CN112961498A - High-compatibility organic silicon phenolic epoxy resin composite material and preparation method thereof - Google Patents
High-compatibility organic silicon phenolic epoxy resin composite material and preparation method thereof Download PDFInfo
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- CN112961498A CN112961498A CN202110173397.4A CN202110173397A CN112961498A CN 112961498 A CN112961498 A CN 112961498A CN 202110173397 A CN202110173397 A CN 202110173397A CN 112961498 A CN112961498 A CN 112961498A
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- epoxy resin
- novolac epoxy
- silicone rubber
- composite material
- room temperature
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000010703 silicon Substances 0.000 title claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003822 epoxy resin Substances 0.000 title claims description 13
- 229920000647 polyepoxide Polymers 0.000 title claims description 13
- 239000004843 novolac epoxy resin Substances 0.000 claims abstract description 85
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 60
- 239000004945 silicone rubber Substances 0.000 claims abstract description 50
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 6
- 238000001723 curing Methods 0.000 claims description 36
- -1 ethyl phenylene Chemical group 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 8
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000011324 bead Substances 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 claims description 4
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- XZTUYISAOWDOSC-UHFFFAOYSA-N 1-(4-chlorophenyl)-1,3-dimethylurea Chemical compound CNC(=O)N(C)C1=CC=C(Cl)C=C1 XZTUYISAOWDOSC-UHFFFAOYSA-N 0.000 claims description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 3
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000006004 Quartz sand Substances 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 claims description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 claims description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229920005560 fluorosilicone rubber Polymers 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 3
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims description 3
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 3
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- JWVJCWBVQNCBGA-UHFFFAOYSA-N 3-(dimethylamino)-2-methylphenol Chemical compound CN(C)C1=CC=CC(O)=C1C JWVJCWBVQNCBGA-UHFFFAOYSA-N 0.000 claims description 2
- JADPMLASHMUWSC-BTJKTKAUSA-N C(CCCCCCC)(=O)O.C(\C=C/C(=O)O)(=O)O Chemical compound C(CCCCCCC)(=O)O.C(\C=C/C(=O)O)(=O)O JADPMLASHMUWSC-BTJKTKAUSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 150000002923 oximes Chemical class 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 claims 1
- VNBLTKHUCJLFSB-UHFFFAOYSA-N n-(trimethoxysilylmethyl)aniline Chemical compound CO[Si](OC)(OC)CNC1=CC=CC=C1 VNBLTKHUCJLFSB-UHFFFAOYSA-N 0.000 claims 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims 1
- 238000002679 ablation Methods 0.000 abstract description 12
- 238000005191 phase separation Methods 0.000 abstract description 9
- 238000004132 cross linking Methods 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000000523 sample Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000013068 control sample Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 2
- BTXFTCVNWMNXKH-UHFFFAOYSA-N NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC Chemical compound NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC BTXFTCVNWMNXKH-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- KRJRKEPWQOASJN-UHFFFAOYSA-N aniline;trimethoxy(methyl)silane Chemical compound NC1=CC=CC=C1.CO[Si](C)(OC)OC KRJRKEPWQOASJN-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- DRUVIPAJFTYGKM-UHFFFAOYSA-K C(CCCCCCC)(=O)[O-].[Sn+3].C(CCCCCCC)(=O)[O-].C(CCCCCCC)(=O)[O-] Chemical compound C(CCCCCCC)(=O)[O-].[Sn+3].C(CCCCCCC)(=O)[O-].C(CCCCCCC)(=O)[O-] DRUVIPAJFTYGKM-UHFFFAOYSA-K 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- HNQXCHVZYRDHJN-UHFFFAOYSA-N cyanosilicon Chemical compound [Si]C#N HNQXCHVZYRDHJN-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-compatibility organic silicon novolac epoxy resin composite material and a preparation method thereof, belonging to the technical field of high polymer materials. The preparation method comprises the steps of reacting novolac epoxy resin with a silane coupling agent with amino to obtain modified novolac epoxy resin; adding room temperature vulcanized silicone rubber into the modified novolac epoxy resin, uniformly mixing, then adding a curing agent of the room temperature vulcanized silicone rubber, a catalyst, a curing agent of an epoxy group, an accelerator and a composite filler, standing at room temperature, and then thermally curing to obtain the composite material. The chemically modified novolac epoxy resin has no macroscopic phase separation phenomenon with silicon rubber after co-curing and crosslinking, and the composite material prepared by adding the filler has excellent mechanical property and bonding property, can meet high and low temperature alternating conditions, has good ablation resistance and processability, and is widely applied to the fields of aerospace, missile satellites and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-compatibility organic silicon novolac epoxy resin composite material and a preparation method thereof.
