CN114634783A - Halogen-free flame-retardant high-temperature-resistant epoxy resin sealant and preparation method thereof - Google Patents
Halogen-free flame-retardant high-temperature-resistant epoxy resin sealant and preparation method thereof Download PDFInfo
- Publication number
- CN114634783A CN114634783A CN202210381508.5A CN202210381508A CN114634783A CN 114634783 A CN114634783 A CN 114634783A CN 202210381508 A CN202210381508 A CN 202210381508A CN 114634783 A CN114634783 A CN 114634783A
- Authority
- CN
- China
- Prior art keywords
- parts
- epoxy resin
- agent
- component
- halogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 115
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 115
- 239000003063 flame retardant Substances 0.000 title claims abstract description 71
- 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 62
- 239000000565 sealant Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 78
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 65
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 65
- 229910000077 silane Inorganic materials 0.000 claims abstract description 48
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 47
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 41
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 41
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 41
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical class [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- -1 amide modified graphene Chemical class 0.000 claims abstract description 38
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 32
- 239000007822 coupling agent Substances 0.000 claims abstract description 32
- 239000003085 diluting agent Substances 0.000 claims abstract description 32
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 32
- 238000004383 yellowing Methods 0.000 claims abstract description 32
- 239000012745 toughening agent Substances 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 44
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 229910021389 graphene Inorganic materials 0.000 claims description 29
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 27
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 24
- 239000003292 glue Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 19
- 229910017604 nitric acid Inorganic materials 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 16
- 238000004898 kneading Methods 0.000 claims description 13
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229920001971 elastomer Polymers 0.000 claims description 11
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 10
- 229920000459 Nitrile rubber Polymers 0.000 claims description 10
- 229920004890 Triton X-100 Polymers 0.000 claims description 10
- 239000013504 Triton X-100 Substances 0.000 claims description 10
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 claims description 10
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 229920002545 silicone oil Polymers 0.000 claims description 10
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- KCAMLFCTSSYIFW-UHFFFAOYSA-N 2,4,6-tris(dimethylamino)phenol Chemical compound CN(C)C1=CC(N(C)C)=C(O)C(N(C)C)=C1 KCAMLFCTSSYIFW-UHFFFAOYSA-N 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 8
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 8
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 159000000003 magnesium salts Chemical class 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229940009827 aluminum acetate Drugs 0.000 claims description 4
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 4
- 239000011654 magnesium acetate Substances 0.000 claims description 4
- 229940069446 magnesium acetate Drugs 0.000 claims description 4
- 235000011285 magnesium acetate Nutrition 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 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
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical class CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 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
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 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
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 claims description 2
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims description 2
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 claims description 2
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001408 amides Chemical class 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 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 2
- 230000006872 improvement Effects 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of sealants, and particularly relates to a halogen-free flame-retardant high-temperature-resistant epoxy resin sealant and a preparation method thereof. The sealant comprises A, B components, wherein the component A is a resin matrix, the component B is a curing agent system, and the components comprise the following components in percentage by weight: the component A comprises: 100 parts of epoxy resin, 6-12 parts of polyphosphoric amide modified graphene oxide and carbon nano tubes, 10-14 parts of silane modified magnesium-aluminum hydrotalcite, 16-22 parts of diluent, 1-4 parts of anti-yellowing agent and 0.5-1.5 parts of defoaming agent; and B component: 100 parts of curing agent, 0.5-8 parts of curing accelerator, 3-6 parts of toughening agent, 6-10 parts of coupling agent and 5-10 parts of emulsifier. The mechanical property of the sealant can be effectively improved by adding the polyacrylamide modified graphene oxide, the carbon nano tube and the silane modified magnesium-aluminum hydrotalcite.
Description
Technical Field
The invention belongs to the technical field of sealants. More particularly, relates to a halogen-free flame-retardant high-temperature-resistant epoxy resin sealant and a preparation method thereof.
Background
Epoxy resins (EP) are one of the largest amounts of thermosetting resins because they have high mechanical strength and good adhesion properties and are widely used in the fields of national defense, military, civil industry, and the like. However, it is a flammable material, and has the defects of high brittleness, weak resistance to external impact force, and the like, so that the application of the flame retardant modified epoxy resin in some fields is limited, and therefore, the flame retardant modified epoxy resin is a current research subject.
Flame retardant (Flame retardant) is a substance that can delay the burning rate of polymer materials, and means that the polymer materials achieve the purpose of delaying the burning rate or not being easy to burn by inhibiting one or more burning factors, reducing the heat release rate and the smoke release amount and slowing down the exchange of pyrolysis substances in the burning process of the polymer materials. At the same time, the flame retardant must be able to meet the following requirements: (1) good compatibility: when mechanically blended with a polymer matrix material, the polymer can be well dispersed in the matrix material; (2) high flame-retardant efficiency: the requirement of flame retardance and smoke suppression of the polymer material can be met by adding a small amount of flame retardant; (3) suitable decomposition temperatures are: the material has proper thermal decomposition temperature, and can meet the processing requirements of polymer materials; (4) the chemical inertness is good: the additive flame retardant cannot react with the polymer base material to cause the polymer base material to lose efficacy; (5) no toxicity and no pollution: a large amount of toxic and harmful gas cannot be released during combustion; (6) low cost, wide source and wide application range.
CN110128794A discloses a chlorine-free bromine-free high CTI resin composition and application thereof. The resin composition comprises, by weight, 50-85 parts of epoxy resin, 10-45 parts of phosphorus-containing phenolic resin, 1-15 parts of amine curing agent, 0.01-1 part of curing accelerator, 10-100 parts of filler, 0-20 parts of flame retardant, 1-50 parts of precipitated barium sulfate with the average particle size of 0.1-50 mu m, 1-50 parts of polytetrafluoroethylene micro powder with the average particle size of 0.1-50 mu m, 1-5 parts of dispersing agent, 0.1-2 parts of thixotropic aid and 80-100 parts of organic solvent. The copper-clad plate obtained from the resin composition has the characteristics of good heat resistance, high CTI and good stability.
CN109096493A discloses a polymerization reaction type epoxy resin flame retardant and a preparation method thereof, belonging to the technical field of epoxy resin flame retardants. The structural formula is: wherein the polymerization degree n is an integer between 5 and 200. The preparation method comprises the following steps: under the protection of inert gas, pentaerythritol and distilled phosphorus oxychloride are added into a solvent A, mixed at room temperature until the system is stable, slowly heated until no hydrogen chloride gas is discharged, washed, filtered and dried to obtain the intermediate spiro phosphate diacid chloride. Adding sulfanilamide into a solvent B, stirring until the mixture is clear and transparent, adding an intermediate spiro phosphate diacid chloride, stirring until the system is uniformly mixed, adding an acid binding agent, stirring and refluxing for 2 hours at 50-60 ℃, slowly heating to 60-80 ℃, reacting for 8-12 hours, washing, performing suction filtration, and drying to obtain a white powdery solid. The flame retardant disclosed by the invention is good in moisture absorption resistance and high in flame retardant efficiency, and when the addition amount of the flame retardant in epoxy resin is 10%, the limiting oxygen index reaches 30.2%; the vertical burning test grade can reach UL-94V-0 grade.
