin and 200g of flame retardant.
(2) Mixing 11g of 2, 2-diallyl bisphenol A and 15g of epichlorohydrin, stirring for 12.5min, adding a benzyl triethyl ammonium chloride catalyst, reacting for 2.5h under the protection of nitrogen, dropwise adding 30% sodium hydroxide solution, reacting for 17h, filtering, extracting with ethyl acetate and distilled water, washing and drying to obtain 2,2,1,4-epichlorohydrin-diallyl bisphenol A;
(3) Adding 11g of 2-aminobenzene imidazole and 14.5g of 4-hydroxybenzaldehyde into a reaction kettle, stirring for 17.5min, reacting for 5h, dripping 15.6g of ethanol solution containing 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide into the reaction kettle at 70 ℃ for stirring for 5h, filtering, washing with ethanol, and drying to obtain 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide-BHM;
(4) Mixing and stirring EDPA and 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide-BHM at 120 ℃, vacuumizing, cooling, adding ethanol, completely dissolving, vacuum degassing, and curing at 80 ℃ for 4 hours to obtain modified epoxy resin;
(5) Cutting glass fiber cloth to a required size, taking 10 parts by weight of modified halogen-free flame-retardant epoxy resin, 20 parts by weight of 2-methylimidazole or 4-methyl or 2-ethylimidazole, 20 parts by weight of methanol or ethanol or acetone, ball-milling and mixing for 40min, coating the mixture on the glass fiber cloth, and baking at 160 ℃ for 3min to obtain the halogen-free flame-retardant epoxy resin prepreg.
It can be seen from fig. 1 that the water absorption decreases with increasing gel content, and that when the resin content is small, the water absorption of the laminate plate generally decreases with increasing gel content, and the water absorption also decreases with increasing gel content, but slows down to a final substantially constant level. The reason for this phenomenon is: the water absorption of the matrix resin is smaller than that of the glass cloth, when the glue content is increased, the fiber gaps in the glass cloth are continuously filled with the resin, and the data show that the water absorption is continuously reduced; when the gel content reaches a certain value, the matrix resin substantially fills the gaps between the fibers in the glass cloth, and the water absorption rate tends to decrease.
The halogen-free flame retardant epoxy resin prepregs obtained in examples 1,2 and 3 and comparative examples 1 and 2 were selected according to the standard that the thickness is 0.3mm and the number of bubbles within the 10 x 10cm area is not more than 5, and performance comparison is performed, as shown in table 1. The glass transition temperature of the halogen-free flame-retardant epoxy resin prepregs of the examples 1 and 2 is higher than that of the comparative examples, so that the prepreg can keep a higher temperature state at a higher temperature, and the prepreg is wide in application temperature range and higher in viscosity.
TABLE 1 halogen-free flame retardant epoxy resin prepreg performance comparison
As is clear from the analysis of the above examples and comparative examples, the halogen-free flame-retardant epoxy resin prepreg prepared by the invention has obviously improved glue overflow amount, adhesion and heat resistance, wherein the example 1 has the best glue overflow amount, adhesion and heat resistance effects on the prepregs of the comparative examples 1 and 2 of examples 2 and 3.
Table 2 test of peel strength and stability of halogen-free flame retardant epoxy resin prepreg
As is clear from the analysis of the above examples and comparative examples, the peel strength and dimensional stability of the flame-retardant epoxy resin prepreg prepared by the present invention are significantly improved, wherein example 1 has the highest peel strength and dimensional stability for examples 2 and 3, comparative examples 1 and 2.
Table 3 test of flame retardant properties with different contents of composite halogen-free flame retardant epoxy resins
As can be seen from the analysis of the examples and the comparative examples in Table 3, the flame retardant performance of the halogen-free flame retardant epoxy resin prepreg prepared by the invention is remarkably improved, wherein the flame retardant performance of the example 1 is the highest.
Table 4 test mechanical properties of halogen-free flame retardant epoxy resin prepregs
As can be seen from the analysis of the examples and the comparative examples in Table 4, the mechanical properties of the halogen-free flame-retardant epoxy resin prepreg prepared by the invention are remarkably improved, wherein the mechanical properties of the example 1 are the highest.
Claims (8)
1. The halogen-free flame-retardant epoxy resin prepreg is characterized by comprising the following components in parts by weight: 10-20 parts of accelerator, 20-30 parts of solvent, 10-15 parts of curing agent, 40-60 parts of epoxy resin and 30-50 parts of flame retardant.
2. The halogen-free flame retardant epoxy resin prepreg according to claim 1, wherein the curing agent is at least one of imidazoles, imidazolines, trialkyl phosphates and quaternary ammonium salts.
3. The halogen-free flame retardant epoxy resin prepreg according to claim 1, wherein the flame retardant is at least one of diammonium phosphate, melamine cyanurate and sodium triphosphate.
4. The halogen-free flame retardant epoxy resin prepreg according to claim 1, wherein the solvent is at least one of methanol, ethanol, dimethylacetamide, butanone, toluene and cyclohexanone.
5. A preparation method of halogen-free flame-retardant epoxy resin prepreg is characterized by comprising the following steps: the method comprises the following steps:
(1) Mixing 2, 2-diallyl bisphenol A and epichlorohydrin, stirring for 10-15min, adding a catalyst benzyl triethyl ammonium chloride, reacting for 1-4h under the protection of nitrogen, dropwise adding 20-40% sodium hydroxide solution, reacting for 16-18h, filtering, extracting with ethyl acetate and distilled water, washing and drying to obtain 2,2,1,4-epichlorohydrin-diallyl bisphenol A;
(2) Adding 2-aminobenzene imidazole and 4-hydroxybenzaldehyde into a reaction kettle, stirring for 15-20min, reacting for 4-6h, dripping an ethanol solution containing 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide into the reaction kettle at 60-80 ℃ for stirring for 4-6h, filtering, washing with ethanol, and drying to obtain 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide-BHM;
(3) Mixing 2,2,1,4-epichlorohydrin-diallyl bisphenol A and 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide-BHM at 100-120 ℃, stirring, vacuumizing, cooling, adding ethanol, completely dissolving, vacuum degassing, and curing at 60-80 ℃ for 2-4 hours to obtain modified epoxy resin;
(4) Cutting glass fiber cloth to the required size, taking 10-15 parts by weight of modified halogen-free flame-retardant epoxy resin, 20-30 parts by weight of imidazole accelerator, 20-40 parts by weight of solvent, ball-milling and mixing for 40-70min, coating the mixture on the glass fiber cloth, and baking the mixture for 3-6min at 160-180 ℃ to obtain the halogen-free flame-retardant epoxy resin prepreg.
6. The method for preparing the halogen-free flame-retardant epoxy resin prepreg according to claim 4, which is characterized in that: the mass ratio of the 2, 2-diallyl bisphenol A to the epichlorohydrin in the step (1) is 1:1.2-1.5.
7. The method for preparing the halogen-free flame-retardant epoxy resin prepreg according to claim 4, which is characterized in that: in the step (2), the mass ratio of the 2-aminobenzene imidazole to the 4-hydroxybenzaldehyde ethanol to the ethanol is 1:1.1-1.5:1.2-1.6.
8. The method for preparing the halogen-free flame-retardant epoxy resin prepreg according to claim 4, which is characterized in that: and (3) cutting the glass fiber cloth in the step (4) to obtain the glass fiber cloth with the required size of 1-2mm.
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