Background
Space environmental conditions such as space flight and aviation, flying moon exploration and the like are harsh, harsh requirements such as high and low temperature alternation and large ablation heat flow resistance need to be met, the requirements of industries such as adhesive coating, electronic packaging and the like on the overall performance of resin are strict, and the requirements are difficult to meet by the conventional resin system. The silicone rubber has the advantages of excellent high and low temperature resistance, but the pure silicone rubber has low bonding strength and poor ablation resistance. The novolac epoxy resin as a high-temperature resistant material has the characteristics of high ablation carbon residue rate, high bonding strength and the like, and is widely applied to the fields of temperature-resistant adhesives, aerospace and aviation and the like. But the pure phenolic resin has poor temperature resistance and cannot meet the requirements of high-temperature and low-temperature alternation.
Aiming at the urgent need of a novel resin system material of a high and low temperature ablation resistant heat-proof material, the phenolic modified organic silicon rubber resin can combine the advantages of phenolic resin and silicon rubber, and is expected to meet the requirements of space high and low temperature alternating environment and ablation heat-proof of returning to the atmosphere.
Chinese patent CN110922765A discloses a flexible heat-resistant ceramizable silicone rubber composite material and a preparation method thereof, wherein the silicone rubber composite material prepared by blending methyl vinyl silicone rubber with other inorganic fillers and auxiliaries has good mechanical properties at medium and low temperature, higher ceramic conversion rate and high-temperature residual rate at high temperature, and good thermal protection performance. According to the patent, silicon rubber, fillers, vulcanizing agents, reinforcing fibers and the like are mixed and vulcanized by a double-roll open mill and a flat vulcanizing machine to prepare the silicon rubber composite material, and a large amount of fillers can be separated from the silicon rubber in the mixing process to cause the performance reduction of the composite material.
Chinese patent CN106893448B discloses a high-temperature ceramic organosilicon-novolac epoxy anticorrosive paint and a preparation method thereof, wherein the silane coupling agent is used for improving the surface adhesion and corrosion resistance effect of organosilicon resin to a metal substrate, and an anticorrosive coating prepared from the components A and B forms a ceramic shell after the actions of high temperature, flame ablation and the like, so that the ceramic shell plays a role in protection. However, the organosilicon surface energy is low, the polarity and solubility difference of the novolac epoxy resin are large, and the two are often separated when mixed, in the patent, the silane coupling agent is added into a novolac epoxy resin system to modify the resin by a one-step method, although the processing technology is good and the operation is convenient, the phase separation may occur after a period of time, and the macroscopic phase separation is more likely to occur in the curing process, so that the material is not uniform, and the reliability of the material is reduced.
Therefore, how to combine the advantages of the novolac epoxy resin and the silicon rubber to design a novel novolac epoxy resin silicon rubber composite material system, and apply the special material to the fields of aerospace, military satellites and the like is one of the problems to be solved urgently in many colleges and universities and enterprises.
