CN104650291B - Method for preparing reinforced butadiene styrene rubber by olefin metathesis catalyst - Google Patents
Method for preparing reinforced butadiene styrene rubber by olefin metathesis catalyst Download PDFInfo
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- CN104650291B CN104650291B CN201310585220.0A CN201310585220A CN104650291B CN 104650291 B CN104650291 B CN 104650291B CN 201310585220 A CN201310585220 A CN 201310585220A CN 104650291 B CN104650291 B CN 104650291B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 title claims description 44
- 238000005865 alkene metathesis reaction Methods 0.000 title claims description 15
- 238000000034 method Methods 0.000 title claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 65
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000178 monomer Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 29
- 150000001336 alkenes Chemical class 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 14
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 11
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract 2
- -1 carbon Alkane Chemical class 0.000 claims description 27
- 125000001424 substituent group Chemical group 0.000 claims description 27
- 229920001971 elastomer Polymers 0.000 claims description 19
- 239000005060 rubber Substances 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 125000005375 organosiloxane group Chemical group 0.000 claims description 12
- 238000004807 desolvation Methods 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 9
- 239000012763 reinforcing filler Substances 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims description 4
- 230000003014 reinforcing effect Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- QROGIFZRVHSFLM-QHHAFSJGSA-N [(e)-prop-1-enyl]benzene Chemical compound C\C=C\C1=CC=CC=C1 QROGIFZRVHSFLM-QHHAFSJGSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 3
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical group CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 125000005336 allyloxy group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- ONJMNXFNTYIEEA-UHFFFAOYSA-N benzene ethene Chemical compound C1=CC=CC=C1.C=C.C=C.C=C ONJMNXFNTYIEEA-UHFFFAOYSA-N 0.000 claims description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 2
- 150000002118 epoxides Chemical class 0.000 claims description 2
- IRTACFOVZDBFEX-UHFFFAOYSA-N ethenyl-diethoxy-ethylsilane Chemical compound CCO[Si](CC)(C=C)OCC IRTACFOVZDBFEX-UHFFFAOYSA-N 0.000 claims description 2
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims 2
- 229910052801 chlorine Inorganic materials 0.000 claims 2
- HMRKNJNCWFIGOJ-UHFFFAOYSA-N 2-butoxyethylsilane Chemical compound C(CCC)OCC[SiH3] HMRKNJNCWFIGOJ-UHFFFAOYSA-N 0.000 claims 1
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 claims 1
- HYVIYMTYTMCPIU-UHFFFAOYSA-N C(C)(C)OC1=C(C=C2C(CCCC2)P(C2CCCCC2)C2CCCCC2)C=CC=C1.[Cl] Chemical compound C(C)(C)OC1=C(C=C2C(CCCC2)P(C2CCCCC2)C2CCCCC2)C=CC=C1.[Cl] HYVIYMTYTMCPIU-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- QGGUMTNPIYCTSF-UHFFFAOYSA-N hexylsilane Chemical compound CCCCCC[SiH3] QGGUMTNPIYCTSF-UHFFFAOYSA-N 0.000 claims 1
- 239000008234 soft water Substances 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 2
- 230000001112 coagulating effect Effects 0.000 abstract 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 10
- 230000002787 reinforcement Effects 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 235000019394 potassium persulphate Nutrition 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 229960003328 benzoyl peroxide Drugs 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 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 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- PZEWNWAJJVPYEI-UHFFFAOYSA-N ethenyl(hexyl)silane Chemical compound CCCCCC[SiH2]C=C PZEWNWAJJVPYEI-UHFFFAOYSA-N 0.000 description 2
- JEWCZPTVOYXPGG-UHFFFAOYSA-N ethenyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)C=C JEWCZPTVOYXPGG-UHFFFAOYSA-N 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N ethylmethylbenzene Natural products CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 238000007901 in situ hybridization Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 229940096992 potassium oleate Drugs 0.000 description 2
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 125000005401 siloxanyl group Chemical group 0.000 description 2