CN109971406A discloses a halogen-free flame-retardant epoxy resin sealant, which mainly comprises A, B components, wherein the A component is a resin matrix, and the B component is a curing agent system. The method is mainly characterized in that melamine flame retardant is used for modifying the epoxy resin in the adhesive A to form a flame-retardant epoxy resin matrix. The resin matrix fully exerts the flame retardant property, the curing property and the rigid structure of the melamine flame retardant, and obviously improves the flame retardant property, the mechanical property and the high temperature resistance of the sealant. The sealant can be used for sealing LED light sources.
Although the above documents realize the improvement of the flame retardant property, mechanical property, high temperature resistance and other properties of the sealant by adding the flame retardant, the improvement of the above properties is not obvious and can not meet the requirements of severe environment, so that the development of a new halogen-free flame retardant epoxy resin sealant is urgently needed to solve the problems existing in the prior art.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings in the prior art and provides a halogen-free flame-retardant high-temperature-resistant epoxy resin sealant and a preparation method thereof. The sealant comprises A, B components, wherein the component A is a resin matrix, the component B is a curing agent system, and the components comprise the following components in percentage by weight: and (2) component A: 100 parts of epoxy resin, 6-12 parts of polyphosphoric amide modified graphene oxide and carbon nano tubes, 10-14 parts of silane modified magnesium-aluminum hydrotalcite, 16-22 parts of diluent, 1-4 parts of anti-yellowing agent and 0.5-1.5 parts of defoaming agent; and B component: 100 parts of curing agent, 0.5-8 parts of curing accelerator, 3-6 parts of toughening agent, 6-10 parts of coupling agent and 5-10 parts of emulsifier. The mechanical property of the sealant can be effectively improved by adding the polyacrylamide modified graphene oxide, the carbon nano tube and the silane modified magnesium-aluminum hydrotalcite.
The invention aims to provide a halogen-free flame-retardant high-temperature-resistant epoxy resin sealant.
The invention also aims to provide a preparation method of the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant.
The above purpose of the invention is realized by the following technical scheme:
a halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises A, B components, wherein the A component is a resin matrix, the B component is a curing agent system, and the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises the following components in percentage by weight:
the component A comprises: 100 parts of epoxy resin, 6-12 parts of polyphosphoric amide modified graphene oxide and carbon nano tubes, 10-14 parts of silane modified magnesium-aluminum hydrotalcite, 16-22 parts of diluent, 1-4 parts of anti-yellowing agent and 0.5-1.5 parts of defoaming agent;
and B component: 100 parts of curing agent, 0.5-8 parts of curing accelerator, 3-6 parts of toughening agent, 6-10 parts of coupling agent and 5-10 parts of emulsifier.
Preferably, the preparation method of the polyphosphoric amide modified graphene oxide and the carbon nano tube comprises the following steps of respectively treating the graphene oxide and the carbon nano tube by nitric acid; then adding the treated graphene oxide and the carbon nano tube into an organic solvent, and performing ultrasonic dispersion for 2-4 h; and then adding triethylamine and a proper amount of phenylenediamine in an ice bath, slowly dropwise adding a hexachlorocyclotriphosphazene acetonitrile solution in a nitrogen atmosphere, reacting for 1-2 h under an ice bath condition after dropwise adding, heating to 40-60 ℃, refluxing for 20-30 h, finally filtering and washing a product, and drying at 60-80 ℃ for 12-16 h to obtain the polyphosphamide modified graphene oxide and the carbon nano tube.
Preferably, the concentration of the nitric acid is 10-25 wt%, and the treatment time is 1-3 h; the material ratio of the treated graphene oxide to the treated carbon nanotube to the organic solvent to triethylamine is as follows: 1-3 g: 1-3 g; 200-260 mL: 6-10 g, wherein the organic solvent is at least one of acetonitrile, ethanol and methanol.
Preferably, the molar ratio of the phenylenediamine to the hexachlorocyclotriphosphazene is 2: 1; the mass ratio of the sum of the mass of the treated graphene oxide and the treated carbon nano tube to the sum of phenylenediamine and hexachlorocyclotriphosphazene is 1: 2-4.
Preferably, the preparation method of the silane modified magnesium-aluminum hydrotalcite comprises the following steps: weighing magnesium salt and aluminum salt, dissolving in 20-40 vol% ethanol water, and mixingA salt solution, then adding an amount of Mg (OH)2Adding the mixture into the solution, adding an ethanol solution of silane with the concentration of 0.5-1 mol/L, stirring for 10-30 min, then dropwise adding alkali liquor until the pH value of the solution is 10, wherein the alkali concentration is 1-3 mol/L, then transferring the solution into a hydrothermal reaction kettle, reacting for 6-10 h at 120-160 ℃, centrifuging, washing, drying for 12-16 h at 80-100 ℃, and grinding to obtain the silane modified magnesium-aluminum hydrotalcite.
Preferably, the magnesium salt is at least one of magnesium nitrate, magnesium acetate and magnesium chloride; the aluminum is at least one of aluminum nitrate, aluminum acetate and aluminum chloride; the alkali is one of sodium hydroxide, potassium hydroxide, urea and ammonia water; the silane is at least one of KH550, KH560 and KH 570.
Preferably, the molar ratio of the magnesium salt to the aluminum salt is 1: 2-4; the molar ratio of the aluminum to the silane is 1: 0.01-0.03; the Mg (OH)2The addition amount of (B) is 10-30 wt% of the final product.
Preferably, the epoxy resin comprises bisphenol A epoxy resin, phenolic resin epoxy resin and hydrogenated bisphenol A epoxy resin, and the epoxy value of the epoxy resin is between 0.02 and 0.56;
preferably, the diluent comprises one or a mixture of trimethylolpropane triglycidyl ether or C12-14 aliphatic glycidyl ether;
preferably, the anti-yellowing agent is an ultraviolet absorbent and comprises one or more of UV-40, UV-531, UV-9, UV-P, UV-329, UV-326, UV-320, UV-234 and UV-0; preferably, the defoaming agent is dimethyl silicone oil.
Preferably, the curing agent is one or a mixture of more of methylhexahydrophthalic anhydride, phthalic anhydride, maleic anhydride and methylnadic anhydride;
preferably, the curing accelerator is one or more of 2,4, 6-tris (dimethylamino) phenol (TAP), tris (2-ethylhexanoate) salt of 2,4, 6-tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 1, 2-dimethylimidazole;
preferably, the toughening agent is carboxyl-terminated butadiene-acrylonitrile rubber;
preferably, the coupling agent in the component B is one or a mixture of more of methyltrimethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and tetraethoxysilane;
preferably, the emulsifier in the component B is triton X-100.
The preparation method of the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises the following steps:
preparing glue A: mixing epoxy resin, the polyphosphoric acid amide modified graphene oxide, the carbon nano tube and the silane modified magnesium-aluminum hydrotalcite at 75-85 ℃ for 40-80 min, then sequentially adding a diluent, an anti-yellowing agent and a defoaming agent into the mixed components, continuously stirring for 30-50 min, and cooling to room temperature to obtain a component A;
b, preparation of glue B: and (3) sequentially adding a curing agent, a curing accelerator, a toughening agent, a coupling agent and an emulsifier into a kneading machine, fully kneading for 40-70min at 60-90 ℃, cooling and discharging to obtain the component B.