Disclosure of Invention
Aiming at the problems that in the prior art, a composite material prepared by simply and physically blending a silane coupling agent, matrix resin, a filler and the like can generate phase separation during later curing and use, so that the material performance is reduced, the use requirement is difficult to meet and the like. The invention aims to solve the technical problem of providing a preparation method of a high-compatibility organic silicon novolac epoxy resin composite material, wherein the chemically modified novolac epoxy resin has no macroscopic phase separation phenomenon with silicon rubber after co-curing and crosslinking, and the preparation method has the advantages of simple preparation process, low production cost and convenient operation. The invention aims to solve another technical problem of providing a high-compatibility organic silicon phenolic epoxy resin composite material which has excellent mechanical property, adhesive property and heat resistance and can widen the application of the organic silicon modified phenolic resin ablation-resistant material in aerospace and national defense industries.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a preparation method of a high-compatibility organic silicon novolac epoxy resin composite material comprises the following steps:
(1) reacting the novolac epoxy resin with a silane coupling agent with amino to obtain modified novolac epoxy resin;
(2) adding room temperature vulcanized silicone rubber into the modified novolac epoxy resin, uniformly mixing at 0-120 ℃, adding a curing agent of the room temperature vulcanized silicone rubber, a catalyst, a curing agent of an epoxy group, an accelerator and a composite filler, standing at room temperature, and heating and curing after the standing to obtain the high-compatibility organic silicon novolac epoxy resin composite material. The reaction equation is as follows:
according to the method for preparing the high-compatibility organic silicon novolac epoxy resin composite material, the modified novolac epoxy resin is subjected to reflux reaction for 0.1-36 hours at the temperature of 0-160 ℃; when heating and curing, heating to 20-180 ℃ for curing for 0.1-24 h.
In the preparation method of the high-compatibility organic silicon novolac epoxy resin composite material, the silane coupling agent with amino is one or the combination of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, aniline methyl trimethoxysilane or aniline methyl triethoxysilane; the dosage of the silane coupling agent with amino is 1-5% of the mass of the novolac epoxy resin.
According to the preparation method of the high-compatibility organic silicon phenolic epoxy resin composite material, the room-temperature vulcanized silicone rubber is one or a combination of dimethyl silicone rubber, methyl vinyl silicone rubber, methyl phenyl silicone rubber, fluorosilicone rubber, nitrile silicone rubber or ethyl silicone rubber and ethyl phenylene silicone rubber; the mass ratio of the novolac epoxy resin to the room-temperature vulcanized silicone rubber is 1: 0.5-1: 9; the curing agent of the room temperature vulcanized silicone rubber is one or the combination of methyl triacetoxysilane, methyl trimethoxy silane, ethyl orthosilicate, methyl triethoxy silane, methyl tributyrine oxime silane, propyl orthosilicate, methyl diethoxy silane or methyl hydrogen-containing silicone oil; the usage amount of the curing agent of the room temperature vulcanized silicone rubber is 0.5-45% of the mass of the novolac epoxy resin.
According to the preparation method of the high-compatibility organic silicon novolac epoxy resin composite material, the catalyst of the room-temperature vulcanized silicone rubber is one or a combination of dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, stannous octoate, stannous chloride, dibutyltin diacetate and tin dioctoate monocaprylate maleate; the dosage of the catalyst is 0.01-15% of the mass of the novolac epoxy resin.
According to the preparation method of the high-compatibility organic silicon novolac epoxy resin composite material, the dosage of the catalyst is 0.1-10% of the mass of the novolac epoxy resin.
According to the preparation method of the high-compatibility organic silicon phenolic aldehyde epoxy resin composite material, the curing agent of the epoxy group is one or a combination of ethylenediamine, diethylenetriamine, m-phenylenediamine, 4-diaminodiphenylmethane, polyether amine, phthalic anhydride, maleic anhydride, pyromellitic dianhydride or hexahydro-phthalic dianhydride; the dosage ratio of the novolac epoxy resin to the curing agent of the epoxy group is 1: 0.7; the accelerant of the epoxy group is one or the combination of 2,4, 6-tri (dimethylaminomethyl) phenol, triethanolamine, N-p-chlorophenyl-N, N' -dimethyl urea, 2-ethyl-4-methylimidazole, resorcinol, 2-methylimidazole, dimethylaminocresol or boron trifluoride amine complex; the dosage of the accelerant is 0.01-5% of the mass of the novolac epoxy resin.
According to the preparation method of the high-compatibility organic silicon novolac epoxy resin composite material, the using amount of the accelerator is 0.1-1% of the mass of the novolac epoxy resin.