- ITCAUAYQCALGGV-XTICBAGASA-M sodium;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Na+].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O ITCAUAYQCALGGV-XTICBAGASA-M 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- TXISDYBMZCVCNN-UHFFFAOYSA-N CC(C)OC1=C(C=C(CCCC2)C2P(C2CCCCC2)C2CCCCC2)C=CC=C1 Chemical compound CC(C)OC1=C(C=C(CCCC2)C2P(C2CCCCC2)C2CCCCC2)C=CC=C1 TXISDYBMZCVCNN-UHFFFAOYSA-N 0.000 description 1
- VTOJWQWMXSKUCX-UHFFFAOYSA-N CCCCCCCCC[O] Chemical compound CCCCCCCCC[O] VTOJWQWMXSKUCX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical class Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical group CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a preparation method of high-strength styrene-butadiene rubber, which adopts olefin double decomposition catalyst to prepare styrene-butadiene rubber reinforcing agent and carries out ternary polymerization on styrene, butadiene and the styrene-butadiene rubber reinforcing agent. Firstly, synthesizing a styrene butadiene rubber reinforcing agent with good reactivity with styrene and butadiene, mixing an aromatic compound containing an ethylenically unsaturated substituent and an organic siloxane monomer containing an ethylenically unsaturated substituent, adding a toluene solvent and an olefin double decomposition catalyst, isolating air and water, reacting at normal temperature, and removing the toluene solvent by using a vacuum desolventizing device to prepare the styrene butadiene rubber reinforcing agent. Adding styrene, butadiene and the styrene butadiene rubber reinforcing agent into a polymerization kettle in proportion, adding an emulsifier, soft water and an initiator, controlling the reaction temperature and the reaction pressure, reacting for a period of time, and then coagulating, washing and drying to obtain the high-strength styrene butadiene rubber product.
Description
Technical field
The present invention relates to a kind of preparation method of butadiene-styrene rubber, is specifically that fourth is made using olefin metathesis catalyst in one kind
Benzene rubber reinforcing filler, and by the preparation of the high intensity butadiene-styrene rubber of styrene, butadiene and butadiene-styrene rubber reinforcing agent ternary polymerization
Method.
Background technology
Butadiene-styrene rubber green strength is relatively low, typically only 2.3~6.5MPa, and the raising of its intensity is mainly by post-processing process
Reinforcing agent improved, it is general up to 21.5~24.5MPa.Reinforcing agent mainly have carbon black, white carbon, nano-calcium carbonate and
The inorganic particles such as montmorillonite, its reinforcement mechanism are the surface textures or its nano adsorption characteristic enriched by inorganic particle, make rubber
Glue macromolecular and reinforcing agent ask to form physical absorption or chemical bond, so formed by inorganic powder stop centered on networking mechanism
So as to play a part of to reinforcing rubber.Inorganic particle from reuniting than more serious, to realize itself and rubber mixing need it is higher
Energy, generally require and carry out prolonged mediating and being kneaded repeatedly in mill or banbury.
In recent years, the in-situ reinforcement technology of rubber, the process for modifying surface etc. of nano-powder are widely used.
The method of 200910092836.8 silicon in-situ hybridization graft modification latex containing poly-conjugated-diolefin, organosiloxane is incorporated into and contained
There is the unsaturated rubber system of double bond, organosiloxane is grafted in rubber backbone by the reaction between unsaturated bond, silicon
Play a part of reinforcement after the hydrolysis of oxygen alkane.This method needs siloxanes that chemistry occurs instead with the unsaturated double-bond on rubber molecule
The side reactions such as cross-linking reaction, demulsification should easily be caused, it is necessary to add initiator into latex, improve the condition such as reaction temperature.
A kind of 201010114230.2 preparation methods of in-situ hybridization enhancing butadiene-acrylonitrile-isoprene copolymer, use are polynary
VTES is introduced directly into polymer by the mode of copolymerization, reaches the purpose of in-situ reinforcement.This method is gathered
It is complicated to close monomer component, nail body reactivity ratio is differed greatly, and polymerization process is difficult to control.