The invention has the following beneficial effects:
(1) by adopting the polyphosphoric acid amide to modify the carbon nano tube and the graphene oxide and utilizing the mutual synergistic effect between the carbon nano tube and the graphene oxide, the compatibility with the epoxy resin can be improved, and the mechanical property and the flame retardance of the epoxy resin can also be improved.
(2) The hydrotalcite is prepared on the surface of the magnesium hydroxide in situ, and the mechanical property and the flame retardant property of the epoxy resin can be obviously improved through silane modification.
(3) The interaction between the carbon nano tube modified by the polyphosphoric acid amide and the graphene oxide and the silane modified hydrotalcite is utilized, so that the mechanical property and the flame retardant property of the epoxy resin are further improved.
(4) The sealant prepared by the invention has excellent flame retardant property, heat resistance and other properties and also has excellent mechanical properties.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
A halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises A, B components, wherein the A component is a resin matrix, the B component is a curing agent system, and the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises the following components in percentage by weight:
the component A comprises: 100 parts of epoxy resin, 8 parts of polyphosphoric amide modified graphene oxide and carbon nano tubes, 12 parts of silane modified magnesium-aluminum hydrotalcite, 19 parts of diluent, 3 parts of anti-yellowing agent and 1 part of defoaming agent;
and B component: 100 parts of curing agent, 4 parts of curing accelerator, 5 parts of flexibilizer, 8 parts of coupling agent and 8 parts of emulsifier.
The preparation method of the polyphosphamide modified graphene oxide and the carbon nano tube comprises the following steps of respectively treating the graphene oxide and the carbon nano tube for 2 hours by nitric acid with the concentration of 18 wt%; then 2g of the treated nitric acid-treated graphene oxide and 2g of the treated nitric acid-treated carbon nano tube are added into 230mL of ethanol, and ultrasonic dispersion is carried out for 3 hours; then adding 8g of triethylamine and a proper amount of phenylenediamine in an ice bath, slowly dropwise adding a hexachlorocyclotriphosphazene acetonitrile solution in a nitrogen atmosphere, and controlling the molar ratio of the phenylenediamine to the hexachlorocyclotriphosphazene to be 2: 1; the mass ratio of the sum of the mass of the treated graphene oxide and the treated carbon nano tube to the sum of phenylenediamine and hexachlorocyclotriphosphazene is 1: 3; after the dropwise addition, reacting for 1.5h under an ice bath condition, heating to 50 ℃ and refluxing for 25h, finally filtering and washing the product, and drying at 70 ℃ for 14h to obtain the polyphosphoric amide modified graphene oxide and the carbon nano tube;
the preparation method of the silane modified magnesium-aluminum hydrotalcite comprises the following steps: weighing 3mol of magnesium nitrate and 1mol of aluminum nitrate, dissolving the magnesium nitrate and the aluminum nitrate in 80mL of 30 volume percent ethanol water to prepare a mixed salt solution, and then adding a certain amount of Mg (OH)2Is added to the aboveAdding 20mL of ethanol solution with the concentration of 1mol/L KH560 into the solution; stirring for 20min, then dropwise adding sodium hydroxide with the concentration of 2mol/L until the pH value of the solution is 10, then transferring the solution into a hydrothermal reaction kettle, reacting for 8h at 140 ℃, centrifuging, washing, drying for 14h at 90 ℃, and grinding to obtain silane modified magnesium-aluminum hydrotalcite; wherein Mg (OH)2Is added in an amount of 20 wt% of the final product;
the epoxy resin is bisphenol A type epoxy resin, and the epoxy value of the epoxy resin is 0.038;
the diluent is trimethylolpropane triglycidyl ether;
the anti-yellowing agent is UV-329;
the defoaming agent is dimethyl silicone oil;
the curing agent is methyl hexahydrophthalic anhydride;
the curing accelerator is 2,4, 6-tris (dimethylamino) phenol (TAP);
the toughening agent is carboxyl-terminated butadiene-acrylonitrile rubber;
the coupling agent in the component B is methyl trimethoxy silane.
The emulsifier in the component B is triton X-100;
the preparation method of the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant is characterized by comprising the following steps of:
preparation of glue A: mixing epoxy resin, the polyphosphoric amide modified graphene oxide, the carbon nano tube and the silane modified magnesium-aluminum hydrotalcite at 80 ℃ for 60min, then sequentially adding a diluent, an anti-yellowing agent and a defoaming agent into the mixed components, continuously stirring for 40min, and cooling to room temperature to obtain a component A;
b, preparation of glue B: and (3) adding a curing agent, a curing accelerator, a toughening agent, a coupling agent and an emulsifier into a kneader in sequence, fully kneading for 60min at 800 ℃, cooling and discharging to obtain the component B.
Example 2
A halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises A, B components, wherein the A component is a resin matrix, the B component is a curing agent system, and the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises the following components in percentage by weight:
and (2) component A: 100 parts of epoxy resin, 12 parts of polyphosphoric amide modified graphene oxide and carbon nano tubes, 10 parts of silane modified magnesium-aluminum hydrotalcite, 22 parts of diluent, 1 part of anti-yellowing agent and 1.5 parts of defoaming agent;
and B component: 100 parts of curing agent, 8 parts of curing accelerator, 3 parts of toughening agent, 10 parts of coupling agent and 5 parts of emulsifier.
The preparation method of the polyphosphamide modified graphene oxide and the carbon nano tube comprises the following steps of respectively treating the graphene oxide and the carbon nano tube for 2 hours by nitric acid with the concentration of 18 wt%; then adding 3g of the treated graphene oxide and 1g of the treated carbon nano tube into 260mL of acetonitrile solvent, and performing ultrasonic dispersion for 4 hours; then 10g of triethylamine and a proper amount of phenylenediamine are added in an ice bath, and under the nitrogen atmosphere, hexachlorocyclotriphosphazene acetonitrile solution is slowly dripped, and the molar ratio of the phenylenediamine to the hexachlorocyclotriphosphazene is controlled to be 2: 1; the mass ratio of the sum of the mass of the treated graphene oxide and the treated carbon nano tube to the sum of phenylenediamine and hexachlorocyclotriphosphazene is 1: 2; after the dropwise addition is finished, reacting for 2h under an ice bath condition, heating to 60 ℃, refluxing for 20h, finally filtering and washing the product, and drying at 80 ℃ for 12h to obtain the polyphosphoric amide modified graphene oxide and the carbon nano tube;
the preparation method of the silane modified magnesium-aluminum hydrotalcite comprises the following steps: weighing 2mol of magnesium chloride and 1mol of aluminum chloride, dissolving in 80mL of 40 vol% ethanol water to prepare a mixed salt solution, and then adding a certain amount of Mg (OH)2Adding the mixture into the solution, adding 60mL of ethanol solution with the concentration of 0.5mol/L KH550, stirring for 30min, then dropwise adding 3mol/L potassium hydroxide solution until the pH value of the solution is 10, then transferring the solution into a hydrothermal reaction kettle, reacting for 6h at 160 ℃, centrifuging, washing, drying for 12h at 100 ℃, and grinding to obtain silane modified magnesium-aluminum hydrotalcite; wherein Mg (OH)2Is added in an amount of 30 wt% of the final product;
the epoxy resin is phenolic resin type epoxy resin, and the epoxy value of the epoxy resin is 0.56;
the diluent is trimethylolpropane triglycidyl ether;
the anti-yellowing agent is UV-40;
the defoaming agent is dimethyl silicone oil;
the curing agent is phthalic anhydride;
the curing accelerator is 2-methylimidazole;
the toughening agent is carboxyl-terminated butadiene-acrylonitrile rubber;
the coupling agent in the component B is dimethyl dimethoxy silane.