According to the preparation method of the high-compatibility organic silicon phenolic epoxy resin composite material, the composite filler is one or a combination of carbon fiber, hollow quartz, high silica, glass beads, phenolic beads, zirconium boride, silicon micropowder, zinc borate, nano aluminum hydroxide, fumed silica, calcium carbonate or quartz sand; the dosage ratio of the novolac epoxy resin to the composite filler is 1: 1-6: 1.
The high-compatibility organic silicon novolac epoxy resin composite material prepared by the method.
Has the advantages that: compared with the prior art, the invention has the advantages that:
(1) the organic silicon modified novolac epoxy resin prepared by the invention has good compatibility with room temperature vulcanized silicone rubber, and the chemically modified novolac epoxy resin has no macroscopic phase separation phenomenon with the silicone rubber after co-curing and crosslinking. The Si-O bond energy in the organic silicon chain segment introduced into the resin system is far greater than that of a C-O bond, so that the phenolic epoxy resin has excellent ablation resistance.
(2) The microstructure morphology shows that the microspheres formed in the novolac epoxy resin are uniformly dispersed in a resin system to form a soft-hard alternating micro phase separation structure, and the mechanical property, the adhesive property and the thermal property of the composite material prepared by adding the filler are obviously improved, so that the composite material can be widely applied to the fields of aerospace, military, electronics and the like.
Drawings
FIG. 1 is a schematic representation of the resin of example 2, example 3, and example 5, as well as the control before (left) and after (right) mixing.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
Example 1
A preparation method of a high-compatibility organic silicon novolac epoxy resin composite material comprises the following steps:
(1) adding 0.1g of gamma-aminopropyltrimethoxysilane and 0.1g of gamma-aminopropyltriethoxysilane into 10g of novolac epoxy resin, stirring and mixing uniformly, carrying out reflux treatment at 0 ℃ for 36h, and removing unreacted raw materials under reduced pressure to obtain modified novolac epoxy resin;
(2) adding 90g of dimethyl room-temperature vulcanized silicone rubber into the modified novolac epoxy resin, stirring and mixing uniformly at 0 ℃, simultaneously adding 4.3g of a curing agent methyl triacetoxysilane of the silicone rubber, 0.625g of a catalyst dibutyltin dilaurate, 7g of a curing agent ethylenediamine of an epoxy group, 0.03g of an accelerator 2,4, 6-tris (dimethylaminomethyl) phenol, 5g of carbon fibers and 5g of hollow quartz, standing at room temperature for 6h, heating and curing at 20 ℃ for 24h, and cooling to obtain the composite material.
Example 2
A preparation method of a high-compatibility organic silicon novolac epoxy resin composite material comprises the following steps:
(1) adding 0.4g of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane into 20g of novolac epoxy resin, stirring and mixing uniformly, carrying out reflux treatment at 160 ℃ for 0.1h, and removing unreacted raw materials under reduced pressure to obtain the modified novolac epoxy resin.
(2) Adding 80g of methyl vinyl silicone rubber into the modified novolac epoxy resin, stirring and mixing uniformly at 120 ℃, simultaneously adding 3.6g of curing agent methyl trimethoxy silane of the silicone rubber, 0.556g of catalyst dioctyl tin dilaurate, 14g of curing agent diethylene triamine of an epoxy group, m-phenylenediamine, 0.06g of accelerator triethanolamine, 5g of high silica and 5g of zirconium boride, standing for 6h at room temperature, heating and curing for 0.1h at 180 ℃, and cooling to room temperature to obtain the composite material.
Example 3
A preparation method of a high-compatibility organic silicon novolac epoxy resin composite material comprises the following steps:
(1) 0.6g of N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane is added into 30g of novolac epoxy resin, the mixture is stirred and mixed evenly, the reflux treatment is carried out for 1h at the temperature of 120 ℃, and the unreacted raw materials are removed under reduced pressure, thus obtaining the modified novolac epoxy resin.
(2) Adding 70g of methyl phenyl silicone rubber into modified novolac epoxy resin, stirring and mixing uniformly at 100 ℃, simultaneously adding 1.936g of curing agent ethyl orthosilicate of the silicone rubber, 1g of propyl orthosilicate, 0.486g of catalyst dibutyltin diacetate, 21g of curing agent phthalic anhydride of an epoxy group, maleic anhydride, 0.09g of accelerator N-p-chlorophenyl-N, N' -dimethyl urea, 5g of glass beads and 5g of phenolic beads, heating and curing at 140 ℃ for 2h at room temperature for 6h, and cooling to room temperature to obtain the composite material.