The content of the invention
It is an object of the present invention to provide a kind of a kind of method for preparing reinforced type butadiene-styrene rubber by adding rubber reinforcing filler, tool
Body is：According to quality proportioning it is (5~45) by styrene, butadiene and rubber reinforcing filler：(95~50)：(1~45) add poly-
Kettle is closed, sequentially adds emulsifying agent, water and initiator, controlling reaction temperature is 3~80 DEG C, and reaction pressure is 1.5~2.5MPa, instead
5~15h is answered, reacted emulsion obtains high intensity butadiene-styrene rubber through condensing, washing, dry.
Rubber reinforcing filler of the present invention is represented by
Rubber reinforcing filler is by the aromatic compound of the substituent of unsaturation containing alkeneWith containing alkene
The organosiloxane monomer of unsaturated substituentBy made from olefin metathesis reaction.
Specific preparation method includes：The aromatic compound of the substituent of unsaturation containing alkene and the substituent of unsaturation containing alkene it is organic
Siloxanyl monomers are with l：(0.1~5.0) mixed in molar ratio, the monomer that the mass concentration of l%~30% is configured to toluene solvant are molten
Liquid, 0.01~0.1% olefin metathesis catalyst of the amount for accounting for monomeric substance is added into solution, completely cut off air and water, often
After 0.5~8h of temperature reaction, toluene solvant is deviate from using vacuum desolvation agent device, butadiene-styrene rubber reinforcing agent is made.
The aromatic compound of the substituent of unsaturation containing alkene of the present inventionIn structural formula
R5Can be-H or C1~C20 straight chain or the saturation substituent of ring-type, R5Any substitution position that may be coupled on phenyl ring；
R6Can be-H or C1~C20 straight chain or the saturation substituent of ring-type；The aromatic compound of the substituent of unsaturation containing alkene can be with
It is the aromatic compound of the different carbon chain lengths such as styrene, propenylbenzene, methyl styrene substituent of unsaturation containing alkene, preferably benzene
Ethene.
Its structural formula of the organosiloxane monomer of the substituent of unsaturation containing alkene is：
Wherein：
R4- unsaturated olefin aliphatic the segment containing 2~18 carbon, can be vinyl, acrylic, isopropenyl,
Isopentene group or 1- heptenyls, preferred vinyl；
R1、R3- the alkoxy containing l~12 carbon, the aryloxy group of 6~12 carbon, the siloxy of 3~12 carbon, Ke Yishi
Methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, hexyloxy, amoxy, positive epoxide in heptan, different octyloxy, positive nonyl oxygen
Base, phenoxy group, chlorophenoxy, allyloxy, benzyloxy, acetoxyl group, trimethylsiloxy group, preferably methoxyl group, ethyoxyl；Rl
And R3It is to hydrolyze alkoxy by the effect of heat and acid when butadiene-styrene rubber is processed to be set as the purpose containing alkoxy, so as to
It is interior formation-O-Si- spacial frameworks to stop in rubber, so as to play strengthening action to base rubber；If organosiloxane
There was only an alkoxy in monomer, it then only forms dimerization after hydrolyzing and stopped, it is impossible to forms-O-Si- spacial frameworks, rises not
To the effect of reinforcement.
R2Can be with R1 identical groups, can also be the saturation segment containing 1~20 carbon, the ring-type alkane of l~8
Hydrocarbon, aromatic hydrocarbon；It is preferred that methyl, ethyl, methoxyl group, ethyoxyl.
The organosiloxane monomer of the substituent of unsaturation containing alkene of the present invention can be VTES,
Vinyl diethoxy-ethylsilane, vinyltrimethoxy silane, two amoxys of vinyl-hexyl silane, isopropenyl two
N-butoxyethyl silane etc..