The emulsifier in the component B is triton X-100;
the preparation method of the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant is characterized by comprising the following steps of:
preparation of glue A: mixing epoxy resin, the polyphosphoric amide modified graphene oxide, the carbon nano tube and the silane modified magnesium-aluminum hydrotalcite at 85 ℃ for 40min, then sequentially adding a diluent, an anti-yellowing agent and a defoaming agent into the mixed components, continuously stirring for 50min, and cooling to room temperature to obtain a component A;
b, preparation of glue B: and (3) adding a curing agent, a curing accelerator, a toughening agent, a coupling agent and an emulsifier into a kneader in sequence, fully kneading for 40min at 90 ℃, cooling and discharging to obtain the component B.
Example 3
A halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises A, B components, wherein the A component is a resin matrix, the B component is a curing agent system, and the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises the following components in parts by weight:
the component A comprises: 100 parts of epoxy resin, 6 parts of polyphosphoric amide modified graphene oxide and carbon nano tubes, 14 parts of silane modified magnesium-aluminum hydrotalcite, 16 parts of diluent, 4 parts of anti-yellowing agent and 0.5 part of defoaming agent;
and B component: 100 parts of curing agent, 0.5 part of curing accelerator, 6 parts of toughening agent, 6 parts of coupling agent and 10 parts of emulsifier.
The preparation method of the polyphosphamide modified graphene oxide and the carbon nano tube comprises the following steps of respectively treating the graphene oxide and the carbon nano tube for 2 hours by nitric acid with the concentration of 18 wt%; then adding 1g of the treated graphene oxide and 3g of the treated carbon nano tube into 200mL of methanol solvent, and performing ultrasonic dispersion for 4 hours; then 6g of triethylamine and a proper amount of phenylenediamine are added in an ice bath, and under the nitrogen atmosphere, hexachlorocyclotriphosphazene acetonitrile solution is slowly dripped, and the molar ratio of the phenylenediamine to the hexachlorocyclotriphosphazene is controlled to be 2: 1; the mass ratio of the sum of the mass of the treated graphene oxide and the treated carbon nano tube to the sum of phenylenediamine and hexachlorocyclotriphosphazene is 1: 4; after the dropwise addition is finished, reacting for 2h under an ice bath condition, heating to 40 ℃ and refluxing for 30h, finally filtering and washing the product, and drying at 60 ℃ for 16h to obtain the polyphosphoric amide modified graphene oxide and the carbon nano tube;
the preparation method of the silane modified magnesium-aluminum hydrotalcite comprises the following steps: weighing 4mol of magnesium acetate and 1mol of aluminum acetate, and dissolving the magnesium acetate and the aluminum acetate in 80mL of 20 vol% ethanol water to prepare a mixed salt solution; then adding a certain amount of Mg (OH)2Adding the mixture into the solution, adding 10mL of ethanol solution with the concentration of 1mol/L KH570, stirring for 10min, then dropwise adding 1mol/L ammonia water solution until the pH value of the solution is 10, then transferring the solution into a hydrothermal reaction kettle, reacting for 10h at 120 ℃, centrifuging, washing, drying for 16h at 80 ℃, and grinding to obtain silane modified magnesium-aluminum hydrotalcite; wherein Mg (OH)2Is added in an amount of 10 wt% of the final product;
the epoxy resin is hydrogenated bisphenol A type epoxy resin, and the epoxy value of the epoxy resin is 0.02;
the diluent is trimethylolpropane triglycidyl ether;
the anti-yellowing agent is UV-531;
the defoaming agent is dimethyl silicone oil;
the curing agent is maleic anhydride;
the curing accelerator is tris (2-ethylhexanoate) salt of 2,4, 6-tris (dimethylaminomethyl) phenol;
the toughening agent is carboxyl-terminated butadiene-acrylonitrile rubber;
the coupling agent in the component B is vinyl triethoxysilane.
The emulsifier in the component B is triton X-100;
the preparation method of the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant is characterized by comprising the following steps of:
preparing glue A: mixing epoxy resin, the polyphosphoric amide modified graphene oxide, the carbon nano tube and the silane modified magnesium-aluminum hydrotalcite at 75 ℃ for 80min, then sequentially adding a diluent, an anti-yellowing agent and a defoaming agent into the mixed components, continuously stirring for 50min, and cooling to room temperature to obtain a component A;
b, preparation of glue B: and (3) sequentially adding a curing agent, a curing accelerator, a toughening agent, a coupling agent and an emulsifier into a kneading machine, fully kneading for 70min at 60 ℃, cooling and discharging to obtain the component B.
Comparative example 1
A halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises A, B components, wherein the A component is a resin matrix, the B component is a curing agent system, and the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises the following components in percentage by weight:
the component A comprises: 100 parts of epoxy resin, 8 parts of polyphosphoric amide modified graphene oxide, 12 parts of silane modified magnesium-aluminum hydrotalcite, 19 parts of diluent, 3 parts of anti-yellowing agent and 1 part of defoaming agent;
and B component: 100 parts of curing agent, 4 parts of curing accelerator, 5 parts of flexibilizer, 8 parts of coupling agent and 8 parts of emulsifier.
The preparation method of the polyphosphoric amide modified graphene oxide comprises the following steps of treating the graphene oxide for 2 hours by nitric acid with the concentration of 18 wt%; then adding 4g of the treated nitric acid-treated graphene oxide into 230mL of ethanol, and performing ultrasonic dispersion for 3 hours; then adding 8g of triethylamine and a proper amount of phenylenediamine in an ice bath, slowly dropwise adding a hexachlorocyclotriphosphazene acetonitrile solution in a nitrogen atmosphere, and controlling the molar ratio of the phenylenediamine to the hexachlorocyclotriphosphazene to be 2: 1; the mass ratio of the treated graphene oxide to the sum of phenylenediamine and hexachlorocyclotriphosphazene is 1: 3; after the dropwise addition, reacting for 1.5h under an ice bath condition, heating to 50 ℃ and refluxing for 25h, finally filtering and washing the product, and drying at 70 ℃ for 14h to obtain the polyphosphoric acid amide modified graphene oxide;
the preparation method of the silane modified magnesium-aluminum hydrotalcite comprises the following steps: weighing 3mol of magnesium nitrate and 1mol of aluminum nitrate, dissolving the magnesium nitrate and the aluminum nitrate in 80mL of 30 volume percent ethanol water to prepare a mixed salt solution, and then adding a certain amount of Mg (OH)2Is added toAdding 20mL of ethanol solution with the concentration of 1mol/L KH560 into the solution; stirring for 20min, then dropwise adding sodium hydroxide with the concentration of 2mol/L until the pH value of the solution is 10, then transferring the solution into a hydrothermal reaction kettle, reacting for 8h at 140 ℃, centrifuging, washing, drying for 14h at 90 ℃, and grinding to obtain silane modified magnesium-aluminum hydrotalcite; wherein Mg (OH)2Is added in an amount of 20 wt% of the final product;
the epoxy resin is bisphenol A type epoxy resin, and the epoxy value of the epoxy resin is 0.038;
the diluent is trimethylolpropane triglycidyl ether;
the anti-yellowing agent is UV-329;
the defoaming agent is dimethyl silicone oil;
the curing agent is methyl hexahydrophthalic anhydride;
the curing accelerator is 2,4, 6-tris (dimethylamino) phenol (TAP);
the toughening agent is carboxyl-terminated butadiene-acrylonitrile rubber;
the coupling agent in the component B is methyl trimethoxy silane.
