CN116003878B - Composite heat-resistant agent, high-temperature resistant silicone rubber and preparation method thereof - Google Patents
Composite heat-resistant agent, high-temperature resistant silicone rubber and preparation method thereof Download PDFInfo
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- CN116003878B CN116003878B CN202211495286.6A CN202211495286A CN116003878B CN 116003878 B CN116003878 B CN 116003878B CN 202211495286 A CN202211495286 A CN 202211495286A CN 116003878 B CN116003878 B CN 116003878B
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- silicone rubber
- agent
- resistant
- parts
- high temperature
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 166
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 146
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title description 5
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims abstract description 52
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 18
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 18
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 15
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 55
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 42
- 229920002554 vinyl polymer Polymers 0.000 claims description 42
- 229920001971 elastomer Polymers 0.000 claims description 37
- 239000005060 rubber Substances 0.000 claims description 36
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 26
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 24
- 229920002545 silicone oil Polymers 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- -1 vinyl hydroxyl Chemical group 0.000 claims description 20
- 239000006229 carbon black Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- YEECOJZAMZEUBB-UHFFFAOYSA-N 2,2,3,3,6,6,7,7-octamethyloctane Chemical compound CC(C)(C)C(C)(C)CCC(C)(C)C(C)(C)C YEECOJZAMZEUBB-UHFFFAOYSA-N 0.000 claims description 8
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 5
- 239000006082 mold release agent Substances 0.000 claims description 5
- 239000012044 organic layer Substances 0.000 claims description 5
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004513 sizing Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims description 3
- FRYRJNHMRVINIZ-UHFFFAOYSA-N B1CCOO1 Chemical compound B1CCOO1 FRYRJNHMRVINIZ-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 claims description 3
- 238000003818 flash chromatography Methods 0.000 claims description 3
- QNLOWBMKUIXCOW-UHFFFAOYSA-N indol-2-one Chemical compound C1=CC=CC2=NC(=O)C=C21 QNLOWBMKUIXCOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 claims description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-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
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- BJZBHTNKDCBDNQ-UHFFFAOYSA-L magnesium;dodecanoate Chemical compound [Mg+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BJZBHTNKDCBDNQ-UHFFFAOYSA-L 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 150000003071 polychlorinated biphenyls Chemical group 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229940098697 zinc laurate Drugs 0.000 claims description 2
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims 1
- 239000001307 helium Substances 0.000 claims 1
- 229910052734 helium Inorganic materials 0.000 claims 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 description 34
- 239000000203 mixture Substances 0.000 description 28
- 230000032683 aging Effects 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001816 cooling Methods 0.000 description 12
- 230000004580 weight loss Effects 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 239000000498 cooling water Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 238000004898 kneading Methods 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- BUEPLEYBAVCXJE-UHFFFAOYSA-N [ethenyl-methyl-(trimethylsilylamino)silyl]ethene Chemical compound C(=C)[Si](N[Si](C)(C)C)(C=C)C BUEPLEYBAVCXJE-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920004482 WACKER® Polymers 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000407 epitaxy Methods 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910018557 Si O Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000003878 thermal aging Methods 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- IVSQMSIRHKTHCB-UHFFFAOYSA-N 1,3,2,4-diazadisiletidine Chemical compound N1[SiH2]N[SiH2]1 IVSQMSIRHKTHCB-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- SHWQWXGIWFEYTA-UHFFFAOYSA-N 2,2,4,4,6,6-hexakis-phenyl-1,3,5,2,4,6-triazatrisilinane Chemical compound N1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)N[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)N[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 SHWQWXGIWFEYTA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- BPYFPNZHLXDIGA-UHFFFAOYSA-N diphenylsilicon Chemical compound C=1C=CC=CC=1[Si]C1=CC=CC=C1 BPYFPNZHLXDIGA-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- MRSTVOBCOHGVEW-UHFFFAOYSA-N methylidenesilicon Chemical compound [Si]=C MRSTVOBCOHGVEW-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical class O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of silicon rubber, and provides a composite heat-resistant agent which is used for silicon rubber resistant to high temperature of 350 ℃, and the composite heat-resistant agent consists of 15-40% of cerium oxide, 50% of methyl vinyl silicon rubber compound, 5-30% of titanium dioxide, 3-19% of zirconium oxide and 1-10% of GW heat-resistant auxiliary agent in percentage by mass. The composite heat resistant agent can be used for improving the high temperature resistance of the silicone rubber at the high temperature of 350 ℃ so that the silicone rubber still has good elasticity and mechanical properties.
Description
Technical Field
The invention belongs to the technical field of silicon rubber, and particularly relates to a composite heat-resistant agent, high-temperature-resistant silicon rubber and a preparation method thereof.
Background
The silicon rubber is a semi-organic semi-inorganic polymer material with a main chain of Si-O-Si bonds and a side chain of organic groups. The silicone rubber is linear polysiloxane with high molecular weight when not vulcanized, and is a netlike elastomer after vulcanization, and the special structure endows the silicone rubber with the characteristics of high temperature resistance, low temperature resistance, high air permeability, weather resistance and the like, and is widely applied to the fields of automobiles, living kitchens and bathrooms, aviation and the like.
The Si-O bond energy in the main chain of the silicone rubber is 444kJ/mol, the C-C bond energy of the main chain of the common organic polymer is 356kJ/mol, the C-O bond energy is 339kJ/mol, the higher Si-O bond energy gives the silicone rubber material excellent heat stability, the silicone rubber can be used for a long time below 260 ℃, but the application of the silicone rubber is limited after the temperature exceeds 300 ℃, particularly when the temperature reaches 350 ℃, the silicone rubber is fragile and broken, so the application in the fields of kitchen and toilet, aviation and the like which need to resist the high-temperature environment of 350 ℃ and above is limited, for example, the application of the steam-baking integrated sealing ring is limited. In order to widen the application range of the silicone rubber in a high-temperature environment, the high-temperature resistance of the silicone rubber needs to be further improved, and thermal aging is avoided.