Olefin metathesis catalyst of the present invention is a kind of Ru carbene complex catalyst, can be that dichloro is (o-
Isopropoxy benzylidene) (tricyclohexyl phosphine) conjunction ruthenium (II)Dichloro (o- isopropoxy
Benzylidene) (1,3- double (2,4,6- trimethylphenyl) -2- imidazolines alkylidenes) conjunction ruthenium
Deng the Grubbs catalyst series with identity function or other metal carbene catalysts with olefin metathesis function, preferably
" part " being not specifically noted in the present invention each means mass parts.
The emulsifying agent and initiator added in the present invention is auxiliary agent generally in the art, can be used commonly used in the art
Species；Its addition is also required normal well known to a person skilled in the art being reacted according to butadiene and styrene monomer
Dosage is advised, therefore, the present invention does not do particular determination.It is preferred as 100 parts of juice, emulsifying agent using styrene and divinylic monomer gross mass
Addition is 1~10 part, and the initiator amount of being preferably added to is 0.01~0.1 part, and the amount of being preferably added to of water is l50~200 part.
Emulsifying agent of the present invention can use the anionics such as sodium soap, aliphatic acid potassium, sodium abietate, potassium oleate
Emulsifying agent.
Initiator of the present invention can use benzoyl peroxide ((PhCO2)2), dicumyl peroxide, hydrogen peroxide
Diisopropylbenzene (DIPB) or potassium peroxydisulfate etc..
The technical principle of wooden invention foundation is：
Formula (1)
Formula (2)
As shown in above-mentioned chemical equation (1) and formula (2), the aromatics of the substituent of unsaturation containing alkene in the present invention
Olefin metathesis reaction occurs for the organosiloxane monomer of thing and the substituent of unsaturation containing alkene, with styrene and the ethoxy of vinyl 3
Olefin metathesis reaction reaction occurs in the case where toluene makees solvent Grubbs bis- generations catalyst actions, under normal temperature for base silane, generation
Benzene substituted ethylene ethyl triethoxy silicane alkane is butadiene-styrene rubber reinforcing agent.Butadiene-styrene rubber reinforcing agent is with styrene, butadiene in peroxide
The effect of compound initiator issues raw emulsion terpolymer reaction generation Reinforcing Styrene-butadiene Rubber.
The butadiene-styrene rubber makes reinforcement group hydrolyze to form (- Si-O-Si-) in application process by heating or acid condition
Sky ask network structure, so as to playing a part of reinforcement to rubber mass.Simultaneously it is emphasized that the butadiene-styrene rubber reinforcing agent
Phenyl ring or aromatic structure and double bond form big conjugated system, make double bond be easy to participate in polymerisation, and reinforcing agent is in rubber
It is easily dispersed also because of similar compatibility in glue.The enhanced butadiene-styrene rubber and common designations butadiene-styrene rubber phase of the present invention
Than tensile strength can improve more than 30%.
Embodiment
Material auxiliary agent needed for present invention specific implementation is as described below：
(1) the organosiloxane monomer of the substituent of unsaturation containing alkene：VTES, vinyl diethyl one
Ethoxysilane, vinyl trimethoxy siloxanes, SILVER REAGENT, Shanghai Hui Pu siloxanes Co., Ltd；
(2) aromatic compound of the substituent of unsaturation containing alkene：The different carbon chains such as styrene, propenylbenzene, methyl styrene
The aromatic compound of length and alkene unsaturation substituent, optimization styrene.T industry levels, Lanzhou Petrochemical；
(3) olefin metathesis catalyst：Ruthenium card
Guest's catalyst, 500mg/ bottles, purity >=98%w, lark prestige Science and Technology Ltd.；
(4) styrene monomer, divinylic monomer, technical grade, Lanzhou Petrochemical；
(5) sodium soap, aliphatic acid potassium, sodium abietate, potassium oleate, technical grade, Lanzhou Petrochemical；
(6) benzoyl peroxide ((PhCO2)2), dicumyl peroxide, di-isopropylbenzene hydroperoxide, potassium peroxydisulfate, industry
Level, Lanzhou Petrochemical.