The emulsifier in the component B is triton X-100;
the preparation method of the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant is characterized by comprising the following steps of:
preparation of glue A: mixing epoxy resin, the polyphosphoric amide modified graphene oxide and the silane modified magnesium-aluminum hydrotalcite at 80 ℃ for 60min, then sequentially adding a diluent, an anti-yellowing agent and a defoaming agent into the mixed components, continuously stirring for 40min, and cooling to room temperature to obtain a component A;
b, preparation of glue B: and (3) adding a curing agent, a curing accelerator, a toughening agent, a coupling agent and an emulsifier into a kneader in sequence, fully kneading for 60min at 800 ℃, cooling and discharging to obtain the component B.
Comparative example 2
A halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises A, B components, wherein the A component is a resin matrix, the B component is a curing agent system, and the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises the following components in percentage by weight:
and (2) component A: 100 parts of epoxy resin, 8 parts of a carbon nano tube modified by polyphosphoric acid amide, 12 parts of silane modified magnesium-aluminum hydrotalcite, 19 parts of a diluent, 3 parts of an anti-yellowing agent and 1 part of a defoaming agent;
and B component: 100 parts of curing agent, 4 parts of curing accelerator, 5 parts of flexibilizer, 8 parts of coupling agent and 8 parts of emulsifier.
The preparation method of the carbon nano tube modified by the polyphosphoric acid amide comprises the following steps of treating the carbon nano tube for 2 hours by nitric acid with the concentration of 18 wt% respectively; then adding 4g of the treated nitric acid-treated carbon nano tube into 230mL of ethanol, and performing ultrasonic dispersion for 3 hours; then adding 8g of triethylamine and a proper amount of phenylenediamine in an ice bath, slowly dropwise adding a hexachlorocyclotriphosphazene acetonitrile solution in a nitrogen atmosphere, and controlling the molar ratio of the phenylenediamine to the hexachlorocyclotriphosphazene to be 2: 1; the mass ratio of the treated carbon nano tube to the sum of phenylenediamine and hexachlorocyclotriphosphazene is 1: 3; after the dropwise addition, reacting for 1.5h under an ice bath condition, heating to 50 ℃ and refluxing for 25h, finally filtering and washing the product, and drying at 70 ℃ for 14h to obtain the polyphosphoric amide modified graphene oxide and the carbon nano tube;
the preparation method of the silane modified magnesium-aluminum hydrotalcite comprises the following steps: weighing 3mol of magnesium nitrate and 1mol of aluminum nitrate, dissolving the magnesium nitrate and the aluminum nitrate in 80mL of 30 volume percent ethanol water to prepare a mixed salt solution, and then adding a certain amount of Mg (OH)2Adding into the above solution, adding 20mL ethanol solution with concentration of 1mol/L KH 560; stirring for 20min, then dropwise adding sodium hydroxide with the concentration of 2mol/L until the pH value of the solution is 10, then transferring the solution into a hydrothermal reaction kettle, reacting for 8h at 140 ℃, centrifuging, washing, drying for 14h at 90 ℃, and grinding to obtain silane modified magnesium-aluminum hydrotalcite; wherein Mg (OH)2Is added in an amount of 20 wt% of the final product;
the epoxy resin is bisphenol A type epoxy resin, and the epoxy value of the epoxy resin is 0.038;
the diluent is trimethylolpropane triglycidyl ether;
the anti-yellowing agent is UV-329;
the defoaming agent is dimethyl silicone oil;
the curing agent is methyl hexahydrophthalic anhydride;
the curing accelerator is 2,4, 6-tris (dimethylamino) phenol (TAP);
the toughening agent is carboxyl-terminated butadiene-acrylonitrile rubber;
the coupling agent in the component B is methyl trimethoxy silane.
The emulsifier in the component B is triton X-100;
the preparation method of the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant is characterized by comprising the following steps of:
preparing glue A: mixing epoxy resin, a carbon nano tube modified by polyphosphoric acid amide and silane modified magnesium-aluminum hydrotalcite at 80 ℃ for 60min, then sequentially adding a diluent, an anti-yellowing agent and a defoaming agent into the mixed components, continuously stirring for 40min, and cooling to room temperature to obtain a component A;
b, preparation of glue B: and (3) adding a curing agent, a curing accelerator, a toughening agent, a coupling agent and an emulsifier into a kneader in sequence, fully kneading for 60min at 800 ℃, cooling and discharging to obtain the component B.
Comparative example 3
A halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises A, B components, wherein the A component is a resin matrix, the B component is a curing agent system, and the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises the following components in percentage by weight:
the component A comprises: 100 parts of epoxy resin, 8 parts of polyphosphoric amide modified graphene oxide and carbon nano tubes, 12 parts of silane modified magnesium-aluminum hydrotalcite, 19 parts of diluent, 3 parts of anti-yellowing agent and 1 part of defoaming agent;
and B component: 100 parts of curing agent, 4 parts of curing accelerator, 5 parts of flexibilizer, 8 parts of coupling agent and 8 parts of emulsifier.
The preparation method of the polyphosphamide modified graphene oxide and the carbon nano tube comprises the following steps of respectively treating the graphene oxide and the carbon nano tube for 2 hours by nitric acid with the concentration of 18 wt%; then 2g of the treated nitric acid-treated graphene oxide and 2g of the treated nitric acid-treated carbon nano tube are added into 230mL of ethanol, and ultrasonic dispersion is carried out for 3 hours; then adding 8g of triethylamine and a proper amount of phenylenediamine in an ice bath, slowly dropwise adding a hexachlorocyclotriphosphazene acetonitrile solution in a nitrogen atmosphere, and controlling the molar ratio of the phenylenediamine to the hexachlorocyclotriphosphazene to be 2: 1; the mass ratio of the sum of the mass of the treated graphene oxide and the treated carbon nano tube to the sum of phenylenediamine and hexachlorocyclotriphosphazene is 1: 3; after the dropwise addition is finished, reacting for 1.5h under an ice bath condition, heating to 50 ℃, refluxing for 25h, finally filtering and washing the product, and drying for 14h at 70 ℃ to obtain the polyphosphoric amide modified graphene oxide and the carbon nano tube;
the preparation method of the silane modified magnesium-aluminum hydrotalcite comprises the following steps: weighing 3mol of magnesium nitrate and 1mol of aluminum nitrate, dissolving the magnesium nitrate and the aluminum nitrate in 80mL of 30-volume percent ethanol water to prepare a mixed salt solution, and adding 20mL of 1mol/LKH560 ethanol solution; stirring for 20min, then dropwise adding sodium hydroxide with the concentration of 2mol/L until the pH value of the solution is 10, then transferring the solution into a hydrothermal reaction kettle, reacting for 8h at 140 ℃, centrifuging, washing, drying for 14h at 90 ℃, and grinding to obtain silane modified magnesium-aluminum hydrotalcite;
the epoxy resin is bisphenol A type epoxy resin, and the epoxy value of the epoxy resin is 0.038;
the diluent is trimethylolpropane triglycidyl ether;
the anti-yellowing agent is UV-329;
the defoaming agent is dimethyl silicone oil;
the curing agent is methyl hexahydrophthalic anhydride;
the curing accelerator is 2,4, 6-tris (dimethylamino) phenol (TAP);
the toughening agent is carboxyl-terminated butadiene-acrylonitrile rubber;
the coupling agent in the component B is methyl trimethoxy silane.