There are two kinds of thermal aging phenomena of silicone rubber, one is that the main chain of the silicone rubber is broken to form cyclosiloxane or oligomer so as to reduce the hardness, and the other is that the methyl of a side chain is oxidized so as to increase the crosslinking point so as to increase the hardness. At present, the heat resistance or high temperature resistance of the silicone rubber is mainly improved by 5 ways of (1) changing the main chain or side chain structure, introducing heat-resistant large-volume chain segments such as cyclodisilazane, phenylene, carbodecaborane and the like into the main chain, introducing groups such as phenyl and the like into the side chain, (2) eliminating silicon hydroxyl, eliminating silicon hydroxyl at the end of the silicone rubber by trimethyl silicon-based end capping, reducing the end hydroxyl unbuckling reaction, reducing the silicon hydroxyl on the surface of the silicone rubber and white carbon black by hexamethyldisilazane, (3) adding metal oxides such as SnO 2、CeO2、Fe2O3 or metal oxide for compounding into a system, preventing the oxidation of a side chain methyl, improving the heat resistance, and (4) adding heat-resistant auxiliary agents such as phenyl silicone resin, inhibiting the unbuckling degradation of the main chain, and (5) other methods such as positive ions after bismaleimide oxidation, inhibiting the oxidation of the side chain methyl.
Patent CN111073057B adopts nano zirconium hydroxide, nano yttrium oxide and hexaphenyl cyclotrisilazane to match to improve heat resistance, but the quality loss of the aged silicone rubber is larger. The patent CN113278290a adopts a mixture of polydimethylsiloxane, nano-alumina, nano-iron oxide, lanthanum oxide, cerium oxide and the like as a heat-resistant agent, and can maintain certain mechanical and ageing-resistant properties within 300 ℃ (7-10) h, but no mention is made of ageing-resistant properties at temperatures of 350 ℃ and above. The phenyl-containing methyl vinyl polysiloxane is added in the CN109401330A, the tensile strength reaches 4.6MPa after aging for 24 hours at 350 ℃, the elongation is 102%, and the phenyl silicone rubber has good high temperature resistance, but is easy to adhere to rollers, high in price and limited in yield, so that the application of the phenyl silicone rubber is limited. The oil-resistant additives such as diphenyl silicon glycol, methyl phenyl vinyl silicone oil and modified ferric oxide are added in the CN111909525A to improve the ageing resistance, the tensile strength retention rate is 63.2% and the elongation retention rate is 52.7% after ageing for 24 hours at 315 ℃, but the ageing performance at the temperature of 350 ℃ and above is not mentioned. Patent CN109867965A adopts a boron-based heat-resistant agent, and studies on the aging condition of silicone rubber at high temperature, but the mass loss of silicone rubber is large.
In view of this, the present invention has been made.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims at providing a composite heat-resistant agent which can be used for improving the high temperature resistance of silicon rubber at a high temperature of 350 ℃ so that the silicon rubber still has good elasticity and mechanical properties.
In order to achieve the technical effects, the basic conception of the technical scheme of the invention is as follows:
the composite heat resistant agent is used for silicon rubber resistant to high temperature of 350 ℃, and consists of 15-40% of cerium oxide, 50% of methyl vinyl silicon rubber compound, 5-30% of titanium dioxide, 3-19% of zirconium oxide and 1-10% of GW heat resistant auxiliary agent in percentage by mass;
wherein, the chemical structural formula of the GW heat-resistant auxiliary agent is as follows:
As an example, the heat-resistant auxiliary GW is prepared by reacting 2-indolone and 2- (4-bromophenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in a mixed solution of potassium acetate, 1, 4-dioxane and [1,1' -bis (diphenylphosphino) ferrocene ] palladium (II) dichloride, washing an organic portion with water after the reaction is completed, extracting the obtained aqueous layer with ethyl acetate, combining the organic layers, drying the organic layers with anhydrous sodium sulfate, filtering and concentrating to obtain a crude product, and purifying by flash column chromatography to obtain a purified heat-resistant auxiliary GW;
preferably, the reaction is carried out at 90 ℃ for 24 hours.
The invention provides high-temperature-resistant silicone rubber, which comprises any one of the composite heat-resistant agents, has the characteristics of certain elasticity, mechanical property and the like after being aged for 5h at 350 ℃, has good high-temperature resistance, and can be applied to the high-temperature conditions of the automobile field, household appliances, aviation and the like.
As an example, the high temperature resistant silicone rubber comprises 100 parts of methyl vinyl silicone rubber raw rubber, 30-50 parts of white carbon black, 0.2-10 parts of structural control agent, 0.5-10 parts of composite heat resistant agent and 0.05-0.3 part of internal mold release agent.
As an example, the methyl vinyl silicone rubber raw rubber has a molar mass of 500000-750000g/mol, and the vinyl content is 0.05-1.0% in terms of mole percent.
As an example, the white carbon black is gas phase white carbon black and is silicon dioxide with a specific surface area of 200-380m 2/g.
As an example, the internal mold release agent is one or more of zinc stearate, calcium stearate, barium stearate, magnesium stearate, zinc laurate, magnesium laurate, palmitic acid, lauric acid, and stearic acid.
As an example, the structuring control agent includes one or more of hydroxyl silicone oil, vinyl hydroxyl silicone oil, diphenyl dihydroxy silicone oil, dimethyl dimethoxy silane, dimethyl diethoxy silane, methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, hexamethyldisilazane, vinyl silazane, vinyl trimethoxy silane, vinyl triethoxy silane.
As an example, the purity of the methylphenyl dimethoxy silane is more than or equal to 99%, the refractive index (n 25 D) is 1.469+/-0.005, and the polychlorinated biphenyl content is 0.
As an example, the viscosity (25 ℃) of the vinyl hydroxyl silicone oil is less than or equal to 35mm 2/s, the hydroxyl content (mol%) is less than or equal to 6.0%, and the vinyl content (mol%) is 6.5-7.5.
The invention further provides a preparation method of the high-temperature-resistant silicon rubber, which comprises the following steps:
(1) Placing raw methyl vinyl silicone rubber, a structuring control agent and an internal release agent into a kneader to obtain a first mixed material;
(2) Adding white carbon black into the first mixed material in batches, uniformly mixing at 100 ℃, and standing for 4-8 hours to obtain a second mixed material;
(3) And (3) banburying the second mixed material for 2-5 hours under the conditions of 0.04-0.08MPa and 120-170 ℃ to obtain a mixed base rubber, adding the composite heat-resistant agent into the mixed base rubber under the condition that the temperature is less than or equal to 100 ℃ to obtain a mixed sizing material, and discharging.
As an example, the compounded rubber material is further added with a vulcanizing agent for molding, wherein the vulcanizing agent is selected from one of2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, dicumyl peroxide, benzoyl peroxide, 2, 4-dichloro benzoyl peroxide or platinum vulcanizing agent.
Compared with the prior art, the invention has the following beneficial effects:
1. The heat-resistant auxiliary GW and the metal oxide used in the composite heat-resistant agent can be used together to obviously improve the thermal decomposition temperature of the silicone rubber, improve the thermal stability, effectively inhibit unbuckling degradation of a main chain and methyl group oxidation of a side chain, improve the heat resistance of the silicone rubber at a high temperature of 350 ℃, and facilitate the widening of the application range of the silicone rubber at a high temperature.
2. The high-temperature resistant silicone rubber provided by the invention has the characteristics of certain elasticity, mechanical property and the like after being aged for 5 hours at 350 ℃, has good high-temperature resistance, and can be applied to the fields of automobiles, household appliances, aviation and other high-temperature conditions.
3. The composite heat resistant agent has good dispersibility in silicon rubber.
4. The high-temperature-resistant silicone rubber disclosed by the invention has small weight loss after being aged for 5 hours at 350 ℃.
Drawings
FIG. 1 is a graph of thermal weight loss of silicone rubber of comparative example 3 (WATERS TGA Q, 50, room temperature to 800 ℃,10 ℃ per minute, nitrogen atmosphere).
FIG. 2 is a graph of thermal weight loss of the silicone rubber of example 6 (WATERS TGA Q50, room temperature to 800 ℃,10 ℃ per minute, nitrogen atmosphere.).
FIG. 3 is a graph of thermal weight loss of the silicone rubber of example 9 (WATERS TGA Q. Sup.50, room temperature to 800 ℃,10 ℃ per minute, nitrogen atmosphere).
FIG. 4 is a nuclear magnetic resonance spectrum of a heat resistant additive GW (using AVANCE400 or 500MHz nuclear magnetic resonance spectrometer from Bruker, germany, using deuterated chloroform solvent, the peak at 1.26ppm is hydrocarbon in a, the peak at 7.2ppm is hydrocarbon in b, the peak at 7.6ppm is hydrocarbon in c, the peak at 3.49ppm is hydrocarbon in d, the peak at 7.52ppm is hydrocarbon in e and g coincident, the peak at 6.88ppm is hydrocarbon in f, and the peak at 7.04ppm is hydrocarbon in h).
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The "parts" in the following examples are "parts by weight", and the "parts" or "parts by weight" in the same examples are unified in terms of the same concept as the technical proposal defined by the specific parts by weight, without affecting the feasibility thereof.
Unless otherwise indicated, the term "%" refers to the mole percentage of the vinyl content, and "%" in the heat-resistant agent is the weight percentage of "wt%".
Unless otherwise specified, the raw materials according to the present invention may be obtained by means of market purchase.
As an example, the preparation method of the heat-resistant auxiliary GW is as follows:
2-indolone (4.4 g,0.033 mol), 2- (4-bromophenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan (9.4 g,0.033 mol), a mixed solution of potassium acetate (7.0 g,0.072 mol), 1, 4-dioxane (20 mL) and [1,1' -bis (diphenylphosphine) ferrocene ] palladium (II) dichloride (Pd (dppf) Cl 2) (1.2 g,1.64 mmol) was added to a round bottom flask and reacted at 90℃to wash the organic portion with water (100 mL), the aqueous layer was further extracted with ethyl acetate (240 mL), and the organic layer was dried over anhydrous sodium sulfate, filtered and concentrated to give a crude product, which was then purified by flash column chromatography to give a purified heat resistant adjuvant GW.
As an example, the methyl vinyl silicone rubber compound was a laboratory-made 50HA silicone rubber compound prepared as follows:
(1) 100 parts of methyl vinyl silicone rubber raw rubber with the average molecular weight of 66-72 ten thousand and the average vinyl content of 0.16-0.21mol percent, 3.0-4.0 parts of structuring control agent and a proper amount of internal mold release agent are put into a kneader to obtain a first mixed material;
(2) Adding 32-38 parts of gas-phase white carbon black into the first mixed material in 4-6 batches, uniformly mixing at 100 ℃, and standing for 4-8 hours to obtain a second mixed material;
(3) And banburying the second mixed material for 2-5 hours under the conditions of 0.04-0.08MPa and 120-170 ℃ to obtain the silicon rubber compound with 50HA, wherein the secondary vulcanization hardness is 51+/-3 HA, the secondary vulcanization tensile strength is more than or equal to 8.5MPa, the secondary vulcanization elongation at break is more than or equal to 350%, and the secondary vulcanization tearing strength is more than or equal to 18.0KN/m.
Of course, the methyl vinyl silicone rubber compound can be obtained in a commercial purchasing manner without affecting the basic beneficial effects to be achieved by the invention.
Example 1
100 Parts of methyl vinyl silicone rubber with an average molecular weight of 68.5 ten thousand and an average vinyl content of 0.193mol percent (75 parts of methyl vinyl silicone rubber with a molecular weight of 68 ten thousand and a vinyl content of 0.09mol percent, 25 parts of methyl vinyl silicone rubber with a molecular weight of 70 ten thousand and a vinyl content of 0.5mol percent), 1.5 parts of hexamethyldisilazane (content more than or equal to 99%), 1.0 part of vinylhydroxyl silicone oil (viscosity (25 ℃) and mm 2/s: 35, hydroxyl content (mol%) of 6.0 and vinyl content (mol%) of 7.0), 2.5 parts of methylphenyl dimethoxy silane (HY-PS-9116, hangzhi technology product center), 1.2 parts of tetramethyl divinyl disilazane (New sub-strong silicon chemical Co., ltd.), 0.4 parts of deionized water and 0.08 parts of zinc stearate (oil chemical Co., ltd.) are put into a gas phase chemical industry machine to obtain a first mixed material, 34 parts of white carbon black (HL-300) and a second mixed material is evenly stirred and stirred at an upper temperature of 5 ℃ until the temperature reaches a lower temperature of 100 ℃, and then the mixed material is cooled to a lower temperature of 100 ℃ until the mixed material is cooled. Adding 4.5 parts of heat resistant agent (29% cerium oxide, 50% methyl vinyl silicone rubber compound, 12% titanium dioxide, 7% zirconium oxide and 2% GW), continuously kneading (cooling water is required to be introduced, the temperature cannot exceed 100 ℃) for 30 minutes, discharging to obtain high temperature resistant silicone rubber, dividing the rubber material into sheet rubber materials, cooling for more than 30 minutes, carrying out open mill, rubber filtering, weighing and packaging to obtain a high temperature resistant silicone rubber finished product.
Taking 100 parts of the high-temperature-resistant silicone rubber finished product, firstly mixing and dispersing 1 part of 2, 5-dimethyl-2, 5-di-tert-butyl-hexane peroxide by using a 150mm open mill to prepare a curable silicone rubber composition, performing press vulcanization on the curable silicone rubber composition at 170 ℃ for 10min to obtain a first-stage vulcanization, and simultaneously performing post vulcanization at 200 ℃ for 2h to obtain a second-stage vulcanization, and detecting the mechanical properties of the cured silicone rubber composition.
Example 2
100 Parts of methyl vinyl silicone rubber with an average molecular weight of 70.6 ten thousand and an average vinyl content of 0.183mol percent (wherein 5 parts of methyl vinyl silicone rubber with a molecular weight of 65 ten thousand and a vinyl content of 0.03mol percent, 53 parts of methyl vinyl silicone rubber with a molecular weight of 70 ten thousand and a vinyl content of 0.16mol percent, 42 parts of methyl vinyl silicone rubber with a molecular weight of 72 ten thousand and a vinyl content of 0.23mol percent), 0.8 parts of hydroxyl silicone oil (viscosity of 25 ℃ C. Is 25mm 2/s, hydroxyl content is 8.5 wt%) 1.2 parts of hexamethyldisilazane (content is more than or equal to 99%), 0.5 parts of vinyl hydroxyl silicone oil (viscosity (25 ℃ C.), mm 2/s is 35, hydroxyl content is (mol%) 6.0, vinyl content is (mol%) 7.0), 2.0 parts of diphenyl dimethoxy silane (DP-820, two-peach fine chemical industry Co., guangjiang, inc.), 1.5 parts of tetramethyl divinyl disilazane (new methylene chemical compound), 0.5 parts of 5 parts of hydroxyl silicone rubber stock, 5 ℃ C. Is kneaded into a high-temperature mixer (temperature: 2.5 ℃ C., 5 ℃ C.), and mixed with a heat insulation mixer (temperature: 3 ℃ C.) to obtain a mixed solution, and the mixed material is cooled until the mixed material is cooled to obtain a high temperature, and the mixed material is cooled to a low temperature (100 ℃ C.) and the mixed material is cooled at a temperature of 3 ℃ until the high temperature is equal to 3.5 ℃ to 3 ℃ to 100 ℃ C. Of the high-75 ℃ C. And the final product.
Adding 4.0 parts of heat-resistant agent (31% cerium oxide, 50% methyl vinyl silicone rubber compound, 13% titanium dioxide, 3% zirconium oxide and 3% GW), continuously kneading (cooling water is required to be introduced, the temperature cannot exceed 100 ℃) for 30 minutes, discharging to obtain high-temperature-resistant silicone rubber, dividing the rubber material into sheet-shaped rubber materials, cooling for more than 30 minutes, carrying out open-mixing, rubber filtering, weighing and packaging to obtain a high-temperature-resistant silicone rubber finished product.
Taking 100 parts of the high-temperature-resistant silicone rubber finished product, firstly mixing and dispersing 1 part of 2, 5-dimethyl-2, 5-di-tert-butyl-hexane peroxide by using a 150mm open mill to prepare a curable silicone rubber composition, performing press vulcanization on the curable silicone rubber composition at 170 ℃ for 10min to obtain a first-stage vulcanization, and simultaneously performing post vulcanization at 200 ℃ for 2h to obtain a second-stage vulcanization, and detecting the mechanical properties of the cured silicone rubber composition.
Example 3
100 Parts of methyl vinyl silicone rubber with an average molecular weight of 69.7 ten thousand and an average vinyl content of 0.196mol percent (wherein, the average molecular weight of 68 ten thousand is 21 parts of methyl vinyl silicone rubber with a vinyl content of 0.09mol percent, the average molecular weight of 70 ten thousand is 73 parts of methyl vinyl silicone rubber with a vinyl content of 0.16mol percent, the average molecular weight of 72 ten thousand is 6 parts of methyl vinyl silicone rubber with a vinyl content of 1.0mol percent), 0.3 parts of hydroxyl silicone oil (the viscosity of 25 ℃ is 25mm 2/s, the hydroxyl content is 8.5 wt%) 1.0 part of hexamethyldisilazane (the content is more than or equal to 99%), 0.5 parts of vinyl hydroxyl silicone oil (the viscosity is 25 ℃, the hydroxyl content is 35, the hydroxyl content is 6.0, the vinyl content is 7.0 percent), 2.0 parts of diphenyl dimethoxy silane (Hubei river, technology, inc.), 0.8 parts of tetramethyl divinyl disilazane (new silicon rubber, lasiosphaer, inc.), 0.3 parts of 0.15 parts of silicon dioxide, 25 ℃ C. And 3 parts of white carbon black (3 ℃ C.) are evenly mixed, placed in a high-temperature mixer, cooled to a low-temperature mixer, cooled to obtain a mixed material, and mixed, cooled to obtain a high-temperature, and mixed material, and the mixed material is cooled to obtain a low-temperature-phase mixed material (100 ℃ by 3 ℃ until the high-phase silicon black material) is cooled to be placed in a high-temperature of 3 silicon white silicon (3).
Adding 5.0 parts of heat resistant agent (27% cerium oxide, 50% methyl vinyl silicone rubber compound, 18% titanium dioxide, 4% zirconium oxide and 1% GW), continuously kneading (cooling water is required to be introduced, the temperature cannot exceed 100 ℃) for 30 minutes, discharging to obtain high temperature resistant silicone rubber, dividing the rubber material into sheet rubber materials, cooling for more than 30 minutes, carrying out open mill, rubber filtering, weighing and packaging to obtain a high temperature resistant silicone rubber finished product.
Taking 100 parts of the high-temperature-resistant silicone rubber finished product, firstly mixing and dispersing 1 part of 2, 5-dimethyl-2, 5-di-tert-butyl-hexane peroxide by using a 150mm open mill to prepare a curable silicone rubber composition, performing press vulcanization on the curable silicone rubber composition at 170 ℃ for 10min to obtain a first-stage vulcanization, and simultaneously performing post vulcanization at 200 ℃ for 2h to obtain a second-stage vulcanization, and detecting the mechanical properties of the cured silicone rubber composition.
Example 4
100 Parts of methyl vinyl silicone rubber with an average molecular weight of 68.7 ten thousand and an average vinyl content of 0.202mol percent (wherein the average molecular weight of 70 ten thousand is 23 parts of methyl vinyl silicone rubber with a vinyl content of 0.05mol percent, the average molecular weight of 68 ten thousand is 72 parts of methyl vinyl silicone rubber with a vinyl content of 0.23mol percent, the average molecular weight of 72 ten thousand is 5 parts of methyl vinyl silicone rubber with a vinyl content of 0.5mol percent), 0.4 parts of hydroxyl silicone oil (viscosity of 25 ℃ is 25mm 2/s, hydroxyl content is 8.5 wt%) 1.3 parts of hexamethyldisilazane (content is more than or equal to 99%), 0.8 parts of vinyl hydroxyl silicone oil (viscosity (25 ℃) is 2/s: 35, hydroxyl content is (mol%) 6.0, vinyl content is (mol%) 7.0), 2.5 parts of methyl phenyl diethoxysilane (limited in Hubei Xingxing, heng, 1.0 parts of tetramethyl disilazane (limited by Nitsumade, nitsui), 0.3 parts of tetramethyl disilazane (limited by Nitsche), 0.12 ℃ C. 25 ℃ C. And 25 ℃ C. Are kneaded, and then mixed and cooled to obtain a high-temperature state carbon black mixture by placing the high-temperature chemical and low-temperature mixing materials in a vacuum mixer (30 ℃ C.) at a temperature of 30 ℃ for cooling, and mixing.
Adding 4.3 parts of heat resistant agent (25% cerium oxide, 50% methyl vinyl silicone rubber compound, 10% titanium dioxide, 12% zirconium oxide and 3% GW), continuously kneading (cooling water is required to be introduced, the temperature cannot exceed 100 ℃) for 30 minutes, discharging to obtain high temperature resistant silicone rubber, dividing the rubber material into sheet rubber materials, cooling for more than 30 minutes, carrying out open mill, rubber filtering, weighing and packaging to obtain a high temperature resistant silicone rubber finished product.
Taking 100 parts of the high-temperature-resistant silicone rubber finished product, firstly mixing and dispersing 1 part of 2, 5-dimethyl-2, 5-di-tert-butyl-hexane peroxide by using a 150mm open mill to prepare a curable silicone rubber composition, performing press vulcanization on the curable silicone rubber composition at 170 ℃ for 10min to obtain a first-stage vulcanization, and simultaneously performing post vulcanization at 200 ℃ for 2h to obtain a second-stage vulcanization, and detecting the mechanical properties of the cured silicone rubber composition.
Example 5
100 Parts of methyl vinyl silicone rubber with an average molecular weight of 68.2 ten thousand and an average vinyl content of 0.194mol percent (13 parts of methyl vinyl silicone rubber with a molecular weight of 65 ten thousand and a vinyl content of 0.03mol percent, 72 parts of methyl vinyl silicone rubber with a molecular weight of 68 ten thousand and a vinyl content of 0.16mol percent, 15 parts of methyl vinyl silicone rubber with a molecular weight of 72 ten thousand and a vinyl content of 0.5mol percent), 0.1 part of hydroxyl silicone oil (viscosity of 25 ℃ is 25mm 2/S, hydroxyl content is 8.5 wt%) 0.6 part of hexamethyldisilazane (content is more than or equal to 99%), 0.5 part of vinyl hydroxyl silicone oil (viscosity (25 ℃), mm 2/S: 35, hydroxyl content (mol%) 6.0, vinyl content (mol%) 7.0), 2.0 parts of diphenyl dimethoxy silane (Hubei super-carrier, technology Co., ltd.), 1.2 parts of tetramethyl divinyl disilazane (new sub-strong rubber stock, 0.08 parts of Lae, 25 ℃ C.) and 25 to 25 ℃ C., 25 to 30 ℃ C., 25 to obtain a mixed material, adding the mixed material, cooling to a high temperature, placing the mixed material in a 25 ℃ to 30 ℃ C., and mixing, cooling until the mixed material is uniform, and placing the mixed material in a high temperature, and cooling down to obtain 30 ℃ heat-insulating and 30% silicon black material.
Adding 3.5 parts of heat resistant agent (30% cerium oxide, 50% methyl vinyl silicone rubber compound, 11% titanium dioxide, 3% zirconium oxide and 6% GW), continuously kneading (cooling water is required to be introduced, the temperature cannot exceed 100 ℃) for 30 minutes, discharging to obtain high temperature resistant silicone rubber, dividing the rubber material into sheet rubber materials, cooling for more than 30 minutes, carrying out open mill, rubber filtering, weighing and packaging to obtain a high temperature resistant silicone rubber finished product.
Taking 100 parts of the high-temperature-resistant silicone rubber finished product, firstly mixing and dispersing 1 part of 2, 5-dimethyl-2, 5-di-tert-butyl-hexane peroxide by using a 150mm open mill to prepare a curable silicone rubber composition, performing press vulcanization on the curable silicone rubber composition at 170 ℃ for 10min to obtain a first-stage vulcanization, and simultaneously performing post vulcanization at 200 ℃ for 2h to obtain a second-stage vulcanization, and detecting the mechanical properties of the cured silicone rubber composition.
Example 6
100 Parts of methyl vinyl silicone rubber with an average molecular weight of 68.9 ten thousand and an average vinyl content of 0.193mol percent (25 parts of methyl vinyl silicone rubber with a molecular weight of 70 ten thousand and a vinyl content of 0.05mol percent, 65 parts of methyl vinyl silicone rubber with a molecular weight of 68 ten thousand and a vinyl content of 0.20mol percent, 10 parts of methyl vinyl silicone rubber with a molecular weight of 72 ten thousand and a vinyl content of 0.5mol percent), 0.2 parts of hydroxyl silicone oil (viscosity of 25 ℃ is 25mm 2/S, hydroxyl content is 8.5 wt%) 0.5 parts of hexamethyldisilazane (content is more than or equal to 99%), 0.8 parts of vinyl hydroxyl silicone oil (viscosity (25 ℃), mm 2/S is 35, hydroxyl content is (mol%) 6.0, vinyl content is (mol%) 7.0), 2.4 parts of methyl phenyl dimethoxy silane (HY-PS-9116, the center of Hangzhou chemical product technology), 1.3 parts of tetramethyl divinyl disilazane (new methylene silicon rubber, high-1 part, 5% of high-temperature-chemical industry, 5 ℃ C.) and 5 ℃ C. Are kneaded, mixed, and then mixed, cooled, and mixed, and the mixture is cooled until the mixture is cooled to obtain a mixed solution of the white carbon black, the white carbon black and the white carbon black is cooled to a high-phase, the white carbon black and the white silicon rubber is cooled to a high-saturated silicon rubber.
Adding 4.0 parts of heat resistant agent (30% cerium oxide, 50% methyl vinyl silicone rubber compound, 15% titanium dioxide, 4% zirconium oxide and 1% GW), continuously kneading (cooling water is required to be introduced, the temperature cannot exceed 100 ℃) for 30 minutes, discharging to obtain high temperature resistant silicone rubber, dividing the rubber material into sheet rubber materials, cooling for more than 30 minutes, carrying out open mill, rubber filtering, weighing and packaging to obtain a high temperature resistant silicone rubber finished product.
Taking 100 parts of the high-temperature-resistant silicone rubber finished product, firstly mixing and dispersing 1 part of 2, 5-dimethyl-2, 5-di-tert-butyl-hexane peroxide by using a 150mm open mill to prepare a curable silicone rubber composition, performing press vulcanization on the curable silicone rubber composition at 170 ℃ for 10min to obtain a first-stage vulcanization, and simultaneously performing post vulcanization at 200 ℃ for 2h to obtain a second-stage vulcanization, and detecting the mechanical properties of the cured silicone rubber composition.
Example 7
100 Parts of methyl vinyl silicone rubber raw rubber with an average molecular weight of 67.8 ten thousand and an average vinyl content of 0.181mol percent (24 parts of methyl vinyl silicone rubber raw rubber with a molecular weight of 65 ten thousand and a vinyl content of 0.05mol percent, 62 parts of methyl vinyl silicone rubber raw rubber with a molecular weight of 68 ten thousand and a vinyl content of 0.16mol percent, 14 parts of methyl vinyl silicone rubber raw rubber with a molecular weight of 72 ten thousand and a vinyl content of 0.5mol percent), 0.2 parts of hydroxyl silicone oil (viscosity of 25 ℃ C. Of 25mm 2/s and a hydroxyl content of 8.5 wt%), 0.8 parts of hexamethyldisilazane (content of 99 percent or more), 0.5 parts of vinyl hydroxyl silicone oil (viscosity of 25 ℃ C., mm 2/s: 35, a hydroxyl content of (mol%) 6.0, a vinyl content of (mol%) 7.0), 2.0 parts of methyl phenyl dimethoxy silane (HY-PS-9116, a scientific and technological center of Hangzhou chemical engineering product), 0.8 parts of tetramethyl divinyl disilazane (new methylene chemical product center), 0.10 parts of water and 30.10 parts of a limited polyethylene glycol (Hemson) are kneaded to obtain a mixed solution; adding 33 parts of gas-phase white carbon black (Yingchangdai R106, yingchangdai Co., ltd.) into the above materials for 5 times, uniformly mixing at 100 ℃, standing for 4 hours to obtain a second mixed material, then adding into a kneader, heating to about 170 ℃ for banburying at high temperature, preserving heat, removing low molecular substances, and cooling the sizing material to below 100 ℃.
Adding 4.0 parts of heat-resistant agent (28% cerium oxide, 50% methyl vinyl silicone rubber compound, 13% titanium dioxide, 4% zirconium oxide and 5% GW), continuously kneading (cooling water is required to be introduced, the temperature cannot exceed 100 ℃) for 30 minutes, discharging to obtain high-temperature-resistant silicone rubber, dividing the rubber material into sheet-shaped rubber materials, cooling for more than 30 minutes, carrying out open-mixing, rubber filtering, weighing and packaging to obtain a high-temperature-resistant silicone rubber finished product. Taking 100 parts of the high-temperature-resistant silicone rubber finished product, firstly mixing and dispersing 1 part of 2, 5-dimethyl-2, 5-di-tert-butyl-hexane peroxide by using a 150mm open mill to prepare a curable silicone rubber composition, performing press vulcanization on the curable silicone rubber composition at 170 ℃ for 10min to obtain a first-stage vulcanization, and simultaneously performing post vulcanization at 200 ℃ for 2h to obtain a second-stage vulcanization, and detecting the mechanical properties of the cured silicone rubber composition.
Example 8
The difference from example 2 is that 4 parts of a heat-resistant agent (50% methyl vinyl silicone rubber compound, 29% titanium dioxide, 18% zirconium oxide, 3% GW) are added.
Example 9
The difference from example 2 is that 4 parts of the heat-resistant auxiliary GW mixture (80% methyl vinyl silicone rubber compound, 20% GW) are added.
Example 10
The difference from example 2 is that 4 parts of a heat-resistant agent (30% cerium oxide, 50% methyl vinyl silicone rubber compound, 15% titanium dioxide, 5% zirconium oxide) are added.
Example 11
The difference from example 2 is that 4 parts of a heat-resistant agent (10% cerium oxide, 50% methyl vinyl silicone rubber compound, 13.5% titanium dioxide, 26% zirconium oxide, 0.5% GW) are added.
Comparative example 1
The difference from example 6 is that 5 parts of commercially available WACKER H6 are used for the heat-resistant agent, the other is identical to example 6.
Comparative example 2
The difference from example 6 is that 5 parts of the commercial RBM9012 was used for the heat resistant agent, and the other was the same as in example 6.
Comparative example 3
The difference from example 6 is that 3.0 parts of the commercially available heat-resistant agent WACKER H6 and 2.0 parts of the commercially available heat-resistant agent cerium oxide paste (JC-CeOC, shenzhen Crystal chemical Co., ltd.) are used instead of the heat-resistant agent, otherwise the same as in example 6.
The silicone rubber data measured in the following table are respectively tested according to the national standard for Shore hardness, tensile strength, elongation at break, tear strength, rebound resilience and hot air aging of the silicone rubber prepared by the embodiment and the comparative example, and the specific test method comprises the following steps of testing the Shore hardness according to the GB/T531.1-2008 standard, testing the tensile strength and the elongation at break according to the GB/T528-2009 standard, testing the tearing strength according to the GB/T529-2008 standard and testing the hot air aging according to the GB/T3512-2004 standard. The experimental data obtained are shown in tables 1-2 below for the secondary vulcanization and hot air aging properties of the silicone rubber.
TABLE 1
TABLE 2
As can be seen from tables 1-2, the heat-resistant agent used in comparative example 1 was replaced with commercially available WACKER H6, the heat-resistant agent used in comparative example 2 was replaced with commercially available Dow RBM9012, the heat-resistant agent used in comparative example 3 was replaced with commercially available WACKER H6 and commercially available cerium oxide paste used in combination with example 6, and the hardness of the silicone rubbers of comparative example 1 and comparative example 3 after heat air aging at 350 ℃ was significantly increased due to oxidation of the side chain groups of the silicone rubber, the increase in the crosslinking point caused by the increase in hardness, and the samples were significantly embrittled after aging, losing mechanical properties. Comparative example 2 also has certain mechanical properties over a period of 350 ℃ x 5h, but is yellow in appearance and higher in price, which limits its application to a certain extent.
Examples 1-7 use the novel heat-resistant agent of the formulation of the invention, the mass loss rate of the silicone rubber after 350 ℃ 5h hot air aging is lower, about 11%, and good mechanical properties are still maintained, and the mass loss of the silicone rubber is increased after the commercial heat-resistant agent is added, and the rubber material even embrittles and breaks to lose mechanical properties.
Example 8, which lacks the synergistic heat resistance of the ceria metal oxide, shows a slight decrease in tensile strength and elongation at break after hot air aging at 350 ℃ for 5 hours, and example 9, which uses only the heat resistant additive GW mixture, shows no embrittlement after hot air aging at 350 ℃ for 5 hours, but shows a slight decrease in aging strength, compared to example 2, which has a higher cost of the heat resistant agent. In example 10, the tensile strength was significantly reduced compared to example 2 without adding the heat-resistant auxiliary agent GW. In example 11, the amounts of cerium oxide, zirconium oxide and GW were not within the preferred ranges of the present invention, and the decrease in tensile strength after aging at 350℃for 5 hours was remarkable, as compared with example 2.
As an example, the present invention gives the results of thermal weight loss performance test of inventive example 6, example 9 and comparative example 3. FIG. 1 is a graph of thermal weight loss of the silicone rubber of comparative example 3 (3.0 parts H6 and 2.0 parts cerium oxide paste added), at a temperature of 419.36 ℃for 5% weight loss, and 446.88 ℃for epitaxy initiation. FIG. 2 is a graph of thermal weight loss of the silicone rubber of example 6 (4.0 parts of a mixed heat resistant agent consisting of 30% cerium oxide, 50% methyl vinyl silicone rubber compound, 15% titanium dioxide, 4% zirconium oxide, 1% GW was added), the temperature of 5% weight loss was 451.73 ℃, and the onset of epitaxy was 486.67 ℃. FIG. 3 is a graph of thermal weight loss of the silicone rubber of example 9 (4 parts of GW mixed heat resistant agent consisting of 80% methyl vinyl silicone rubber compound and 20% GW was added), the temperature of 5% weight loss was 433.58 ℃and the epitaxy initiation temperature was 457.04 ℃.
As can be seen from the thermal weight loss curves of fig. 1-3 in combination with the test data of tables 1-2, comparative example 3 embrittles to lose its performance after being aged by hot air at 350 ℃ for 5 hours, whereas examples 6 and 9 of the present invention have better mechanical properties after being aged by hot air at 350 ℃ for 5 hours due to the use of the heat-resistant agent of the present invention.
Claims (13)
1. The composite heat resistant agent is characterized by comprising, by mass, 15-40% of cerium oxide, 50% of methyl vinyl silicone rubber compound, 5-30% of titanium dioxide, 3-19% of zirconium oxide and 1-10% of GW heat resistant auxiliary agent, wherein the silicon rubber is used for resisting high temperature of 350 ℃;
wherein, the chemical structural formula of the GW heat-resistant auxiliary agent is as follows:
2. The composite heat-resistant agent according to claim 1, wherein the heat-resistant auxiliary agent GW is prepared by reacting 2-indolone and 2- (4-bromophenyl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan in a mixed solution of potassium acetate, 1, 4-dioxane and [1,1' -bis (diphenylphosphine) ferrocene ] palladium (II) dichloride, washing an organic portion with water after the reaction is completed, extracting an obtained water layer with ethyl acetate, combining the organic layers, drying the organic layers with anhydrous sodium sulfate, filtering and concentrating to obtain a crude product, and purifying by flash column chromatography to obtain the purified heat-resistant auxiliary agent GW.
3. The composite heat resistant agent of claim 2 wherein the reaction is carried out at 90 ℃ for 24 hours.
4. A high temperature resistant silicone rubber characterized by the addition of the composite heat resistant agent according to any one of claims 1 to 3.
5. The high temperature resistant silicone rubber according to claim 4, wherein the high temperature resistant silicone rubber comprises 100 parts of methyl vinyl silicone rubber, 30-50 parts of white carbon black, 0.2-10 parts of structuring control agent, 0.5-10 parts of composite heat resistant agent and 0.05-0.3 part of internal mold release agent.
6. The high temperature resistant silicone rubber according to claim 5, wherein the molar mass of the methyl vinyl silicone rubber raw rubber is between 500000 and 750000g/mol, and the content of vinyl is 0.05 to 1.0 percent in terms of mole percent.
7. The high temperature resistant silicone rubber according to claim 5, wherein the white carbon black is fumed silica with a specific surface area of 200-380m 2/g.
8. The high temperature resistant silicone rubber according to claim 5, wherein the internal mold release agent is one or more of zinc stearate, calcium stearate, barium stearate, magnesium stearate, zinc laurate, magnesium laurate, palmitic acid, lauric acid, stearic acid.
9. The high temperature resistant silicone rubber according to claim 5, wherein the structuring control agent comprises one or more of hydroxyl silicone oil, vinyl hydroxyl silicone oil, diphenyl dihydroxy silicone oil, dimethyl dimethoxy silane, dimethyl diethoxy silane, methyl phenyl dimethoxy silane, methyl phenyl diethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, hexamethyldisilazane, vinyl silazane, vinyl trimethoxy silane, vinyl triethoxy silane.
10. The high temperature resistant silicone rubber according to claim 9, wherein the purity of the methyl phenyl dimethoxy silane is not less than 99%, the refractive index of the methyl phenyl dimethoxy silane is 1.469+/-0.005 at 25 ℃ when helium yellow line with the wavelength of 587.56 nanometers is taken as incident light, and the polychlorinated biphenyl content is 0.
11. The high temperature resistant silicone rubber according to claim 9, wherein the viscosity of the vinyl hydroxyl silicone oil at 25 ℃ is less than or equal to 35mm 2/s, the hydroxyl content is more than or equal to 6.0% in mol%, and the vinyl content is 6.5-7.5 in mol%.
12. The method for preparing high temperature resistant silicone rubber according to any one of claims 4 to 11, characterized in that the method comprises the steps of:
(1) Placing raw methyl vinyl silicone rubber, a structuring control agent and an internal release agent into a kneader to obtain a first mixed material;
(2) Adding white carbon black into the first mixed material in batches, uniformly mixing at 100 ℃, and standing for 4-8 hours to obtain a second mixed material;
(3) And (3) banburying the second mixed material for 2-5 hours under the conditions of 0.04-0.08MPa and 120-170 ℃ to obtain a mixed base rubber, adding the composite heat-resistant agent into the mixed base rubber under the condition that the temperature is less than or equal to 100 ℃ to obtain a mixed sizing material, and discharging.
13. The method for preparing high temperature resistant silicone rubber according to claim 12, wherein the mixed sizing material is further added with a vulcanizing agent for molding, and the vulcanizing agent is selected from one of 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, dicumyl peroxide, benzoyl peroxide, 2, 4-dichloro benzoyl peroxide and platinum vulcanizing agent.
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