Embodiment 1
Styrene and VTES monomer are with 1：1 mixed in molar ratio, 10% matter is configured to toluene solvant
The monomer solution of concentration is measured, adds monomer 0.01%mol's into solutionCatalyst, every
Exhausted air and water, toluene solvant after 25 DEG C are reacted 2h, is deviate from, butadiene-styrene rubber reinforcing agent is made using vacuum desolvation agent device.
Styrene, butadiene and above-mentioned butadiene-styrene rubber reinforcing agent are put into according to the ratio that quality proportioning is 28/70/2 and gathered
Kettle is closed, adds the sodium soap emulsifying agent for accounting for monomer gross mass 5%w, 180%w soft water and 0.05%w hydrogen peroxide isopropyl
Benzene initiator, controlling reaction temperature are 5 DEG C, reaction pressure 2.0MPa, react 8h.By emulsion after reaction through condensing, washing, doing
It is dry, obtain high intensity butadiene-styrene rubber.After tested, compared with common butylbenzene Green tensile strength (18.6MPa), the increasing of embodiment 1
Strong type butylbenzene Green tensile strength 25.3MPa, improves 36.0%.
Comparative example 1
Butadiene-styrene rubber reinforcing agent is directly kneaded by this comparative example with butadiene-styrene rubber.Specially：Styrene and the second of vinyl three
TMOS monomer is with l：L mixed in molar ratio, the monomer solution of 10% mass concentration is configured to toluene solvant, added into solution
Enter monomer 0.01%mol'sCatalyst, completely cut off air and water, after 25 DEG C are reacted 2h, use
Vacuum desolvation agent device deviates from toluene solvant, and butadiene-styrene rubber reinforcing agent is made.
Sample is made after reinforcing agent and butadiene-styrene rubber are directly kneaded, the addition of reinforcing agent is butadiene-styrene rubber quality
5%.After tested, compared with common butylbenzene Green tensile strength (18.6MPa), comparative example l enhanced butylbenzene Green tensile is strong
20.8MPa is spent, only improves 11.8%.
Embodiment 2
By styrene and vinyl diethoxymethylsilane monomer with l：0.1 mixed in molar ratio, is configured with toluene solvant
Into the monomer solution of 30% mass concentration, add monomer 0.04mol's into solutionCatalyst,
Completely cut off air and water, after 25 DEG C are reacted 8h, deviate from toluene solvant using vacuum desolvation agent device, butadiene-styrene rubber reinforcement is made
Agent.
Styrene, butadiene and above-mentioned butadiene-styrene rubber reinforcing agent are put into according to the ratio that quality proportioning is l5/70/15 and gathered
Kettle is closed, adds monomer mass 10%w potassium rosinate emulsifying agent, 200%w soft water, 0.1%w potassium peroxydisulfate initiator, control
Reaction temperature processed is 80 DEG C, reaction pressure 2.5Mpa, reacts 8h.By emulsion after reaction through condensing, washing, dry, height is obtained
Intensity butadiene-styrene rubber.After tested, compared with common butylbenzene Green tensile strength (19.6MPa), the enhanced butylbenzene life of embodiment 2
Glue tensile strength 25.9MPa, improves 32.1%.
Comparative example 2：
This comparative example replaces VTES to be carried out instead with styrene with vinyl ethoxy dimethylsilane
Should.Specially：Styrene and ethenylethoxy dimethylsilane monomer are with l：0.1 mixed in molar ratio, is configured with toluene solvant
Into the monomer solution of 30% mass concentration, add monomer 0.04%mol's into solutionCatalysis
Agent, completely cut off air and water, after 25 DEG C are reacted 8h, deviate from toluene solvant using vacuum desolvation agent device, butadiene-styrene rubber is made and mends
Strong agent.
Styrene, butadiene and above-mentioned butadiene-styrene rubber reinforcing agent are put into according to the ratio that quality proportioning is 15/70/15 and gathered
Kettle is closed, adds monomer mass 10%w potassium rosinate emulsifying agent, 200%w soft water, 0.1%w potassium peroxydisulfate initiator, control
Reaction temperature processed is 80 DEG C, reaction pressure 2.5Mpa, reacts 8h.By emulsion after reaction through condensing, washing, dry, height is obtained
Intensity butadiene-styrene rubber.After tested, compared with common butylbenzene Green tensile strength (17.9MPa), the enhanced butylbenzene life of comparative example 2
Glue tensile strength l8.4MPa, intensity improve unobvious.
Embodiment 3：
By methyl styrene and vinyltrimethoxy silane monomer with l：5 mixed in molar ratio, are configured to toluene solvant
The list of 1% mass concentration stops solution, adds monomer 0.10%mol's into solutionCatalyst, every
Exhausted air and water, toluene solvant after 25 DEG C are reacted 0.5h, is deviate from, butadiene-styrene rubber reinforcement is made using vacuum desolvation agent device
Agent.
Styrene, butadiene and above-mentioned butadiene-styrene rubber reinforcing agent are put into according to the ratio that quality proportioning is 5/50/45 and gathered
Kettle is closed, adds monomer mass 3%w potassium rosinate emulsifying agent, 190%w soft water, 0.07%w di-isopropylbenzene hydroperoxide
Initiator, controlling reaction temperature are 6 DEG C, reaction pressure 2.5Mpa, react 8h.By emulsion after reaction through condensing, washing, doing
It is dry, obtain high intensity butadiene-styrene rubber.After tested, compared with common butylbenzene Green tensile strength (20.1MPa), the increasing of embodiment 3
Strong type butylbenzene Green tensile strength 25.5MPa, improves 26.8%.
Comparative example 3：
Compared with Example 3, other conditions are identical, and difference is to be reacted instead of styrene using butylene, tool
Body is：By butylene and vinyltrimethoxy silane monomer with l：5 mixed in molar ratio, it is dense to be configured to l% mass with toluene solvant
The monomer solution of degree, add monomer 0.10%mol's into solutionCatalyst, isolation air and
Water, after 25 DEG C are reacted 0.5h, toluene solvant is deviate from using vacuum desolvation agent device, butadiene-styrene rubber reinforcing agent is made.
Styrene, butadiene and above-mentioned butadiene-styrene rubber reinforcing agent are put into according to the ratio that quality proportioning is 5/50/45 and gathered
Kettle is closed, adds monomer mass 3%w potassium rosinate emulsifying agent, 190%w soft water, the 0.07%w different interior benzene of hydrogen peroxide two
Initiator, controlling reaction temperature are 6 DEG C, reaction pressure 2.5Mpa, react 8h.By emulsion after reaction through condensing, washing, doing
It is dry, a large amount of unreacted monomers are found in coacervation process, obtain a small amount of butadiene-styrene rubber.After tested, with common butylbenzene Green tensile
Intensity (17.9MPa) is compared, and the enhanced butylbenzene Green tensile strength 18.5MPa of comparative example 3, is not significantly improved.
Embodiment 4：
By two amoxys of styrene and vinyl-hexyl silane monomer with 1：1.9 mixed in molar ratio, are configured with toluene solvant
Into the monomer solution of 20% mass concentration, add monomer 0.03%mol's into solutionUrge
Agent completely cuts off air and water, after 25 DEG C are reacted 4h, is deviate from toluene solvant using vacuum desolvation agent device, and butadiene-styrene rubber is made and mends
Strong agent.
Styrene, butadiene and above-mentioned butadiene-styrene rubber reinforcing agent are put into polymerization according to the ratio that quality proportioning is 8/90/2
Kettle, addition monomer mass 1%w sodium soap emulsifying agent, 150%w soft water, 0.01%w benzoyl peroxide initiator,
Controlling reaction temperature is 3 DEG C, reaction pressure 1.5Mpa, reacts 15h.By emulsion after reaction through condensing, washing, dry, obtain
High intensity butadiene-styrene rubber.After tested, compared with common butylbenzene Green tensile strength (19.1MPa), the enhanced butylbenzene of embodiment 4
Green tensile strength 26.2MPa, improves 37.1%.