The emulsifier in the component B is triton X-100;
the preparation method of the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant is characterized by comprising the following steps of:
preparing glue A: mixing epoxy resin, the polyphosphoric amide modified graphene oxide, the carbon nano tube and the silane modified magnesium-aluminum hydrotalcite at 80 ℃ for 60min, then sequentially adding a diluent, an anti-yellowing agent and a defoaming agent into the mixed components, continuously stirring for 40min, and cooling to room temperature to obtain a component A;
b, preparation of glue B: and (3) adding a curing agent, a curing accelerator, a toughening agent, a coupling agent and an emulsifier into a kneader in sequence, fully kneading for 60min at 800 ℃, cooling and discharging to obtain the component B.
Comparative example 4
A halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises A, B components, wherein the A component is a resin matrix, the B component is a curing agent system, and the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises the following components in percentage by weight:
the component A comprises: 100 parts of epoxy resin, 20 parts of polyphosphoric amide modified graphene oxide and carbon nano tubes, 19 parts of diluent, 3 parts of anti-yellowing agent and 1 part of defoaming agent;
and B component: 100 parts of curing agent, 4 parts of curing accelerator, 5 parts of flexibilizer, 8 parts of coupling agent and 8 parts of emulsifier.
The preparation method of the polyphosphamide modified graphene oxide and the carbon nano tube comprises the following steps of respectively treating the graphene oxide and the carbon nano tube for 2 hours by nitric acid with the concentration of 18 wt%; then 2g of the treated nitric acid-treated graphene oxide and 2g of the treated nitric acid-treated carbon nano tube are added into 230mL of ethanol, and ultrasonic dispersion is carried out for 3 hours; then adding 8g of triethylamine and a proper amount of phenylenediamine in an ice bath, slowly dropwise adding a hexachlorocyclotriphosphazene acetonitrile solution in a nitrogen atmosphere, and controlling the molar ratio of the phenylenediamine to the hexachlorocyclotriphosphazene to be 2: 1; the mass ratio of the sum of the mass of the treated graphene oxide and the treated carbon nano tube to the sum of phenylenediamine and hexachlorocyclotriphosphazene is 1: 3; after the dropwise addition, reacting for 1.5h under an ice bath condition, heating to 50 ℃ and refluxing for 25h, finally filtering and washing the product, and drying at 70 ℃ for 14h to obtain the polyphosphoric amide modified graphene oxide and the carbon nano tube;
the epoxy resin is bisphenol A type epoxy resin, and the epoxy value of the epoxy resin is 0.038;
the diluent is trimethylolpropane triglycidyl ether;
the anti-yellowing agent is UV-329;
the defoaming agent is dimethyl silicone oil;
the curing agent is methyl hexahydrophthalic anhydride;
the curing accelerator is 2,4, 6-tris (dimethylamino) phenol (TAP);
the toughening agent is carboxyl-terminated butadiene-acrylonitrile rubber;
the coupling agent in the component B is methyl trimethoxy silane.
The emulsifier in the component B is triton X-100;
the preparation method of the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant is characterized by comprising the following steps of:
preparation of glue A: mixing epoxy resin, the polyphosphoric acid amide modified graphene oxide and the carbon nano tube at 80 ℃ for 60min, then sequentially adding a diluent, an anti-yellowing agent and a defoaming agent into the mixed components, continuously stirring for 40min, and cooling to room temperature to obtain a component A;
b, preparing glue: and (3) sequentially adding a curing agent, a curing accelerator, a toughening agent, a coupling agent and an emulsifier into a kneading machine, fully kneading for 60min at 800 ℃, cooling and discharging to obtain the component B.
Comparative example 5
A halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises A, B components, wherein the A component is a resin matrix, the B component is a curing agent system, and the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant comprises the following components in percentage by weight:
the component A comprises: 100 parts of epoxy resin, 20 parts of silane modified magnesium aluminum hydrotalcite, 19 parts of diluent, 3 parts of anti-yellowing agent and 1 part of defoaming agent;
and the component B comprises: 100 parts of curing agent, 4 parts of curing accelerator, 5 parts of flexibilizer, 8 parts of coupling agent and 8 parts of emulsifier.
The preparation method of the silane modified magnesium-aluminum hydrotalcite comprises the following steps: weighing 3mol of magnesium nitrate and 1mol of aluminum nitrate, dissolving the magnesium nitrate and the aluminum nitrate in 80mL of 30 volume percent ethanol water to prepare a mixed salt solution, and then adding a certain amount of Mg (OH)2Adding into the above solution, and adding 20mL ethanol solution with concentration of 1mol/L KH 560; stirring for 20min, adding sodium hydroxide with concentration of 2mol/L until pH of the solution is 10, transferring into hydrothermal reaction kettle, reacting at 140 deg.C for 8 hr, centrifuging, washingDrying for 14h at 90 ℃, and grinding to obtain silane modified magnesium-aluminum hydrotalcite; wherein Mg (OH)2Is added in an amount of 20 wt% of the final product;
the epoxy resin is bisphenol A type epoxy resin, and the epoxy value of the epoxy resin is 0.038;
the diluent is trimethylolpropane triglycidyl ether;
the anti-yellowing agent is UV-329; the defoaming agent is dimethyl silicone oil;
the curing agent is methyl hexahydrophthalic anhydride;
the curing accelerator is 2,4, 6-tris (dimethylamino) phenol (TAP);
the toughening agent is carboxyl-terminated butadiene-acrylonitrile rubber;
the coupling agent in the component B is methyl trimethoxy silane.
The emulsifier in the component B is triton X-100;
the preparation method of the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant is characterized by comprising the following steps of: preparation of glue A: mixing epoxy resin and silane modified magnesium-aluminum hydrotalcite at 80 ℃ for 60min, then sequentially adding a diluent, an anti-yellowing agent and a defoaming agent into the mixed components, continuously stirring for 40min, and cooling to room temperature to obtain a component A;
b, preparation of glue B: and (3) adding a curing agent, a curing accelerator, a toughening agent, a coupling agent and an emulsifier into a kneader in sequence, fully kneading for 60min at 800 ℃, cooling and discharging to obtain the component B.