Example 4
A preparation method of a high-compatibility organic silicon novolac epoxy resin composite material comprises the following steps:
(1) adding 0.8g of N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane into 40g of novolac epoxy resin, stirring and mixing uniformly, carrying out reflux treatment at 90 ℃ for 8h, and removing unreacted raw materials under reduced pressure to obtain the modified novolac epoxy resin.
(2) Adding 60g of fluorosilicone rubber into modified novolac epoxy resin, stirring and mixing uniformly at 80 ℃, simultaneously adding 2.105g of a curing agent methyl triethoxysilane of the silicone rubber, 0.215g of a catalyst stannous octoate, 0.2g of a catalyst stannous chloride, 28g of a curing agent 4, 4' diaminodiphenylmethane of an epoxy group, 0.12g of an accelerator resorcinol, 5g of silicon micropowder and 5g of zinc borate, standing at room temperature for 6h, heating and curing at 100 ℃ for 5h, and cooling to room temperature to obtain the composite material.
Example 5
A preparation method of a high-compatibility organic silicon novolac epoxy resin composite material comprises the following steps:
(1) adding 1g of aniline methyl trimethoxy silane into 50g of novolac epoxy resin, stirring and mixing uniformly, carrying out reflux treatment at 60 ℃ for 12h, and removing unreacted raw materials under reduced pressure to obtain the modified novolac epoxy resin.
(2) Adding 50g of cyanosilicone rubber into modified novolac epoxy resin, stirring and mixing uniformly at 60 ℃, simultaneously adding 1.56g of curing agent methyl tributyl ketoxime silane of the silicone rubber, 0.347g of catalyst dibutyltin diacetate, 35g of curing agent polyether amine of epoxy group, 0.075g of accelerator 2-ethyl-4-methylimidazole, 0.075g of 2-methylimidazole, 5g of nano aluminum hydroxide and 5g of fumed silica, standing at room temperature for 6h, heating and curing at 80 ℃ for 10h, and cooling to room temperature to obtain the composite material.
Example 6
A preparation method of a high-compatibility organic silicon novolac epoxy resin composite material comprises the following steps:
(1) adding 1.2g of aniline methyl triethoxysilane into 60g of novolac epoxy resin, stirring and mixing uniformly, carrying out reflux treatment at 40 ℃ for 24h, and removing unreacted raw materials under reduced pressure to obtain the modified novolac epoxy resin.
(2) Adding 40g of ethyl silicone rubber and ethyl phenylene silicone rubber into the modified novolac epoxy resin, stirring and mixing uniformly at 30 ℃, simultaneously adding 0.43g of curing agent methyl diethoxysilane of the silicone rubber, 0.43g of methyl hydrogen-containing silicone oil, 0.289g of catalyst tin dioctanoate monocaprylate of maleic acid, 42g of curing agent pyromellitic dianhydride of epoxy group, hexahydro-phthalic acid dianhydride, 0.09g of accelerator dimethylamino cresol, 0.09g of boron trifluoride amine complex, 5g of calcium carbonate and 5g of quartz sand, standing at room temperature for 6h, heating and curing at 60 ℃ for 20h, and cooling to room temperature to obtain the composite material.
Preparation of a comparative sample: weighing 50g of novolac epoxy resin and 50g of methyl phenyl silicone rubber, adding the materials into a round-bottom flask, uniformly stirring and mixing, adding 1.5g of gamma-aminopropyltrimethoxysilane, 1.56g of tetraethoxysilane as a curing agent of the silicone rubber, 0.3g of dibutyltin diacetate as a silicone rubber catalyst, 35g of 4, 4-diaminodiphenylmethane as an epoxy curing agent, 0.15g of 2-methylimidazole as an epoxy curing accelerator, 5g of nano aluminum hydroxide and 5g of zinc borate, standing at room temperature for 6 hours, heating and curing at 80 ℃ for 10 hours, and cooling to room temperature to obtain a composite material as a comparison sample.
Table 1 shows the storage modulus data at low temperature of examples 2, 3 and 5 and the comparison sample, the modulus of each material at-150 ℃ is 2000-3000MPa, and the system modulus is basically unchanged along with the increase of the novolac epoxy resin content. With the increase of the temperature, the modulus of each material gradually decreases, and the silicon rubber is gradually changed from a glass state to a rubber state. When the novolac epoxy content reaches 50%, the modulus is 388MPa, mainly due to the fact that novolac epoxy has greater stiffness than silicone rubber. For the same sample, the modulus is mainly divided into two change stages, below-50 ℃, the modulus of the system is reduced along with the increase of the temperature, and above-50 ℃, the modulus of the system is basically kept unchanged.
TABLE 1 moduli at different temperatures for examples 2, 3, 5 and the comparative sample
Sample (I) | E(-150℃)/MPa | E(-100℃)/MPa | E(-50℃)/MPa | E(0℃)/MPa | E(50℃)/MPa |
Control sample | 3140 | 24.0 | 0.538 | 0.523 | 0.535 |
Example 2 | 2530 | 54.5 | 0.579 | 0.409 | 0.425 |
Example 3 | 3450 | 210.8 | 0.115 | 0.802 | 0.829 |
Example 5 | 3430 | 388.0 | 9.42 | 5.88 | 4.91 |
Table 2 shows the mechanical tensile data at room temperature of examples 2, 3, 5 and the comparative sample, and the fracture strength and the elongation at break of the material both tend to increase and decrease with the increase of the novolac epoxy resin content, especially when the novolac epoxy resin content is 30%, the whole material system has the characteristics of higher strength and better toughness. With the increase of the content of the novolac epoxy resin, the Young modulus of the system gradually increases, and the rigidity and the crosslinking density are both larger, so that the toughness of the system is reduced.
Table 2 mechanical tensile data at room temperature for examples 2, 3, 5 and comparative samples
Sample (I) | Elongation at break% | Breaking strength/MPa | Young's modulus/MPa |
Control sample | 227.5 | 0.481 | 0.367 |
Example 2 | 263.2 | 0.671 | 0.332 |
Example 3 | 310.9 | 1.438 | 0.565 |
Example 5 | 78.5 | 0.746 | 1.699 |
Table 3 shows the adhesion strength and the ablation carbon residue rate at room temperature for examples 2, 3, 5 and the comparative sample, and the shear modulus of the material reflects the adhesion property between the resin and the metal. With the increase of the content of the novolac epoxy resin, the peel strength of the material generally shows a gradual increase trend, and different materials cured by the novolac epoxy resin are ablated for 30min at 800 ℃ in an air atmosphere, so that the compactness of the system is gradually increased when the content of the novolac epoxy resin is gradually increased, and a good shape can be kept after ablation at high temperature.
TABLE 3 bond Strength at room temperature and ablation carbon residue ratio for examples 2, 3, 5 and the comparative sample
Sample (I) | Tensile shear peel strength/MPa | Residual carbon percentage% (800 ℃ C.) |
Control sample | 0.313 | 10.0 |
Example 2 | 1.144 | 16.87 |
Example 3 | 0.864 | 19.30 |
Example 5 | 1.272 | 13.0 |
FIG. 1 is a photograph showing the mixed resin in examples 2, 3 and 5 and the comparative example, and it can be seen that the resin was uniformly mixed in the whole immediately after the mixing. After 24h, the comparative sample began to have macro phase separation, while examples 2, 3 and 5 did not have phase separation, indicating that the silicone novolac epoxy resin prepared by the two-step method has high compatibility.
Claims (10)
1. A preparation method of a high-compatibility organic silicon novolac epoxy resin composite material is characterized by comprising the following steps:
(1) reacting the novolac epoxy resin with a silane coupling agent with amino to obtain modified novolac epoxy resin;
(2) adding room temperature vulcanized silicone rubber into the modified novolac epoxy resin, uniformly mixing at 0-120 ℃, adding a curing agent of the room temperature vulcanized silicone rubber, a catalyst, a curing agent of an epoxy group, an accelerator and a composite filler, standing at room temperature, and heating and curing after the standing to obtain the high-compatibility organic silicon novolac epoxy resin composite material.
2. The method for preparing the high-compatibility organic silicon novolac epoxy resin composite material according to claim 1, wherein the modified novolac epoxy resin is prepared by a reflux reaction at 0-160 ℃ for 0.1-36 h; when heating and curing, heating to 20-180 ℃ for curing for 0.1-24 h.
3. The method of claim 1 or 2, wherein the amino silane coupling agent is one or a combination of γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane, N- (β -aminoethyl) - γ -aminopropyltrimethoxysilane, N- (β -aminoethyl) - γ -aminopropylmethyldimethoxysilane, N- (β -aminoethyl) - γ -aminopropyltriethoxysilane, anilinomethyltrimethoxysilane or anilinomethyltriethoxysilane; the dosage of the silane coupling agent with amino is 1-5% of the mass of the novolac epoxy resin.
4. The method of the high compatibility silicone novolac epoxy resin composite material according to claim 1 or 2, wherein the room temperature vulcanized silicone rubber is one or a combination of dimethyl silicone rubber, methyl vinyl silicone rubber, methyl phenyl silicone rubber, fluoro silicone rubber, nitrile silicone rubber or ethyl silicone rubber and ethyl phenylene silicone rubber; the mass ratio of the novolac epoxy resin to the room-temperature vulcanized silicone rubber is 1: 0.5-1: 9; the curing agent of the room temperature vulcanized silicone rubber is one or the combination of methyl triacetoxysilane, methyl trimethoxy silane, ethyl orthosilicate, methyl triethoxy silane, methyl tributyrine oxime silane, propyl orthosilicate, methyl diethoxy silane or methyl hydrogen-containing silicone oil; the usage amount of the curing agent of the room temperature vulcanized silicone rubber is 0.5-45% of the mass of the novolac epoxy resin.
5. The method of claim 1 or 2, wherein the catalyst of the room temperature vulcanized silicone rubber is one or a combination of dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, stannous octoate, stannous chloride, dibutyltin diacetate, and tin dioctoate monocaprylate maleate; the dosage of the catalyst is 0.01-15% of the mass of the novolac epoxy resin.
6. The method for preparing the high-compatibility organic silicon phenolic aldehyde epoxy resin composite material as claimed in claim 1 or 2, wherein the amount of the catalyst is 0.1-10% of the mass of the phenolic aldehyde epoxy resin.
7. The method of claim 1 or 2, wherein the curing agent for the epoxy groups is one or a combination of ethylenediamine, diethylenetriamine, m-phenylenediamine, 4-diaminodiphenylmethane, polyetheramine, phthalic anhydride, maleic anhydride, pyromellitic dianhydride, or hexahydrophthalic dianhydride; the dosage ratio of the novolac epoxy resin to the curing agent of the epoxy group is 1: 0.7; the accelerant of the epoxy group is one or the combination of 2,4, 6-tri (dimethylaminomethyl) phenol, triethanolamine, N-p-chlorophenyl-N, N' -dimethyl urea, 2-ethyl-4-methylimidazole, resorcinol, 2-methylimidazole, dimethylaminocresol or boron trifluoride amine complex; the dosage of the accelerant is 0.01-5% of the mass of the novolac epoxy resin.
8. The method for preparing the high-compatibility organic silicon phenolic aldehyde epoxy resin composite material as claimed in claim 1 or 2, wherein the amount of the accelerator is 0.1-1% of the mass of the phenolic aldehyde epoxy resin.
9. The method for preparing the high-compatibility organic silicon phenolic aldehyde epoxy resin composite material according to claim 1 or 2, wherein the composite filler is one or a combination of carbon fiber, hollow quartz, high silica, glass beads, phenolic aldehyde beads, zirconium boride, silicon micropowder, zinc borate, nano aluminum hydroxide, fumed silica, calcium carbonate or quartz sand; the dosage ratio of the novolac epoxy resin to the composite filler is 1: 1-6: 1.
10. The high-compatibility organic silicon phenolic aldehyde epoxy resin composite material prepared by the method of claim 1 or 2.
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