Comparative example 4：
Compared with Example 4, other conditions are identical, and difference is to replace styrene to carry out instead using ethyl methyl benzene
Should, it is specially：Ethyl methyl benzene and vinyl trimethoxy siloxanyl monomers are with l：1.9 mixed in molar ratio, are matched somebody with somebody with toluene solvant
The monomer solution of 20% mass concentration is set to, adds monomer 0.10%mol's into solutionUrge
Agent, completely cut off air and water, after 25 DEG C are reacted 4h, deviate from toluene solvant using vacuum desolvation agent device, butadiene-styrene rubber is made
Reinforcing agent.
Reinforcing agent is calculated into addition with l5% parts of butadiene-styrene rubber quality, sample is made after being directly kneaded with butadiene-styrene rubber
Product.After tested, compared with straight styrene-butadiene rubber tensile strength (18.2MPa), the butadiene-styrene rubber tensile strength 18.9MPa of comparative example 4, by force
Degree is not significantly improved.
Claims (14)
1. the method that Reinforcing Styrene-butadiene Rubber is prepared using olefin metathesis catalyst, it is characterised in that comprise the following steps：By benzene
Ethene, butadiene and rubber reinforcing filler are (5~45) according to quality proportioning：(95~50)：(1~45) polymeric kettle is added,
Emulsifying agent, water and initiator are sequentially added, controlling reaction temperature is 3~80 DEG C, and reaction pressure is 1.5~2.5MPa, instead
5~15h is answered, reacted emulsion obtains butadiene-styrene rubber through condensing, washing, dry；Described rubber reinforcing filler isWherein, R1、R3For the alkoxy containing 1~12 carbon, the aryloxy group or 3 of 6~12 carbon
The siloxy of~12 carbon；R2For with R1Identical group, or saturation segment or 1~8 ring-type containing 1~20 carbon
Alkane, aromatic hydrocarbon；R5It is H or Cl~C20 straight chain or the saturation substituent of ring-type.
2. the preparation method as described in claim l, it is characterised in that using styrene and divinylic monomer gross mass as 100 parts
Meter, emulsifying agent addition are 1~10 part.
3. the preparation method as described in claim l, it is characterised in that gross mass is stopped as 100 parts using styrene and butadiene list
Meter, the addition of water is 150~200 parts.
4. the preparation method as described in claim l, it is characterised in that using styrene and divinylic monomer gross mass as 100 parts
Meter, initiator addition are 0.01~0.1 part.
5. the preparation method as described in claim l, it is characterised in that described rubber reinforcing filler is by unsaturated containing alkene
The aromatic compound of substituentWith the organosiloxane monomer of the substituent of unsaturation containing alkeneBy made from olefin metathesis reaction, wherein R4For the unsaturated olefin aliphatic chain containing 2~18 carbon
Section；R6It is H or Cl~C20Straight chain or ring-type saturation substituent.
6. the preparation method as described in claim l, it is characterised in that described rubber reinforcing filler preparation method includes：Containing alkene not
The organosiloxane monomer of the aromatic compound of saturation substituent and the substituent of unsaturation containing alkene is with 1：(0.1~5.0) mol ratio
Mixing, the monomer solution of 1%~30% mass concentration is configured to toluene solvant, the amount that accounts for monomeric substance is added into solution
0.01~0.1% olefin metathesis catalyst, completely cuts off air and water, after 0.5~8h of normal-temperature reaction, is filled using vacuum desolvation agent
Put and deviate from toluene solvant, butadiene-styrene rubber reinforcing agent is made.
7. the preparation method as described in claim 5 or 6, it is characterised in that the aromatics of the substituent of unsaturation containing alkene
ThingMiddle substituent R5、R6It is H or C1~C20 straight chain or the saturation substituent of ring-type.
8. the preparation method as described in claim 5 or 6, it is characterised in that the aromatics of the substituent of unsaturation containing alkene
Thing is styrene, propenylbenzene or methyl styrene.
9. the preparation method as described in claim 5 or 6, it is characterised in that the organosilicon of the substituent of unsaturation containing alkene
Its structural formula of oxygen alkane monomer is：Wherein：R1、R3For the alkoxy containing 1~12 carbon, the virtue of 6~12 carbon
The siloxy of epoxide or 3~12 carbon；R2For with R1Identical group, or the saturation segment or 1~8 containing 1~20 carbon
Cyclic alkane, aromatic hydrocarbon；R4For the unsaturated olefin aliphatic segment containing 2~18 carbon.
10. preparation method as claimed in claim 9, it is characterised in that the organosiloxane of the substituent of unsaturation containing alkene
R in structural formula1、R3；Selected from methoxyl group, ethyoxyl, propoxyl group, isopropoxy, n-butoxy, hexyloxy, amoxy, positive oxygen in heptan
Base, different octyloxy, positive nonyl epoxide, phenoxy group, chlorophenoxy, allyloxy, benzyloxy, acetoxyl group, trimethylsiloxy group.
11. preparation method as claimed in claim 9, it is characterised in that the organosiloxane of the substituent of unsaturation containing alkene
R in structural formula4Selected from vinyl, acrylic, isopropenyl, isopentene group or 1- heptenyls.
12. the preparation method as described in claim 5 or 6, it is characterised in that the described substituent of unsaturation containing alkene present invention choosing
From VTES, vinyl diethoxy ethylsilane, vinyltrimethoxy silane, the amoxy of vinyl two
Hexyl silane or the n-butoxyethyl silane of isopropenyl two.
13. the preparation method as described in claim 5 or 6, it is characterised in that described olefin metathesis catalyst is selected from two
Chlorine (o- isopropoxy benzylidene) (tricyclohexyl phosphine) closes ruthenium (II) or dichloro [o- isopropoxy benzene methylene
Base] [1,3- double (2,4,6- trimethylphenyl) -2- imidazolines alkylidenes] conjunction ruthenium.
14. the preparation method as described in claim 5 or 6, it is characterised in that described olefin metathesis catalyst is selected from
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| WO2018221694A1 (en) | 2017-05-31 | 2018-12-06 | 古河電気工業株式会社 | Hydrodesulfurization catalyst structure, hydrodesulfurization device provided with said catalyst structure, and production method of hydrodesulfurization catalyst structure |
| AU2018276617B2 (en) | 2017-05-31 | 2021-03-25 | Furukawa Electric Co., Ltd. | Functional structure and production method for functional structure |
| AU2018277967B2 (en) | 2017-05-31 | 2021-05-27 | Furukawa Electric Co., Ltd. | Functional structure and production method for functional structure |
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| CN110730687A (en) | 2017-05-31 | 2020-01-24 | 古河电气工业株式会社 | Catalyst structure for catalytic cracking or hydrodesulfurization, catalytic cracking device and hydrodesulfurization device each having the catalyst structure, and method for producing catalyst structure for catalytic cracking or hydrodesulfurization |
| AU2018276618B2 (en) | 2017-05-31 | 2021-05-27 | Furukawa Electric Co., Ltd. | Functional structure and production method for functional structure |
| JP7328145B2 (en) | 2017-05-31 | 2023-08-16 | 古河電気工業株式会社 | Steam reforming catalyst structure, reformer equipped with the steam reforming catalyst structure, and method for producing the steam reforming catalyst structure |
| WO2018221696A1 (en) | 2017-05-31 | 2018-12-06 | 古河電気工業株式会社 | Oxidation catalyst structure for exhaust gas purification and production method thereof, exhaust gas treatment device for vehicle, catalyst molded body, and gas purification method |
| US11161101B2 (en) | 2017-05-31 | 2021-11-02 | Furukawa Electric Co., Ltd. | Catalyst structure and method for producing the catalyst structure |
| EP3632542A4 (en) | 2017-05-31 | 2021-01-06 | Furukawa Electric Co., Ltd. | Co shift or reverse shift catalyst structure and production method thereof, co shift or reverse shift reaction device, production method of carbon dioxide and hydrogen, and production method of carbon monoxide and water |
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