In order to test the performances of examples 1-3 and comparative examples 1-5, the prepared glue A and glue B are prepared into a rubber plate according to a ratio of 3.5:1, and parameters such as tensile strength, elongation at break, light transmittance, limiting oxygen index and the like are respectively tested according to specific test standards: tensile strength GB/T1040.2: 2006; elongation at break GB/T1040.2: 2006; the light transmittance GB/T2410-2008; the Limiting Oxygen Index (LOI) was measured according to ASTM D2863, and the sample specification was 140 mm. times.6 mm. times.3 mm, and the glass transition temperature was measured by using a glass transition temperature tester DSC-100 (Shanghai Miyuan electric Co., Ltd.). The specific test results are as follows:
as can be seen from comparison between examples 1-3 and comparative examples 1-5, the halogen-free flame-retardant high-temperature-resistant epoxy resin sealant prepared by the method has excellent mechanical properties and flame retardancy due to mutual matching of the components.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A halogen-free flame-retardant high-temperature-resistant epoxy resin sealant is characterized in that: the adhesive comprises A, B components, wherein the A component is a resin matrix, the B component is a curing agent system, and the specific compositions of the components are as follows by weight:
the component A comprises: 100 parts of epoxy resin, 6-12 parts of polyphosphoric amide modified graphene oxide and carbon nano tubes, 10-14 parts of silane modified magnesium-aluminum hydrotalcite, 16-22 parts of diluent, 1-4 parts of anti-yellowing agent and 0.5-1.5 parts of defoaming agent;
and B component: 100 parts of curing agent, 0.5-8 parts of curing accelerator, 3-6 parts of toughening agent, 6-10 parts of coupling agent and 5-10 parts of emulsifier.
2. The halogen-free flame retardant high temperature resistant epoxy resin sealant as claimed in claim 1, characterized in that: the preparation method of the polyphosphamide modified graphene oxide and the carbon nano tube comprises the following steps of respectively treating the graphene oxide and the carbon nano tube by nitric acid; then adding the treated graphene oxide and the treated carbon nano tube into an organic solvent, and performing ultrasonic dispersion for 2-4 h; and then adding triethylamine and a proper amount of phenylenediamine in an ice bath, slowly dropwise adding a hexachlorocyclotriphosphazene acetonitrile solution in a nitrogen atmosphere, reacting for 1-2 h under an ice bath condition after dropwise adding, heating to 40-60 ℃, refluxing for 20-30 h, finally filtering and washing a product, and drying at 60-80 ℃ for 12-16 h to obtain the polyphosphamide modified graphene oxide and the carbon nano tube.
3. The halogen-free flame retardant high temperature resistant epoxy resin sealant as claimed in claim 2, characterized in that: the concentration of the nitric acid is 10-25 wt%, and the treatment time is 1-3 h; the material ratio of the treated graphene oxide to the treated carbon nanotube to the organic solvent to triethylamine is as follows: 1-3 g: 1-3 g; 200-260 mL: 6-10 g, wherein the organic solvent is at least one of acetonitrile, ethanol and methanol.
4. The halogen-free flame retardant high temperature resistant epoxy resin sealant as claimed in claim 2, characterized in that: the molar ratio of the phenylenediamine to the hexachlorocyclotriphosphazene is 2: 1; the mass ratio of the sum of the mass of the treated graphene oxide and the treated carbon nano tube to the sum of phenylenediamine and hexachlorocyclotriphosphazene is 1: 2-4.
5. The halogen-free flame retardant high temperature resistant epoxy resin sealant as claimed in claim 1, characterized in that: the preparation method of the silane modified magnesium-aluminum hydrotalcite comprises the following steps: weighing magnesium salt and aluminum salt, dissolving the magnesium salt and the aluminum salt in 20-40 vol% ethanol water to prepare a mixed salt solution, and then adding a certain amount of Mg (OH)2Adding the mixture into the solution, adding an ethanol solution of silane with the concentration of 0.5-1 mol/L, stirring for 10-30 min, then dropwise adding alkali liquor until the pH value of the solution is 10, wherein the alkali concentration is 1-3 mol/L, then transferring the solution into a hydrothermal reaction kettle, reacting for 6-10 h at 120-160 ℃, centrifuging, washing, drying for 12-16 h at 80-100 ℃, and grinding to obtain the silane modified magnesium-aluminum hydrotalcite.
6. The halogen-free flame retardant high temperature resistant epoxy resin sealant as claimed in claim 5, characterized in that: the magnesium salt is at least one of magnesium nitrate, magnesium acetate and magnesium chloride; the aluminum is at least one of aluminum nitrate, aluminum acetate and aluminum chloride; the alkali is one of sodium hydroxide, potassium hydroxide, urea and ammonia water; the silane is at least one of KH550, KH560 and KH 570.
7. The halogen-free flame retardant high temperature resistant epoxy resin sealant as claimed in claim 5, characterized in that: the molar ratio of the magnesium salt to the aluminum salt is 1: 2-4; the molar ratio of the aluminum to the silane is 1: 0.01-0.03; the Mg (OH)2The addition amount of (B) is 10-30 wt% of the final product.
8. The halogen-free flame retardant high temperature resistant epoxy resin sealant as claimed in claim 1, characterized in that:
the epoxy resin comprises bisphenol A type epoxy resin, phenolic resin type epoxy resin and hydrogenated bisphenol A type epoxy resin, and the epoxy value of the epoxy resin is between 0.02 and 0.56; the diluent comprises one or a mixture of trimethylolpropane triglycidyl ether or C12-14 aliphatic glycidyl ether; preferably, the anti-yellowing agent is an ultraviolet absorbent and comprises one or more of UV-40, UV-531, UV-9, UV-P, UV-329, UV-326, UV-320, UV-234 and UV-0; preferably, the defoaming agent is dimethyl silicone oil.
9. The halogen-free flame retardant high temperature resistant epoxy resin sealant as claimed in claim 1, characterized in that: the curing agent is one or a mixture of more of methylhexahydrophthalic anhydride, phthalic anhydride, maleic anhydride and methylnadic anhydride; preferably, the curing accelerator is one or more of 2,4, 6-tris (dimethylamino) phenol (TAP), tris (2-ethylhexanoate) salt of 2,4, 6-tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 1, 2-dimethylimidazole; preferably, the toughening agent is carboxyl-terminated butadiene-acrylonitrile rubber; preferably, the coupling agent in the component B is one or a mixture of more of methyltrimethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane and tetraethoxysilane; the emulsifier in the component B is triton X-100.
10. The preparation method of the halogen-free flame retardant high temperature resistant epoxy resin sealant according to any one of claims 1 to 9, which is characterized by comprising the following steps:
preparation of glue A: mixing epoxy resin, the polyphosphoric acid amide modified graphene oxide, the carbon nano tube and the silane modified magnesium-aluminum hydrotalcite at 75-85 ℃ for 40-80 min, then sequentially adding a diluent, an anti-yellowing agent and a defoaming agent into the mixed components, continuously stirring for 30-50 min, and cooling to room temperature to obtain a component A;
b, preparing glue: and (3) adding a curing agent, a curing accelerator, a toughening agent, a coupling agent and an emulsifier into a kneader in sequence, fully kneading for 40-70min at 60-90 ℃, cooling and discharging to obtain the component B.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210381508.5A CN114634783B (en) | 2022-04-13 | 2022-04-13 | Halogen-free flame-retardant high-temperature-resistant epoxy resin sealant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210381508.5A CN114634783B (en) | 2022-04-13 | 2022-04-13 | Halogen-free flame-retardant high-temperature-resistant epoxy resin sealant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114634783A true CN114634783A (en) | 2022-06-17 |
| CN114634783B CN114634783B (en) | 2023-11-10 |
Family
ID=81952297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210381508.5A Active CN114634783B (en) | 2022-04-13 | 2022-04-13 | Halogen-free flame-retardant high-temperature-resistant epoxy resin sealant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114634783B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115678287A (en) * | 2022-11-05 | 2023-02-03 | 台州市黄岩区武汉理工高性能复合材料技术研究院 | Preparation and application of high-temperature-resistant epoxy resin |
| CN116536014A (en) * | 2023-05-31 | 2023-08-04 | 广东欧利雅化工有限公司 | Functional sealant for building and production method thereof |
| CN116705620A (en) * | 2023-06-07 | 2023-09-05 | 江苏耀鸿电子有限公司 | Halogen-free epoxy resin IC packaging board and preparation method thereof |
| CN116814206A (en) * | 2023-06-29 | 2023-09-29 | 深圳未来新材料实业有限公司 | Epoxy sealant for flexible display screen and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103241752A (en) * | 2013-05-29 | 2013-08-14 | 肇庆学院 | Preparation method of surface-modified hydrotalcite |
| CN110982465A (en) * | 2019-12-02 | 2020-04-10 | 上海康达化工新材料集团股份有限公司 | Efficient halogen-free flame-retardant epoxy adhesive and preparation method thereof |
| CN111073307A (en) * | 2019-12-31 | 2020-04-28 | 苏州和塑美科技有限公司 | Halogen-free flame retardant composition, halogen-free flame retardant master batch and high-fluidity high-oxygen-index glass fiber reinforced halogen-free flame retardant polyamide |
-
2022
- 2022-04-13 CN CN202210381508.5A patent/CN114634783B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103241752A (en) * | 2013-05-29 | 2013-08-14 | 肇庆学院 | Preparation method of surface-modified hydrotalcite |
| CN110982465A (en) * | 2019-12-02 | 2020-04-10 | 上海康达化工新材料集团股份有限公司 | Efficient halogen-free flame-retardant epoxy adhesive and preparation method thereof |
| CN111073307A (en) * | 2019-12-31 | 2020-04-28 | 苏州和塑美科技有限公司 | Halogen-free flame retardant composition, halogen-free flame retardant master batch and high-fluidity high-oxygen-index glass fiber reinforced halogen-free flame retardant polyamide |
Non-Patent Citations (2)
| Title |
|---|
| KHALED RHILI等: "Hexachlorocyclotriphosphazene Functionalized Graphene Oxide as a Highly Efficient Flame Retardant", 《ACS OMEGA》, pages 6252 - 6260 * |
| 许佳等: "棉织物的六氯环三磷腈改性氧化石墨烯阻燃整理", 《印染》, no. 16, pages 6 - 11 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115678287A (en) * | 2022-11-05 | 2023-02-03 | 台州市黄岩区武汉理工高性能复合材料技术研究院 | Preparation and application of high-temperature-resistant epoxy resin |
| CN116536014A (en) * | 2023-05-31 | 2023-08-04 | 广东欧利雅化工有限公司 | Functional sealant for building and production method thereof |
| CN116536014B (en) * | 2023-05-31 | 2024-05-14 | 广东欧利雅化工有限公司 | Functional sealant for building and production method thereof |
| CN116705620A (en) * | 2023-06-07 | 2023-09-05 | 江苏耀鸿电子有限公司 | Halogen-free epoxy resin IC packaging board and preparation method thereof |
| CN116705620B (en) * | 2023-06-07 | 2023-11-03 | 江苏耀鸿电子有限公司 | Halogen-free epoxy resin IC packaging board and preparation method thereof |
| CN116814206A (en) * | 2023-06-29 | 2023-09-29 | 深圳未来新材料实业有限公司 | Epoxy sealant for flexible display screen and preparation method thereof |
| CN116814206B (en) * | 2023-06-29 | 2024-03-01 | 深圳未来新材料实业有限公司 | Epoxy sealant for flexible display screen and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114634783B (en) | 2023-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114634783B (en) | Halogen-free flame-retardant high-temperature-resistant epoxy resin sealant and preparation method thereof | |
| CN100343336C (en) | Organic silicon fibre retardant containing phosphorus and epoxy radical and its preparation method | |
| CN108997714B (en) | Reactive flame retardant for epoxy resin and flame-retardant epoxy resin thereof | |
| CN113667277B (en) | Low-heat-release, low-smoke and high-flame-retardance epoxy resin material and preparation method thereof | |
| CN111040293B (en) | Intumescent flame-retardant polypropylene and preparation method thereof | |
| CN100560632C (en) | A kind of silicon-phosphor-containing heat-stable hybridized epoxide resin and its production and application | |
| CN109369958B (en) | Preparation method and application of organically modified zirconium phosphate | |
| CN115010993A (en) | Preparation method and application of graphene oxide hybrid flame retardant | |
| CN111500234A (en) | Flame-retardant epoxy resin halogen-free potting material and preparation method thereof | |
| CN103194063B (en) | Trapezoidal polysiloxane modified thermosetting resin and preparation method thereof | |
| CN111253437A (en) | P/N/Si-containing multi-element reactive epoxy resin flame retardant and preparation method thereof | |
| CN105086925A (en) | Novel environment-friendly flame-retardant silicone sealant and preparation method thereof | |
| CN113881192A (en) | Low-smoke flame-retardant epoxy resin composite material and preparation method thereof | |
| CN110156958B (en) | Bio-based phosphaphenanthrene curing agent flame-retardant epoxy resin material and preparation method thereof | |
| CN105907087A (en) | Flame retardant nylon material and preparation method thereof | |
| CN111635618A (en) | Phosphazene-based organic metal complex flame-retardant epoxy resin and preparation method thereof | |
| CN113150386A (en) | Modified ammonium polyphosphate intumescent flame retardant and preparation method and application thereof | |
| CN113234228A (en) | Boron-containing polyphosphazene amide flame retardant with efficient flame retardance and smoke suppression as well as preparation method and application thereof | |
| CN112409397A (en) | Bio-based epoxy resin containing silicon phenylene structure, composition and preparation method thereof | |
| CN114230978B (en) | Flame-retardant epoxy resin based on phosphorus-containing nickel silicate whisker and preparation method thereof | |
| CN115073888B (en) | Method for preparing transparent flame-retardant epoxy resin by using compound flame retardant | |
| CN116179130A (en) | Anti-yellowing flame-retardant epoxy resin electronic pouring sealant and preparation method thereof | |
| CN114574138A (en) | Halogen-free flame-retardant epoxy resin sealant | |
| CN114685937A (en) | Flame-retardant epoxy resin composite material and preparation method thereof | |
| CN107501526A (en) | A kind of new DOPO types epoxy curing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20221207 Address after: 510420 room a879, 3 / F, No. 22, Qixiang, Yongtai Zhihe street, Yongping street, Baiyun District, Guangzhou, Guangdong Province Applicant after: Guangzhou Runtai New Material Technology Co.,Ltd. Address before: 511660 room 229-06, building 3, 48 chebei Road, Tianhe District, Guangzhou City, Guangdong Province Applicant before: Guangzhou Huineng New Material Technology Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20231013 Address after: 412000, 2nd Floor, Building 4, Phase III, Standard Factory Building, Liling Economic Development Zone, Zhuzhou City, Hunan Province Applicant after: LILING JINGLU NEW MATERIALS Co.,Ltd. Address before: 510420 room a879, 3 / F, No. 22, Qixiang, Yongtai Zhihe street, Yongping street, Baiyun District, Guangzhou, Guangdong Province Applicant before: Guangzhou Runtai New Material Technology Co.,Ltd. |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |