CN102617846A - Process for production of polyether and process for production of solid acid catalyst - Google Patents
Process for production of polyether and process for production of solid acid catalyst Download PDFInfo
- Publication number
- CN102617846A CN102617846A CN2012100264941A CN201210026494A CN102617846A CN 102617846 A CN102617846 A CN 102617846A CN 2012100264941 A CN2012100264941 A CN 2012100264941A CN 201210026494 A CN201210026494 A CN 201210026494A CN 102617846 A CN102617846 A CN 102617846A
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- China
- Prior art keywords
- solid acid
- acid catalyst
- catalyzer
- polyethers
- catalyst
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 275
- 239000011973 solid acid Substances 0.000 title claims abstract description 213
- 229920000570 polyether Polymers 0.000 title claims abstract description 153
- 238000000034 method Methods 0.000 title claims abstract description 137
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 72
- 230000008569 process Effects 0.000 title abstract description 18
- 239000004721 Polyphenylene oxide Substances 0.000 title abstract description 7
- 238000001556 precipitation Methods 0.000 claims description 171
- 229910052751 metal Inorganic materials 0.000 claims description 105
- 239000011148 porous material Substances 0.000 claims description 63
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 41
- 150000004692 metal hydroxides Chemical class 0.000 claims description 41
- 150000004292 cyclic ethers Chemical group 0.000 claims description 34
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 26
- 239000004927 clay Substances 0.000 claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000010457 zeolite Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- ZKRXZOLGLXXMEA-UHFFFAOYSA-N dioxosilane zirconium Chemical compound [Zr].[Si](=O)=O ZKRXZOLGLXXMEA-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 133
- 150000001875 compounds Chemical class 0.000 abstract description 68
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 59
- 238000006116 polymerization reaction Methods 0.000 abstract description 18
- 230000006866 deterioration Effects 0.000 abstract description 17
- 238000009826 distribution Methods 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000006482 condensation reaction Methods 0.000 abstract description 8
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- 229910010272 inorganic material Inorganic materials 0.000 abstract 2
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- 239000002243 precursor Substances 0.000 description 120
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- 238000010438 heat treatment Methods 0.000 description 76
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- 239000002253 acid Substances 0.000 description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 54
- 239000003513 alkali Substances 0.000 description 54
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 45
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- 230000000052 comparative effect Effects 0.000 description 38
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- 238000002360 preparation method Methods 0.000 description 34
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 32
- 239000004202 carbamide Substances 0.000 description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 26
- -1 polyoxyethylene Polymers 0.000 description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 229910052748 manganese Inorganic materials 0.000 description 23
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 22
- 238000006460 hydrolysis reaction Methods 0.000 description 22
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- 239000007789 gas Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 20
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 15
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- 235000010724 Wisteria floribunda Nutrition 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
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- 235000012239 silicon dioxide Nutrition 0.000 description 13
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 12
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 12
- 239000011491 glass wool Substances 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 10
- 230000008859 change Effects 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 238000005755 formation reaction Methods 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- 229910052726 zirconium Inorganic materials 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
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- 239000012456 homogeneous solution Substances 0.000 description 9
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- 229910052758 niobium Inorganic materials 0.000 description 8
- 239000010955 niobium Substances 0.000 description 8
- QHUNJMXHQHHWQP-UHFFFAOYSA-N trimethylsilyl acetate Chemical compound CC(=O)O[Si](C)(C)C QHUNJMXHQHHWQP-UHFFFAOYSA-N 0.000 description 8
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 7
- 239000001099 ammonium carbonate Substances 0.000 description 7
- 238000012856 packing Methods 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- JQZUMFHYRULBEN-UHFFFAOYSA-N diethyl(methyl)silicon Chemical compound CC[Si](C)CC JQZUMFHYRULBEN-UHFFFAOYSA-N 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000003016 phosphoric acids Chemical class 0.000 description 6
- 238000012797 qualification Methods 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical group NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 150000003672 ureas Chemical group 0.000 description 6
- 239000003377 acid catalyst Substances 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
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- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 5
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- 229910002651 NO3 Inorganic materials 0.000 description 4
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- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical class [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
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- 125000002252 acyl group Chemical group 0.000 description 3
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- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229940059936 lithium bromide Drugs 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Inorganic materials [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910021647 smectite Inorganic materials 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 2
- 229940094989 trimethylsilane Drugs 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 108091071338 17 family Proteins 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical class CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B01J35/30—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
- C08G65/10—Saturated oxiranes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
Abstract
Disclosed is a process for production of a polyether by polymerization or condensation of a raw material compound in the presence of a solid acid catalyst, which is characterized by using a catalyst that is improved in deterioration in catalytic performance with elapse of time to reduce the amount of the catalyst required for the reaction and produce a polyether having a narrow molecular weight distribution with a high conversion rate and in a stable manner for a long period of time. A solid acid catalyst having a hydroxyl group on the surface is allowed to contact with an organic compound other than a polyether and/or an inorganic compound which can react or interact with the hydroxyl group and then subjected to polymerization or condensation reaction. Since a hydrophobic group derived from the organic compound and/or the inorganic compound is bound to the hydroxyl group on the surface of the catalyst, the hydrophobic property of the surface of the catalyst can be improved, any influence of water which may adversely affect the performance of the catalyst can be eliminated, and the deterioration in catalytic performance with elapse of time can be prevented. Further, since a hydrophobic group is already bound to the reactive hydroxyl group on the surface of the catalyst, the binding or interaction of a polyether (i.e., a reaction product) to or with the hydroxyl group on the surface of the catalyst can be prevented, and the deterioration in catalytic performance with elapse of time can be prevented.
Description
The application divides an application; The international application no of its original application is PCT/JP2006/317497; International filing date is on September 5th, 2006; The China national application number is 200680032753.4, and the date that gets into China is on March 6th, 2008, and denomination of invention is " method of manufacture of polyethers and the method for manufacture of solid acid catalyst ".
Technical field
The present invention relates to the method for manufacture of polyethers.The invention still further relates to the method for manufacture of solid acid catalyst and solid acid catalyst.
Background technology
Polyethers is to be used for the raw material of urethane, ammonia ester urea, polyester etc. and to have other polymkeric substance of purposes widely with headed by soft section raw material of spandex fiber, thermoplastic elastomer etc.
As the representative of polyethers, known polyoxyethylene glycol, gather (1, the 2-Ucar 35), polytetramethylene ether diol etc.Wherein, through the ring-opening polymerization of THF (THF) the synthetic polytetramethylene ether diol at aspects such as retractility, elasticity excellent receiving publicity.
[background of the 1st, the 2nd aspect]
Polyether viscosity is than higher; With it is that raw material is further made under the situation of urethane etc.; In its reaction process, need dilution or heating, thereby hope to have the polyethers of a kind of LV (distribution of low molecular weight (MWD=weight-average molecular weight (Mw)/number-average molecular weight (Mn))).Make in industriallization under the situation of polyethers, think that the MWD of the polyethers that obtains can receive the considerable influence of employed catalyst for polymerization.Certainly, the performance of catalyst for polymerization also can influence the transformation efficiency when making polyethers.
As the catalyzer that when making polyethers, uses, the solid acid catalyst that on oxide carriers such as zeolite, silicon-dioxide load has MOX is disclosed in the patent documentation 1 and 2.
Patent documentation 1: japanese kokai publication hei 9-241374 communique
Patent documentation 2: TOHKEMY 2000-327770 communique
According to the inventor's research,, make under the situation of polyethers the polyethers that can't obtain to have the quality that can fully satisfy in industriallization for catalyzer like the existing use of patent documentation 1 and 2 disclosed.That is, for existing catalyzer, along with continuing of reaction; The deterioration of catalyst performance strengthens; Thereby make active deterioration and the MWD that generates polyethers through the time deterioration become significantly, therefore, a large amount of catalyzer of needs in order stably to make polyethers; And also can only make resulting polyethers is the polyethers with wider molecular weight distribution.
[background of the 3rd aspect]
The soda acid intensity that known metal oxyhydroxide and/or MOX have because of himself plays the effect of acid base catalysator.And; Can process composite oxides or with a kind of or metal oxide supported on the different kinds of metals oxide carrier more than 2 kinds through compound two or more MOX; Obtain the stronger strength of acid that shown not second to the separate metal oxide compound, this point is known for people.
In the past; As preparation method with the metal oxide supported solid acid catalyst that on carrier, forms; Usually use following method: after being carried on metallic salt on the carrier, the metal-salt on the carrier is hydrolyzed, processes metal hydroxides with alkali etc.; Heating is fired then, converts metal hydroxides into MOX (patent documentation 3).
As the purposes of such solid acid catalyst, can enumerate the ring-opening polymerization manufacturing polyethers (patent documentation 4) that is used for for example utilizing THF cyclic ethers such as (THF).When utilizing this solid acid catalyst to make polyethers; Certainly much less expectation reacts this point with high conversion; Expect that also the polyethers that produces is a LV in operating aspect; For this reason, preferably produce MWD, be weight-average molecular weight (Mw) and the little polyethers of ratio (Mw/Mn) of number-average molecular weight (Mn).
Patent documentation 3: TOHKEMY 2003-113238 communique
Patent documentation 4: TOHKEMY 2004-161893 communique
According to the inventor's research,, be difficult to metal hydroxides and/or the MOX state with fine dispersion is loaded on the carrier for patent documentation 3 disclosed methods.And even prepare solid acid catalyst with this method, its soda acid amount is also few sometimes, and also broad of the distribution of strength of acid.According to thinking that its reason is; Under the situation about being hydrolyzed with alkali after being carried on metallic salt on the carrier, because alkali is supplied with by carrier is outside, the feed rate of alkali can be different because of the position of carrier inside; Thereby cause hydrolysis rate different; And when metal hydroxides was separated out, metallic salt can be owing to concentration gradient is moved.Promptly; According to thinking, the metal hydroxides of carrier inside can the big aggegation of metal hydroxides occur because of different big part of concentration and the little parts of occurring in the position of carrier inside in the big part of concentration; The less aggegation of metal hydroxides appears in the little part of concentration; Its result, metal hydroxides loads in the carrier unevenly, and this uneven degree broadens relevant with the minimizing of soda acid amount with the distribution of strength of acid.
According to thinking, the strength of acid of this solid acid catalyst distributes to broaden and for example can cause the reduction of transformation efficiency in the ring-opening polymerization of THF etc., so cause the polymerization degree to broaden, be that the MWD of the polyethers of target broadens.
[background of the 4th aspect]
In the patent documentation 1 and 2, the catalyzer that uses when making polyethers such as polytetramethylene ether diol through the ring-opening polymerization of THF etc. discloses the solid acid catalyst that on oxide carriers such as zeolite, silicon-dioxide load has MOX.
For the polyethers that so produces, because necessary molecular-weight average can be according to its purposes and difference, even therefore need the also various polyethers of identical its molecular-weight average of composition of manufacturing polyethers.
The method of the molecular-weight average of resulting polyethers being controlled when making polyethers, past adopts the method for change reaction conditions, promptly changes the method for temperature of reaction, transformation efficiency etc.
Patent documentation 1: japanese kokai publication hei 9-241374 communique
Patent documentation 2: TOHKEMY 2000-327770 communique
When the molecular-weight average of resulting polyethers being changed, for example, increase under the situation of molecular-weight average according to reaction conditions; Reduce temperature of reaction and just can access the big polyethers of molecular-weight average; But through reducing temperature of reaction, reactive behavior is reduced, productivity reduces.And, reduces transformation efficiency and also can access the big polyethers of molecular-weight average, but productivity also reduces in this case.
Also can increase the molecular-weight average of resulting polyethers through reducing the hold concurrently working concentration of terminator of initiators such as diacetyl oxide, but also can cause productivity to reduce because of the reduction of reaction starting velocity in this case.
Conversely, in the time of making the little polyethers of molecular-weight average, improve temperature of reaction just can, but in this case, can cause MWD increase (deterioration), polyether viscosity increases, and also is easy to painted.
And; Also can reduce the molecular-weight average of resulting polyethers through improving the hold concurrently working concentration of terminator of initiators such as diacetyl oxide, but can increase because of diacetyl oxide content remaining in the reaction solution and in separation circuit thereafter, have a negative impact in this case.
Based on these problems, a kind of molecular-weight average of demand with resulting polyethers be controlled at desired value and can be to the characteristic of reactive behavior, polyethers, handle other performances such as operation and produce dysgenic method.
Summary of the invention
[content of the 1st, the 2nd aspect]
1st, the purpose of the 2nd aspect solid acid catalyst that is that following method is provided and is used for this method: in the manufacturing of polyethers; Through use catalyst performance through the time deterioration catalyzer that is inhibited; Thereby cut down necessary catalytic amount, and can make the method for the little polyethers of MWD steadily in the long term with high conversion.
The method of manufacture of the polyethers of the 1st aspect is in the presence of solid acid catalyst, to make starting compound carry out the method that polyethers is made in polyreaction or condensation reaction; The method is characterized in that; As said solid acid catalyst, using the surface hydroxyl amount is 0.1 μ mol/m
2～2.5 μ mol/m
2, the acid amount below the pKa-5.6 is the above solid acid catalysts of 20 μ mol/g.
And the 1st aspect also provides a kind of solid acid catalyst, and the surface hydroxyl amount of this solid acid catalyst is 0.1 μ mol/m
2～2.5 μ mol/m
2, the acid amount below the pKa-5.6 is more than the 20 μ mol/g.
The method of manufacture of the polyethers of the 2nd aspect is in the presence of solid acid catalyst, to make starting compound carry out the method that polyethers is made in polyreaction or condensation reaction; The method is characterized in that; The solid acid catalyst that will have a surface hydroxyl with can use it for said polyreaction or condensation reaction again with after this surface hydroxyl reaction or the organic cpds beyond interactional, the said polyethers and/or mineral compound contact.
[content of the 3rd aspect]
The purpose of the 3rd aspect is to provide a kind of method of making solid acid catalyst; This method loads on the carrier with extremely even and trickle dispersion state through making metal hydroxides, MOX, makes more than the soda acid amount and the solid acid catalyst of strength of acid narrowly distributing.
The method of manufacture of the solid acid catalyst of the 3rd aspect is the method for manufacture with metal hydroxides and/or the metal oxide supported solid acid catalyst that on carrier, forms; It is characterized in that this method comprises that the sluggish precipitation that utilizes in the carrier pore is in the pore internal burden metal hydroxides of carrier and/or the operation of MOX.
[content of the 4th aspect]
The purpose of the 4th aspect is to provide a kind of method of manufacture of polyethers; It is through in the presence of catalyzer, making the cyclic ether ring-opening polymerization make the method for polyethers, this method can be simply and effectively with the molecular-weight average of resulting polyethers be controlled at desired value and can be to the characteristic of reactive behavior, polyethers, handle other performances such as operation and bring detrimentally affect.
The method of manufacture of the polyethers of the 4th aspect is through in the presence of catalyzer, making the cyclic ether ring-opening polymerization make the method for polyethers; It is characterized in that; As catalyzer; Use the catalyzer obtain as follows: be selected from by at least a element in the group of periodictable the 1st, 2,4,6,8,9,12,13,14,15,16 and 17 group compositions and can make it contain being selected from of not comprising in this solid acid catalyst with itself solid acid catalyst with the cyclic ether ring-opening polymerization by at least a metallic element in the group of periodictable the 3rd, 5,10 and 11 group compositions for containing.
Embodiment
[explanation of the 1st and the 2nd aspect]
The inventor has carried out deep research in order to solve above-mentioned problem; The result finds, through the solid acid catalyst with surface hydroxyl being handled with specific organic cpds and/or mineral compound, the performance that can suppress catalyzer through the time deterioration; Through using said solid acid catalyst through organic cpds and/or mineral compound processing; Can reduce the catalyst consumption that is used to make polyethers, and can dwindle the MWD of polyethers, thereby accomplish the present invention.
Promptly; Have in the method for surface hydroxyl amount of solid acid catalyst of surface hydroxyl in minimizing, comprise the method for at high temperature firing solid acid catalyst, in this case; Because the surface-area of solid acid catalyst reduces with the acid amount together, so the initial performance of catalyzer can worsen significantly.Relative therewith; Under the situation about handling with organic cpds and/or mineral compound according to the present invention; Can only reduce the surface hydroxyl amount; And can not bring bigger detrimentally affect to the surface-area of solid acid catalyst and acid amount, its result can utilize the surface hydroxyl amount is low and sour amount is big solid acid catalyst to make the polyethers of narrow molecular weight distribution steadily in the long term with high conversion.
Promptly; The 1st aspect of the present invention is a kind of method of manufacture of polyethers; It is in the presence of solid acid catalyst, to make starting compound carry out the method that polyethers is made in polyreaction or condensation reaction; The method is characterized in that as said solid acid catalyst, using the surface hydroxyl amount is 0.1 μ mol/m
2～2.5 μ mol/m
2, the acid amount below the pKa-5.6 is the above solid acid catalysts of 20 μ mol/g.
In addition; The 2nd aspect of the present invention is a kind of method of manufacture of polyethers; It is in the presence of solid acid catalyst, to make starting compound carry out the method that polyethers is made in polyreaction or condensation reaction; The method is characterized in that, the solid acid catalyst that will have a surface hydroxyl with can use it for said polyreaction or condensation reaction again with after this surface hydroxyl reaction or the organic cpds beyond interactional, the said polyethers and/or mineral compound contact.
1st, in the 2nd aspect, solid acid catalyst is to be selected from least a comparatively suitable in the group of being made up of the catalyzer and the clay catalyst of MOX O composite metallic oxide catalyst, load.
1st, in the 2nd aspect, it is comparatively suitable that solid acid catalyst contains at least a metallic element that is selected from by in the group of periodictable the 2nd family, the 3rd family, the 4th family, the 5th family, the 8th family, the 10th family, the 11st family, the 13rd family and the 14th group composition.
In the 2nd aspect, organic cpds is that at least a compound that is selected from the group of being made up of alcohols, silanizing agent and carbonates is comparatively suitable.
1st, in the 2nd aspect, preferably make polyethers through making cyclic ether carry out ring-opening polymerization.Especially preferably make polyethers through in the presence of carboxylic acid anhydride and/or carboxylic acid, making cyclic ether carry out ring-opening polymerization.
1st, in the 2nd aspect, solid acid catalyst is made through in the carrier pore, carrying out sluggish precipitation.
According to the 1st, the 2nd aspect; The solid acid catalyst with surface hydroxyl is handled (with its with can contact with the reaction of this surface hydroxyl or organic cpds and/or mineral compound interactional, beyond the polyethers that generated) after; Use it for reaction again; The polyethers of narrow molecular weight distribution can be stably produced, and employed catalytic amount can be subdued.That is, when making polyethers since the performance (catalyst activity) of catalyzer through the time deterioration be inhibited, be used to make catalyst levels thereby can subdue with the polyethers of amount.And, since MWD through the time deterioration also obtained inhibition, so can make the high-quality polyethers of excellents such as thermotolerance.
With the 1st, the polyethers of the narrow molecular weight distribution of manufacturing is that raw material is further made under the situation of urethane etc. aspect the 2nd; The amount of the necessary thinner of viscosity adjustment that is used for facilitating reaction and carries out can be reduced, aspect cost, also favourable effect can be expected with the productivity aspect.
Be elaborated in the face of the embodiment of the 1st, the 2nd aspect down, but the explanation of the constitutive requirements of following record is merely an example (typical example) of the embodiment of the 1st, the 2nd aspect, only otherwise exceed its main points, the 1st, the 2nd aspect does not receive the restriction of these contents.
[solid acid catalyst]
At first, the solid acid catalyst that uses in the 1st, the 2nd aspect is described.
1st, the solid acid catalyst that uses in the 2nd aspect is that the surface hydroxyl amount is 0.1 μ mol/m
2～2.5 μ mol/m
2, the acid amount below the pKa-5.6 is the above solid acid catalysts of 20 μ mol/g, the solid acid catalyst of this low surface hydroxyl amount, peracid amount for example can obtain through solid acid catalyst with surface hydroxyl is contacted with specific organic cpds and/or mineral compound.
(solid acid catalyst) with surface hydroxyl
1st, so-called solid acid catalyst with surface hydroxyl is the solid acid catalyst that has hydroxyl (OH yl) on the surface (comprising carrier pore internal surface) at metal and/or carrier in the 2nd aspect.
More particularly, as solid acid catalyst, can enumerate the zeolites of crystalline structure such as for example having MFI, X, Y with surface hydroxyl; Metal oxide-type such as silicon-dioxide, aluminum oxide, titanium oxide, zirconium white; The complex metal oxides class that two or more oxide-metal combinations such as silica-titania, silica-alumina, silicon-dioxide-zirconium white, aluminum oxide-titanium oxide form; With MOX, gac is that carrier and load have sulfuric acid, heteropolyacid, high fluoride resin (Nafion) etc. to have the compound of acid matter or be different from the loading type acid catalyst class of the MOX of carrier; Clay classes such as layered silicate; Load has clay class of compound with acid matter or metal, MOX etc.
Wherein, use under the situation of complex metal oxides class, loading type acid catalyst class preferred especially silicon-dioxide-zirconium white, silica-alumina, silicon dioxide carried zirconium white, silicon dioxide carried aluminum oxide.Use under the situation of clay classes such as layered silicate, can enumerate kaolinite, green stone etc. usually, the preferred smectite that uses in the green stone.And the clay class is preferably used with the form of the atlapulgite of pickling, especially preferably uses the atlapulgite that obtains after the smectite pickling.
These solid acid catalysts both can use a kind of separately, and it is two or more also can to mix use.
As this method of manufacture with solid acid catalyst of surface hydroxyl; Can use technique known and not receive special restriction; Specifically, can utilize the method for manufacture of record in above-mentioned japanese kokai publication hei 9-241374 communique, the TOHKEMY 2000-327770 communique etc.
Especially; For the solid acid catalyst that uses in the 1st, aspect the 2nd; Preferably in the pore of carrier, carry out sluggish precipitation, metal hydroxides and/or MOX are loaded in the pore of carrier and the solid acid catalyst that obtains with even and trickle dispersion state.
Provide an example that utilizes the method for the solid acid catalyst that the precipitation from homogeneous solution manufactured has surface hydroxyl below.
Sluggish precipitation is implemented as follows, for example, infiltrate metal-salt and the precipitation agent precursor that in solution, produces precipitation agent simultaneously in carrier through chemical reactions such as hydrolysis after, this impregnated carrier is carried out heat treated etc. is generated precipitation agent by the precipitation agent precursor processing.Owing to be sluggish precipitation, therefore importantly metal-salt and precipitation agent precursor form liquid phase, promptly form solution.That is, the dipping solution that will contain metal-salt and precipitation agent precursor is infiltrated up in the carrier, then, handles making by precipitation agent precursor generation precipitation agent.
(1) carrier
For the not special restriction of carrier; Preferable alloy is oxide-based, complex metal oxides class, zeolites, clay class; More preferably silicon-dioxide, aluminum oxide, zirconium white, titanium oxide, silica-alumina, silicon-dioxide-zirconium white, silica-titania, preferred especially silicon-dioxide, aluminum oxide, zirconium white.
As for particle diameter, fine pore and the pore volume of carrier, can be different because of purposes, use form as solid acid catalyst, cannot treat different things as the same.
These carriers both can use a kind of separately, also can share two or more.
(2) metal hydroxides and/or MOX
Be carried on metal hydroxides and/or the not special restriction of MOX on the carrier for above-mentioned that kind; Be generally the oxyhydroxide and/or the oxide compound of the metallic element of periodictable the 2nd～14 family; Be preferably the oxyhydroxide and/or the oxide compound that are selected from by at least a metallic element in the group of periodictable the 2nd family, the 3rd family, the 4th family, the 5th family, the 8th family, the 10th family, the 11st family, the 13rd family and the 14th group composition; More preferably be selected from the oxyhydroxide and/or the oxide compound of at least a metallic element in the group of forming by Ti, Zr, Hf, Nb, Al, Cu, Ni, Ca, Fe and Si, be preferably the oxyhydroxide and/or the oxide compound that are selected from least a metallic element in the group of forming by Ti, Zr, Al, Cu, Ni and Nb especially.
(3) metal-salt
The metal-salt that is used for sluggish precipitation is to generate the above-mentioned metal hydroxides that is carried on the resulting solid acid catalyst and/or the metal-salt of MOX; Therefore; Be generally the salt of the metallic element of above-mentioned periodictable the 2nd～14 family; Be preferably the salt of the metallic element of the 2nd, 3,4,5,8,10,11,13,14 families, more preferably Ti, Zr, Hf, Nb, Al, Si, Cu, Ni, Ca, Fe salt are preferably Ti, Zr, Al, Nb, Cu, Ni salt especially.
For the not special restriction of the kind of salt, preferably nitrate, acetate, vitriol, oxynitrate, muriate, oxychloride, more preferably oxynitrate, oxychloride, vitriol.
That is, as nitrate salt, acetate, vitriol, oxynitrate, muriate, the oxychloride of metal-salt preferred cycle table the 2～14 family's metals, more preferably Zircosol ZN, basic zirconium chloride, zirconium sulfate, titanium chloride, Tai-Ace S 150, niobium oxychloride.
These metal-salts both can use a kind of separately, also can share two or more.
(4) precipitation agent precursor
The precipitation agent precursor is meant, causes that through processing such as in dipping solution, heating hydrolysis or other chemical reactions are to generate the material of precipitation agent.Precipitation agent be meant with dipping solution in reacting metal salt generate the material of precipitate metal hydroxides.In the precipitation agent precursor, be called " alkali precursor " with the sedimentary material of the form of oxyhydroxide or oxide compound through hydrolysis or other chemical reaction with producing the material (that is, in dipping solution, produce alkali, the pH of solution is risen, make metal-salt) of alkali as precipitation agent.
For the not special restriction of precipitation agent precursor that is used to carry out sluggish precipitation, but use the alkali precursor usually.
As the alkali precursor, the amide compound that use urea, tricyanic acid, alkyl substituted ureas, thiocarbamide, alkyl substituting thioureido, constitutes by amine and carboxylic acid etc.Preferred urea, tricyanic acid, the alkyl substituted ureas of using is from being easy to obtain and the consideration of cost aspect preferred especially urea, tricyanic acid.These alkali precursors can use a kind of separately, also can share two or more.
(5) alkaline matter
In dipping solution, not only can add above-mentioned alkali precursor, and the alkaline matter that can in not generating sedimentary scope, add predetermined amount in advance is to improve pH.Through using alkaline matter, consumption, the minimizing that can reduce the alkali precursor generate the deposition time necessary.
For the not special restriction of alkaline matter; Can enumerate oxyhydroxide, carbonate, supercarbonate, phosphoric acid salt, the acetate of basic metal, earth alkali metal and ammonium; Ammonia; Organic amine etc., preferred ammonia, organic amine, the carbonate of ammonium, supercarbonate, phosphoric acid salt, more preferably volatile salt, bicarbonate of ammonia.
These alkaline matters both can use a kind of separately, also can share two or more.
(6) dipping solution
Dipping solution prepares through above-mentioned metal-salt, precipitation agent precursor and the alkaline matter that uses as required are dissolved in the water usually.
To the not special restriction of the concentration of metal-salt in the dipping solution and precipitation agent precursor; As long as can keep dissolved state and can realize to after state the charge capacity that is fit to of carrier; Usually metal salt concentrations is 0.01 weight %～50 weight %, is preferably 0.1 weight %～40 weight %, is preferably 0.5 weight %～30 weight % especially; As after state; The precipitation agent precursor is 0.1～10 times with respect to being enough to make the whole sedimentary theoretical amount of this metal-salt, is preferably 0.2～8 times, is preferably 0.3～5 times especially.
Can suitably use alkaline matter to obtain required pH condition.That is, owing to generate the necessary pH condition of deposition according to the kind of employed metal-salt and precipitation agent precursor or concentration and different, so can use the alkaline matter of necessary amount according to these conditions.
In addition; In order in carrier, to implement sluggish precipitation; Make before the precipitation agent precursor converts the processing of precipitation agent into, needing at least a metal-salt and precipitation agent precursor is liquid phase in dipping solution, is dissolved state; For except this at least a metal-salt and the material the precipitation agent precursor, in dipping solution, exist and all can with random order.
(7) sluggish precipitation
< dipping solution is to the infiltration method of carrier >
For making above-mentioned dipping solution be infiltrated up to the not special restriction of method in the carrier, load to equably on the carrier in order to make metal-salt, preferably implement with the hole completion method.In this case, the volume that is infiltrated up to the dipping solution in the carrier is preferably 60%～120% of carrier pore volume, and more preferably 70%～110%, be preferably 80%～105% especially.If this hypovolia, then dipping solution can not get in the carrier pore equably, and causes uneven homogenize.Conversely, if this hypervolia, then steeping fluid still can cause uneven homogenize attached to the carrier outside surface.
In addition; The charge capacity that loads on the metal-salt on the carrier through infiltration can be selected to measure arbitrarily; But be 0.01 weight %～50 weight % with respect to vehicle weight usually, be preferably 0.05 weight %～40 weight %, further be preferably 0.1 weight %～30 weight %.Charge capacity for the precipitation agent precursor; If being enough to make the whole sedimentary theoretical amount of the metal-salt that is carried on the carrier is,, in 0.1～10 scope, use the precipitation agent precursor usually at 1 o'clock with molar ratio computing; Be preferably 0.2～8 scope, further be preferably 0.3～5 scope.
< sedimentary generation and post-treating method >
Dipping solution is infiltrated up in the carrier; The state that makes the metal-salt that is carried on the carrier and precipitation agent precursor in the carrier pore, keep solution thus; Implement heating in this state and wait the processing that the precipitation agent precursor is converted into precipitation agent, be utilized in the even precipitation agent that produces of carrier inside and convert metal-salt into corresponding metal hydroxides.
Usually use the alkali precursor as the precipitation agent precursor, in the processing that the alkali precursor is converted into alkali, utilize the hydrolysis of the alkali precursor that causes by heating.
As stated; In order in the carrier pore, to implement sluggish precipitation; Need be before carrying out converting the precipitation agent precursor processing of precipitation agent into; Make at least a metal-salt and precipitation agent precursor be solution state, be liquid phase, and except this at least a metal-salt, material the precipitation agent precursor be that any state all can.
In based on the hydrolysis reaction that adds thermal initiation, the alkali precursor is converted under the situation of alkali,, adopt 50 ℃～300 ℃ scope usually, preferably adopt 60 ℃～200 ℃ scope as Heating temperature.Heating temperature is changed in time.If Heating temperature is low excessively, the reaction of precipitation agent then might not take place to be generated by the precipitation agent precursor, or need expend the very long time; If Heating temperature is too high, then the necessary moisture of hydrolysis sometimes may all be removed before the reaction that is generated precipitation agent by the precipitation agent precursor finishes.In order to implement good and stable sluggish precipitation, preferably when the sedimentary reaction of generation finished, the moisture entrapment in the dipping solution of infiltration in carrier is more than 5%, and was more preferably residual more than 10%.
As the fixed bed heating unit; Can there be the carrier of dipping solution to heat to infiltration at the immobilising state of load carriers; But especially under the situation of a large amount of catalyzer of preparation, more preferably the thermopnore device of working load carrier flow, revolving heating unit etc.According to thinking, when heating, occur under the situation of moisture evaporation, make load carriers mobile method that the water evaporation quantity of every particle loading carrier is changed, thereby further increase uniformity.
In addition; If the moisture evaporation during heating is too fast; Then moisture was all removed before the hydrolysis of alkali precursor finishes fully, can not fully carry out the supply of precipitation agent sometimes, therefore it is desirable to usually; By begin heating through deposition formation reaction finish the back, till removing moisture fully, with more than 1 hour, preferred more than 3 hours, further preferred time more than 6 hours carries out removing fully of moisture.
Thereafter; Water, alkali aqueous solution, aqueous acid, organic solvent etc. clean resulting catalyzer as required; After the drying; Under inert gas atmospheres such as nitrogen, argon gas or oxidizing gas atmosphere such as air or dilution oxygen, fire, thus the solid acid catalyst that can obtain having desired performance.Heating firing temperature as this moment is generally 100 ℃～1200 ℃, is preferably 300 ℃～1100 ℃, further is preferably 500 ℃～1000 ℃.Fire through carrying out such heating, can make the catalyst activity and the improved stability of resulting solid acid catalyst.
Wherein, above-mentioned operation not all is necessary operation, as long as finally can access the solid acid catalyst with surface hydroxyl, to the not restriction especially of its manufacturing process.
In addition, metal hydroxides and/or MOX are preferably 0.05 weight %～40 weight % with respect to the charge capacity of carrier in the solid acid catalyst that is obtained by aforesaid method, are preferably 0.1 weight %～30 weight % especially.
(utilizing the treatment process of organic cpds and/or mineral compound)
The organic cpds and/or the mineral compound that are used to handle the solid acid catalyst (solid acid catalyst with surface hydroxyl that preferably obtains through above-mentioned sluggish precipitation) with surface hydroxyl are meant; With the compound of the surface hydroxyl of solid acid catalyst reaction and/or produce interactional compound, can enumerate particularly: alcohols such as methyl alcohol, ethanol; Ethers such as ether; Ester such as methyl acetate, ETHYLE ACETATE class; Acylation agents such as acetate, Acetyl Chloride 98Min., diacetyl oxide; Carbonates such as methylcarbonate, diethyl carbonate; Silanizing agents such as trimethylsilyl acetate, chlorotrimethylsilane, tertiary butyl dimethyl chloride silicomethane, SWS-F 221, trimethyl silane, diethylmethyl silane, triethyl silicane; Metal hydroxides, metal chloride, metal ammonia complex etc.Here, as the metal of metal hydroxides, metal chloride, metal ammonia complex, can enumerate cupric chloride, nickelous chloride, dichloro four ammonia complex copper, dichloro six amminos and close nickel, four ammino copper dinitrates, hexamine nickel dinitrate etc.Wherein preferred alcohols, ester class, acylation agent, carbonates, silanizing agent; More preferably alcohols, carbonates, silanizing agent; Consider special particular methanol, ethanol, methyl acetate, ETHYLE ACETATE, methylcarbonate, diethyl carbonate, trimethylsilyl acetate, trimethyl silane, diethylmethyl silane, triethyl silicane from aspects such as reactivity, unreacted organic cpds with surface hydroxyl are easy to remove.These organic cpds and/or mineral compound both can use a kind of separately, also can mix two or more uses.
To the restriction especially of treatment process that utilizes the solid acid catalyst that organic cpds and/or mineral compound carry out, can adopt in liquid phase, the gas phase any.And, can adopt in batch-type, the flow type any under the situation of liquid phase.
Be under liquid phase, the batch-wise situation; When utilizing organic cpds and/or mineral compound to carry out the processing of solid acid catalyst; Can the solid acid catalyst with surface hydroxyl be added the organic cpds that into is used for handling and/or mineral compound itself or with inert solvent organic cpds and/or mineral compound diluted the solution that forms, implement to handle through heat treated.
In this case; For the consumption of organic cpds and/or mineral compound,, be limited to below 10 times on usually, be limited to down more than 0.1 times with respect to the volume of catalyzer; Preferred upper limit is below 8 times, is limited to more than 0.2 times down, is limited to below 5 times on more preferably, is limited to more than 0.3 times down.If the consumption of organic cpds and/or mineral compound is too much; Then the cost of organic cpds and/or mineral compound increases; The burden of removing unreacted organic cpds and/or mineral compound also becomes greatly, if said consumption is very few, then undressed catalyzer can occur.
For the not special restriction of diluting solvent, use hydrocarbon usually, preferably use pentane, hexane, heptane, benzene,toluene,xylene.These solvents both can use a kind of separately, also can mix two or more uses.Weaker concn is come suitably decision according to handling with the kind of organic cpds and/or mineral compound.
Heating temperature is according to the kind of organic cpds and/or mineral compound and difference, be limited under usually more than 10 ℃, on be limited to below 200 ℃ preferred especially 20 ℃～150 ℃.
For the heat treated time, it is according to the kind of organic cpds and/or mineral compound and difference, and preferred 0.1 hour～20 hours, preferred especially 0.5 hour～15 hours.
And,, can implement the processing that utilizes organic cpds and/or mineral compound to carry out more than twice in order to handle fully.
Under the situation that is liquid phase, flow type; When utilizing organic cpds and/or mineral compound to carry out the processing of solid acid catalyst; Can in having the solid acid catalyst of surface hydroxyl, circulate to handle organic cpds and/or mineral compound are diluted organic cpds and/or the mineral compound that forms, implement processing through heating simultaneously with organic cpds and/or mineral compound itself or with solvent.
For circulation device, can use in fixed bed and the thermopnore any, consider to be easy to more equably catalyzer handled the preferred streams movable bed.
For the not special restriction of solvent, use hydrocarbon usually, preferably use pentane, hexane, heptane, benzene,toluene,xylene.These solvents both can use a kind of separately, also can mix two or more uses.Weaker concn can be come suitably decision according to handling with the kind of organic cpds and/or mineral compound.
To the not special restriction of its flow, preferred SV0.1h
-1～100h
-1, preferred especially SV0.5h
-1～50h
-1
Heating temperature is different because of the kind of organic cpds and/or mineral compound, be limited under usually more than 10 ℃, on be limited to below 300 ℃ preferred especially 20 ℃～200 ℃.
For the heat treated time, it is according to the kind of organic cpds and/or mineral compound and difference, and preferred 0.1 hour～20 hours, preferred especially 0.5 hour～15 hours.
And,, can implement the processing that utilizes organic cpds and/or mineral compound to carry out more than twice in order to handle fully.
Under the situation that is gas phase; When utilizing organic cpds and/or mineral compound to carry out the processing of solid acid catalyst; Can with the organic cpds that is used for handling solid acid catalyst with surface hydroxyl or with inert gas dilution organic cpds with vaporized state in solid acid catalyst circulation and heating simultaneously, implement thus to handle.
Circulation device can use any in fixed bed and the thermopnore, considers to be easy to more equably catalyzer handled the preferred streams movable bed.
As inert dilution gas, use nitrogen, argon gas, carbonic acid gas, helium, air usually, nitrogen, carbonic acid gas, argon gas.These diluentss both can use a kind of separately, also can mix two or more uses.
For the not special restriction of the concentration of organic compound gas in the rare gas element, be generally 0.05 mole of %～100 mole %, be preferably 0.1 mole of %～80 mole %, be preferably 0.1 mole of %～50 mole % especially.
The temperature of heating is different because of the kind of organic cpds, but preferred 10 ℃～400 ℃, preferred especially 20 ℃～300 ℃.
To the not special restriction of flow, preferred SV10h
-1～5000h
-1, preferred especially SV30h
-1～4000h
-1
The heat treated time is also different because of organic kind, but preferred 0.1 hour～20 hours, preferred especially 0.5 hour～15 hours.
And,, can implement the processing that utilizes organic cpds and/or mineral compound to carry out more than twice in order to handle fully.
In addition, in the processing of solid acid catalyst in used organic cpds and/or mineral compound and the solvent if contain moisture, can make the catalyst performance deterioration on the contrary.Therefore, organic cpds and/or mineral compound and the solvent that is used for the processing of solid acid catalyst preferably utilizes dewatering agent equal altitudes ground to remove moisture in advance and is processed into water cut and is below the 10 weight %, is preferably below the 5 weight %, is preferably below the 2 weight % especially.
Wherein, Organic cpds that is used to handle and/or mineral compound can not decompose because of moisture; And can the solid acid catalyst after handling be fired under the temperature more than 300 ℃ before being used to react; The surface hydroxyl amount of the solid acid catalyst after firing remains under the situation below the 2.5 μ mol/g, does not also have problems even contain moisture.
< through the solid acid catalyst of organic cpds and/or mineral compound processing >
According to thinking, the solid acid catalyst through above-mentioned operation manufacturing has characteristic as follows.
Promptly; Can think,, can improve the hydrophobicity of catalyst surface through being combined with the hydrophobic group that is derived from organic cpds and/or mineral compound on the surface hydroxyl; Inhibition may bring the influence of dysgenic moisture to catalyzer, suppress catalyst performance through the time deterioration.And, owing to be combined with hydrophobic group on reactive surface hydroxyl having, thereby think that can suppress polyethers as reaction product combines with surface hydroxyl or interact, the inhibition catalyst performance through the time deterioration.
In addition; For solid acid catalyst through organic cpds and/or mineral compound processing; As long as the surface hydroxyl amount remains on below the 2.5 μ mol/g; Also can be before being used to react fire, to remove excess treating reagent and moisture the temperature more than 300 ℃, for example 300 ℃～1000 ℃.
Thus; Compare with the solid acid catalyst that does not carry out organic cpds and/or mineral compound processing with prior art for preparing; Through the catalyst performance of the solid acid catalyst handled like this through the time deterioration, catalyst activity through the time deterioration and resulting polyethers MWD through the time worsen and be inhibited, can make the polyethers of narrow molecular weight distribution with a spot of catalyzer steadily in the long term.
(solid acid catalyst that is used to react)
Being used for the polyreaction of starting compound or the solid acid catalyst of condensation reaction is that the surface hydroxyl amount is 0.1 μ mol/m
2～2.5 μ mol/m
2, the acid amount below the pKa-5.6 is the above solid acid catalysts of 20 μ mol/g.
If the surface hydroxyl amount of solid acid catalyst surpasses 2.5 μ mol/m
2, then can't obtain polyethers as the narrow molecular weight distribution of the object of the invention.
And,, thereby when making polyethers, need use a large amount of catalyzer if the acid amount below the pKa-5.6 of solid acid catalyst then can not obtain sufficient polymerization activity less than 20 μ mol/g.
The surface hydroxyl amount of solid acid catalyst is preferably 0.1 μ mol/m
2～2.0 μ mol/m
2, and the acid amount below the pKa-5.6 is preferably more than the 40 μ mol/g, further is preferably more than the 60 μ mol/g.
In addition, the acid amount below the surface hydroxyl amount of solid acid catalyst and the pKa-5.6 for example can be measured as follows.
[surface hydroxyl amount]
0.7g takes a sample in U word pipe; Under with the condition of the speed of 40cc/min circulation high purity Ar in 300 ℃ of dryings 1 hour; Behind the naturally cooling, with under the atmosphere state of contact do not taking off U word pipe, be transferred in the airtight insulation blocking cover (glove bag) of dry gas.
Erlenmeyer flask to putting into airtight insulation blocking cover in advance adds sample, again to wherein adding the 20cc dry toluene.Erlenmeyer flask is installed in speed with the 80cc/min N that circulated
2The titration experiments device on.In the Ar glove box, the ethereal solution of 5cc 1.5M lithium methide-lithiumbromide complex compound is drawn onto in the plastic injector, with rubber seal under the state of needle point with its taking-up, be injected in the Erlenmeyer flask through barrier film.
Capture 10 minutes sweeping gas with capturing bag, with the quantitative methane concentration of GC.Purge gas flow detects with accurate film under meter.Come the surface hydroxyl amount of the catalyzer of Units of Account weight by the methane content of obtaining through methane concentration and purge gas flow that is produced.
Use the HM Mode1-1201 type of Mountech society manufacturing, utilize the surface-area of the catalyzer of nitrogen absorption BET1 point method analytical unit weight, calculate the surface hydroxyl amount of the per surface area of catalyzer thus.
[the acid amount below the pKa-5.6]
With catalyzer in 200 ℃ of vacuum-dryings 3 hours, weighing catalyzer in the glove box under the nitrogen atmosphere.Add 2ml toluene, be installed on the UV determinator, add 0.2 weight % benzylidene acetophenone (pKa≤-5.6 usefulness)/toluene solution 1ml as indicator.As the n-butylamine of titration reagent use 0.01mol/L, calculate the acid amount below the pKa-5.6 by the n-butylamine amount that is dripped till disappearing until UV peak with acid sites (sour point) bonded benzylidene acetophenone.
[method of manufacture of polyethers]
Be 0.1 μ mol/m in the face of use through method of manufacture, the use surface hydroxyl amount of the polyethers of the 2nd aspect of the solid acid catalyst of above-mentioned organic cpds and/or mineral compound processing down
2～2.5 μ mol/m
2, to be the above solid acid catalyst of 20 μ mol/g describe as the method for manufacture of the polyethers of the 1st aspect of catalyst for polymerization the acid amount below the pKa-5.6.
Restriction especially of method of manufacture to the polyethers of the 1st, the 2nd aspect; But preferably carry out, more preferably through being that reaction raw materials makes it carry out the method that ring-opening polymerization is made with the ring-type ethers through the ring-opening polymerization of ring-type ethers or the dehydration condensation of polyvalent alcohol.
Make under the situation of polyethers with the ring-opening polymerization of ring-type ethers, as the cyclic ether as reaction raw materials, the formation carbonatoms that can enumerate ring is 3～10 cyclic ether, and, can use with substituted cyclic ethers such as alkyl, halogen radical, acyl groups.Specifically, can use THF, trimethylene oxide, oxepane, 1,4-dioxane, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran etc.And, any polymerization in the homopolymerization that can only use a kind of ring-type ethers and the copolymerization of using two or more ring-type ethers.
As catalyzer, using as above solid acid catalyst or the surface hydroxyl amount handled through organic cpds and/or mineral compound is 0.1 μ mol/m
2～2.5 μ mol/m
2, the acid amount below the pKa-5.6 is in the above solid acid catalyst of 20 μ mol/g one or more.
Consider that from the aspect of control molecular weight the ring-opening polymerization of cyclic ether preferably carries out in the presence of carboxylic acid anhydride and/or carboxylic acid.As carboxylic acid anhydride and/or carboxylic acid, generally use aliphatics or aromatic carboxylic acid anhydride and/or carboxylic acid, preferred carboxylic acid anhydride and/or the carboxylic acid that use with 2～8 carbon atoms with 2～12 carbon atoms.These carboxylic acid anhydride and/or carboxylic acid both can use a kind of separately, also can share two or more.With respect to cyclic ether, carboxylic acid anhydride and/or carboxylic acid add in the scope of 0.01～1.0 (mol ratio) usually and get final product.
Can in reaction, use inert solvent during polyreaction.As this solvent, use the divided ring polyreaction to be in inert aliphatic hydrocarbon, the aromatic hydrocarbon etc. one or more usually.
Reaction formation uses the general form of using such as grooved, tower, can be any of batch mode, continuous mode.Following method etc. is for example arranged: cyclic ether, catalyzer, carboxylic acid anhydride and/or carboxylic acid are under agitation fed intake carry out polymeric method (batch mode); In containing the reactor drum of catalyzer, supply with cyclic ether, carboxylic acid anhydride and/or carboxylic acid and continuous method (continuous mode) of extracting reaction solution out etc. continuously.Consider preferred continuous mode from the aspect of productivity.
The consumption of solid acid catalyst depends on its kind, not special the qualification, but for example in the batch-type reactor drum, if catalytic amount is very few, then polymerization velocity is slack-off, conversely if too much, then be difficult to remove heat of polymerization.And, because the slurry concentration of reaction system uprises, cause stirring difficulty, and be easy to go wrong in the separatory of catalyzer and reaction solution after polyreaction finishes.Therefore, for catalyst consumption, can be generally 0.001～50 times of weight with respect to liquid phase under the condition of the reaction form of considering batch reactions, circulation reaction, be preferably in the scope of 0.01～20 times of weight and select.Wherein, under the situation of circulation reaction, catalyst consumption is represented the amount with respect to the catalyzer of liquid phase feed rate of time per unit.
Temperature of reaction is generally 0 ℃～200 ℃, is preferably 10 ℃～80 ℃.
Reaction pressure is that reaction system can keep the pressure of liquid phase to get final product, usually from normal pressure～10MPa, preferably select from the pressure range of normal pressure～5MPa.
To not special qualification of reaction times, consider itself and catalytic amount the two, consider yield, economy, the reaction times is 0.1 hour～20 hours scope, is preferably 0.5 hour～15 hours scope.The said here reaction times is meant, in batch mode, plays the time till reaction finishes to begin to cool down when rising to temperature of reaction by temperature; In continuous mode, the residence time of liquid in reactor drum formed in reaction.
The MWD of the polyethers that is generated depends on the kind of starting compound, but according to the present invention, and solid acid catalyst or the surface hydroxyl amount of utilizing organic cpds and/or mineral compound to handle in use are 0.1 μ mol/m
2～2.5 μ mol/m
2, the acid amount below the pKa-5.6 is under the situation of the above solid acid catalyst of the 20 μ mol/g ring-opening polymerization that carries out THF (THF); Can obtain number-average molecular weight (Mn) is 200～80; 000, the polyethers of low～middle molecular weight of about 200～40,000 particularly.And then the polyethers that can easily produce narrow molecular weight distribution also is one of characteristic.Promptly; The Mw/Mn of the polyethers that industrial requirement is bigger is 1.3～2.5; Through utilizing solid acid catalyst of the present invention; Can access Mw/Mn less than 3, for example Mw/Mn is 1.1～3.0 polytetramethylene ether diol (PTMG), particularly through selecting optimum condition of the present invention for use, can also obtain Mw/Mn and be about 1.4～1.7 the very narrow polyethers of MWD.And according to the present invention, the yield that can make product is more than 15%, is preferably more than 20%, further is more than 25%.
And then, since catalyst activity through the time deterioration less, even react the state that also can keep high conversion for a long time.
The polyethers that is produced by the 1st, the 2nd aspect can be used for purposes such as spandex fiber, thermoplastic polyester elastomer, TPUE, coating material.
[embodiment and comparative example]
Enumerate synthetic example, embodiment and comparative example below, to the further explanation particularly of the 1st, the 2nd aspect, but following embodiment does not limit the scope of the 1st, the 2nd aspect.
In addition, in the content below, the GPC (GPC) below the transformation efficiency of polytetramethylene ether diol acetic ester (PTME), number-average molecular weight (Mn), MWD (Mw/Mn) are utilized obtains.
The GPC device: Tosoh society makes GPC 8220
Post: TSK-GEL GMHHR-M (30cm) * 4
Detection method: RI
Column temperature: 40 ℃
Mobile phase: THF
Flow velocity: 1ml/min
Sample IR: 500 μ L
Sample concentration: the concentration that is adjusted to polyethers is about 0.5 weight %
In addition, the surface hydroxyl amount of solid acid catalyst is measured with the acid amount as follows.
[surface hydroxyl amount]
The 0.7g that in U word pipe, takes a sample in 300 ℃ of dryings 1 hour, behind the naturally cooling, with under the atmosphere state of contact is not taking off U word pipe under with the condition of the speed circulation high purity Ar of 40cc/min, is transferred in the airtight insulation blocking cover of dry gas.
Erlenmeyer flask putting into airtight insulation blocking cover in advance adds sample, again to wherein adding the 20cc dry toluene.Erlenmeyer flask is installed in speed with the 80cc/min N that circulated
2The titration experiments device on.In the Ar glove box, the ethereal solution of 5cc 1.5M lithium methide-lithiumbromide complex compound is drawn onto in the plastic injector, with rubber seal under the state of needle point with its taking-up, be injected in the Erlenmeyer flask through barrier film.
Capture 10 minutes sweeping gas with capturing bag, with the quantitative methane concentration of GC.Purge gas flow detects with accurate film under meter.Come the surface hydroxyl amount of the catalyzer of Units of Account weight by the methane content of obtaining through methane concentration and purge gas flow that is produced.
Use the HM Mode1-1201 type of Mountech society manufacturing, utilize the surface-area of the catalyzer of nitrogen absorption BET1 point method analytical unit weight, calculate the surface hydroxyl amount of the per surface area of catalyzer thus.
[the acid amount below the pKa-5.6]
With catalyzer in 200 ℃ of vacuum-dryings 3 hours, weighing catalyzer in the glove box under the nitrogen atmosphere.Add 2ml toluene, be installed on the UV determinator, add 0.2 weight % benzylidene acetophenone (pKa≤-5.6 usefulness)/toluene solution 1ml as indicator.As the n-butylamine of titration reagent use 0.01mol/L, calculate the acid amount below the pKa-5.6 by the n-butylamine amount that is dripped till disappearing until UV peak with acid sites bonded benzylidene acetophenone.
< preparation>with solid acid catalyst of surface hydroxyl
The synthetic routine 1-1 of catalyzer:
(new Japanese metallochemistry society makes ZrO at the 89.66g Zircosol ZN aqueous solution
2Conversion concentration is 18.12 weight %) middle 18.72g de-salted water and the uniform mixing of adding.To wherein adding 11.84g urea uniform mixing, the preparation dipping solution.In this solution, add 80g SiO
2(Silysia of Fuji makes, CARiACT Q15, particle diameter 75 μ m～500 μ m; Median size 200 μ m, pore volume 1.16ml/g, average fine pore 15nm); Vibrate and mixed in about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).
In its 500ml pyriform flask of packing into, jointing and the bend pipe that is plugged with glass wool connect TM in measurement section on flask top.With anchor clamps flask be fixed on the turning axle of rotating dryer on thereafter.Speed rotation turning axle with 10rpm is set at 105 ℃ with the drying machine temperature, carries out 6 hours heating.At this moment, confirm the moisture entrapment 90% in the dipping solution through weight change.Then, unload the bend pipe that is plugged with glass wool on top after, the drying machine temperature is set at 120 ℃, carry out 16 hours heating.
Then, unload the joint on top after, the drying machine temperature is set at 140 ℃, carry out 4 hours heating, moisture is almost completely removed.After 4 hours, stop heating, rotation, take out catalyzer.
Catalyzer is transferred in the beaker of 500ml and naturally cools to room temperature, add the de-salted water of about 300ml then, carry out about 10 minutes suspension cleaning.Next, behind the filtering catalyst, be transferred to once more in the beaker of 500ml, add that the 30g Ammonium Bicarbonate, Food Grade is dissolved in the solution that obtains in the de-salted water of 300ml, carry out about 10 minutes suspension and clean.Next, behind the filtering catalyst, be transferred to once more in the beaker of 500ml, add the 300ml de-salted water, carry out about 10 minutes suspension and clean.After 2 cleanings of this de-salted water repetition, air-dry catalyzer 120 ℃ of dry nights in drying machine, carries out firing in 2 hours in 900 ℃ under airiness then.
Resulting solid acid catalyst is made as " catalyzer 1 ".Obtain through calculating according to the composition of steeping fluid that the zirconic charge capacity with respect to the catalyzer total amount is 16.9 weight % in the catalyzer 1.
And the surface hydroxyl amount of catalyzer 1 is 2.6 μ mol/m
2, the acid amount below the pKa-5.6 is 110 μ mol/g.
The synthetic routine 1-2 of catalyzer
(new Japanese metallochemistry society makes ZrO at the 89.66g Zircosol ZN aqueous solution
2Conversion concentration is 18.12 weight %) in add the 0.44g de-salted water and process homogeneous solution; After wherein little by little add 25 weight % ammonium carbonate solution 26.94g, processing homogeneous solution, little by little add 7.94g urea under stirring; Process dipping solution, in this solution, add 80g SiO
2(Silysia of Fuji makes, CARiACT Q30, particle diameter 75 μ m～500 μ m; Median size 200 μ m, pore volume 1.21ml/g, average fine pore 30nm); Vibrate and mixed in about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).
In its 500ml pyriform flask of packing into, jointing and the bend pipe that is plugged with glass wool connect TM in measurement section on flask top.With anchor clamps flask be fixed on the turning axle of rotating dryer on thereafter.Speed rotation turning axle with 10rpm is set at 105 ℃ with the drying machine temperature, carries out 2 hours heating.Then, unload the bend pipe that is plugged with glass wool on top after, the drying machine temperature is set at 120 ℃, carry out 16 hours heating.
Then, unload the joint on top after, the drying machine temperature is set at 140 ℃, carry out 4 hours heating, moisture is removed fully.After 4 hours, stop heating, rotation, take out catalyzer.
Catalyzer is transferred in the beaker of 500ml and naturally cools to room temperature, add the de-salted water of about 300ml then, carry out about 10 minutes suspension cleaning.Next, behind the filtering catalyst, be transferred to once more in the beaker of 500ml, add that the 30g Ammonium Bicarbonate, Food Grade is dissolved in the solution that obtains in the de-salted water of 300ml, carry out about 10 minutes suspension and clean.Next, behind the filtering catalyst, be transferred to once more in the beaker of 500ml, add the 300ml de-salted water, carry out about 10 minutes suspension and clean.After 2 cleanings of this de-salted water repetition, air-dry catalyzer 120 ℃ of dry nights in drying machine, carries out firing in 2 hours in 900 ℃ under the circulation of air then.
Resulting solid acid catalyst is made as " catalyzer 2 ".Obtain through calculating according to the composition of steeping fluid that the zirconic charge capacity with respect to the catalyzer total amount is 16.9 weight % in the catalyzer 2.
And the surface hydroxyl amount of catalyzer 2 is 3.4 μ mol/m
2, the acid amount below the pKa-5.6 is 100 μ mol/g.
The synthetic routine 1-3 of catalyzer
(new Japanese metallochemistry society makes ZrO at the 88.01g Zircosol ZN aqueous solution
2Conversion concentration is 18.12 weight %) middle 26.13g de-salted water and the uniform mixing of adding.To wherein adding 11.84g urea uniform mixing, the preparation dipping solution.In this solution, add 80g SiO
2(Silysia of Fuji make, CARiACT Q30) vibrates and mixed in about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).
In its 500ml pyriform flask of packing into, jointing and the bend pipe that is plugged with glass wool connect TM in measurement section on flask top.With anchor clamps flask be fixed on the turning axle of rotating dryer on thereafter.Speed rotation turning axle with 10rpm is set at 105 ℃ with the drying machine temperature, carries out 2 hours heating.Then, unload the bend pipe that is plugged with glass wool on top after, the drying machine temperature is set at 120 ℃, carry out 16 hours heating.
Then, unload the joint on top after, the drying machine temperature is set at 140 ℃, carry out 4 hours heating, moisture is removed fully.After 4 hours, stop heating, rotation, take out catalyzer.
Catalyzer is transferred in the beaker of 500ml and naturally cools to room temperature, add the de-salted water of about 300ml then, carry out about 10 minutes suspension cleaning.Next, behind the filtering catalyst, be transferred to once more in the beaker of 500ml, add that the 30g Ammonium Bicarbonate, Food Grade is dissolved in the solution that obtains in the de-salted water of 300ml, carry out about 10 minutes suspension and clean.Next, behind the filtering catalyst, be transferred to once more in the beaker of 500ml, add the 300ml de-salted water, carry out about 10 minutes suspension and clean.After 2 cleanings of this de-salted water repetition, air-dry catalyzer 120 ℃ of dry nights in drying machine, carries out firing in 2 hours in 900 ℃ under the circulation of air then.
Resulting solid acid catalyst is made as " catalyzer 3 ".Obtain through calculating according to the composition of steeping fluid that the zirconic charge capacity with respect to the catalyzer total amount is 16.9 weight % in the catalyzer 3.
And the surface hydroxyl amount of catalyzer 3 is 3.3 μ mol/m
2, the acid amount below the pKa-5.6 is 100 μ mol/g.
The synthetic routine 1-4 of catalyzer
The Tonsil OptimumFF that will make as the Sued Chemie society of clay (atlapulgite) catalyzer fired 1 hour in 400 ℃ under airiness, resulting solid acid catalyst was called " catalyzer 4 ".
The surface hydroxyl amount of this catalyzer 4 is 3.5 μ mol/m
2, the acid amount below the pKa-5.6 is 190 μ mol/g.
<utilizing the processing of the solid acid catalyst that organic cpds and/or mineral compound carry out and the manufacturing of polyethers >
Embodiment 1-1
[utilizing the processing of the solid acid catalyst that organic cpds and/or mineral compound carry out]
The 100ml ethanol (water cut 50ppm) and 98.3g (832.2mmol) diethyl carbonate (water cut 50ppm) that have carried out dewatering with molecular sieve 3a are in advance being mixed in the 500ml flask that has reflux condensing tube under the nitrogen atmosphere.Wherein, under agitation in above-mentioned mixed solution, behind the interpolation 50g catalyzer 1, in oil bath, heat, refluxed 1 hour.Behind the naturally cooling, reflux condensing tube is replaced by still head, in oil bath, heats, slowly heat up, remove ethanol and diethyl carbonate, and then under the nitrogen circulation, in 140 ℃ oil bath, handled 4 hours in 90 ℃～140 ℃ distillations.Behind the naturally cooling, under nitrogen atmosphere, be kept in the encloses container, process to estimate and use catalyzer.
It is 1.5 μ mol/m that the surface hydroxyl amount of catalyzer is used in this evaluation
2, the acid amount below the pKa-5.6 is 110 μ mol/g.
[polyethers manufacturing reaction evaluating]
Catalyzer is used in this evaluation of 22g of in volume is the circulation reaction unit of 520ml, packing into.Mixing solutions (weight ratio is: THF258.6, diacetyl oxide 29.3, acetate 1) with the flow of 87.4ml/h circulation THF, diacetyl oxide, acetate is heated to 35 ℃.Constant time abstraction reaction liquid has at interval carried out the mensuration of yield, number-average molecular weight (Mn) and MWD (Mw/Mn) through GPC.
The transformation efficiency at initial stage is 34.2%, the Mn at initial stage is 2257, the Mw/Mn at initial stage is 1.81, the transformation efficiency behind the reaction 162.5h be 28.3% (with respect to the initial stage, transformation efficiency is 83% relatively), Mn=2232, Mw/Mn be 1.80 (with preliminary phase than worsening-0.01).
Comparative example 1-1
Directly use the above-mentioned catalyzer 1 of 22g, likewise carry out polyethers with embodiment 1-1 and make reaction evaluating.
The transformation efficiency at initial stage is 39.7%, the Mn at initial stage is 1851, the Mw/Mn at initial stage is 1.82, the transformation efficiency behind the reaction 161.5h be 28.2% (with respect to the initial stage, transformation efficiency is 71% relatively), Mn=1813, Mw/Mn be 1.85 (with preliminary phase than worsening+0.03).
Embodiment 1-2
The above-mentioned catalyzer 2 of 40g is filled into fixed bed circulation treatment unit, with the flow circulation nitrogen of 0.8L/min.Then, except circulation nitrogen, also with the flow of 32mg/min with the gaseous phase methyl alcohol (water cut 50ppm) that goes into circulation, be heated to 100 ℃ and kept 5 hours.Stop the circulation of methyl alcohol after 5 hours, the nitrogen that only circulates kept 4 hours.Behind the naturally cooling, under nitrogen atmosphere, be kept in the encloses container, process to estimate and use catalyzer.
It is 2.0 μ mol/m that the surface hydroxyl amount of catalyzer is used in this evaluation
2, the acid amount below the pKa-5.6 is 90 μ mol/g.
Use 22g to estimate and use catalyzer, likewise carry out polyethers with embodiment 1-1 and make reaction evaluating.
The transformation efficiency at initial stage is 34.4%, the Mn at initial stage is 2399, the Mw/Mn at initial stage is 1.76, the transformation efficiency behind the reaction 162.0h be 25.3% (with respect to the initial stage, transformation efficiency is 74% relatively), Mn=2322, Mw/Mn be 1.77 (with preliminary phase than worsening+0.01).
Embodiment 1-3
The above-mentioned catalyzer 2 of 80g is filled into thermopnore circulation treatment unit, with the flow circulation nitrogen of 1.6L/min.Then, except circulation nitrogen, also with the flow of 88mg/min with the gaseous phase trimethylsilyl acetate that goes into circulation, be heated to 100 ℃ and kept 5 hours.Stop the circulation of trimethylsilyl acetate after 5 hours, be heated to 200 ℃, the nitrogen that only circulates kept 4 hours.Behind the naturally cooling, under nitrogen atmosphere, be kept in the encloses container, process to estimate and use catalyzer.
It is 1.4 μ mol/m that the surface hydroxyl amount of catalyzer is used in this evaluation
2, the acid amount below the pKa-5.6 is 100 μ mol/g.
Use 22g to estimate and use catalyzer, likewise carry out polyethers with embodiment 1-1 and make reaction evaluating.
The transformation efficiency at initial stage is 33.0%, the Mn at initial stage is 3090, the Mw/Mn at initial stage is 1.80, the transformation efficiency behind the reaction 162.0h be 27.0% (with respect to the initial stage, transformation efficiency is 82% relatively), Mn=2967, Mw/Mn be 1.78 (with preliminary phase than worsening-0.02).
Comparative example 1-2
Directly use the above-mentioned catalyzer 2 of 22g, likewise carry out polyethers with embodiment 1-1 and make reaction evaluating.
The transformation efficiency at initial stage is 32.0%, the Mn at initial stage is 2287, the Mw/Mn at initial stage is 1.76, the transformation efficiency behind the reaction 163.7h be 23.5% (with respect to the initial stage, transformation efficiency is 73% relatively), Mn=2282, Mw/Mn be 1.81 (with preliminary phase than worsening+0.05).
Embodiment 1-4
The above-mentioned catalyzer 3 of 80g is filled into thermopnore circulation treatment unit, with the flow circulation nitrogen of 1.6L/min.After being heated to 100 ℃, except circulation nitrogen, also with the flow of 88mg/min with the gaseous phase trimethylsilyl acetate (below the water cut 10ppm) that goes into circulation, and kept 5 hours.Stop the circulation of trimethylsilyl acetate after 5 hours, be heated to 200 ℃, the nitrogen that only circulates kept 4 hours.Behind the naturally cooling, under nitrogen atmosphere, be kept in the encloses container, process to estimate and use catalyzer.
It is 1.6 μ mol/m that the surface hydroxyl amount of catalyzer is used in this evaluation
2, the acid amount below the pKa-5.6 is 100 μ mol/g.
Use 22g to estimate and use catalyzer, likewise carry out polyethers with embodiment 1-1 and make reaction evaluating.
The transformation efficiency at initial stage is 28.8%, the Mn at initial stage is 2022, the Mw/Mn at initial stage is 1.64, the transformation efficiency behind the reaction 142.5h be 23.5% (with respect to the initial stage, transformation efficiency is 82% relatively), Mn=1890, Mw/Mn be 1.66 (with preliminary phase than worsening+0.02).
Embodiment 1-5
The above-mentioned catalyzer 3 of 80g is filled into thermopnore circulation treatment unit, with the flow circulation nitrogen of 1.6L/min.After being heated to 100 ℃, except circulation nitrogen, also with the flow of 68mg/min with the gaseous phase diethylmethyl silane (below the water cut 10ppm) that goes into circulation, and kept 5 hours.Stop the circulation of diethylmethyl silane after 5 hours, be heated to 200 ℃, the nitrogen that only circulates kept 4 hours.Behind the naturally cooling, under nitrogen atmosphere, be kept in the encloses container, process to estimate and use catalyzer.
It is 2.0 μ mol/m that the surface hydroxyl amount of catalyzer is used in this evaluation
2, the acid amount below the pKa-5.6 is 100 μ mol/g.
Use 22g to estimate and use catalyzer, likewise carry out polyethers with embodiment 1-1 and make reaction evaluating.
The transformation efficiency at initial stage is 31.4%, the Mn at initial stage is 1746, the Mw/Mn at initial stage is 1.64, the transformation efficiency behind the reaction 139.7h be 25.3% (with respect to the initial stage, transformation efficiency is 81% relatively), Mn=1797, Mw/Mn be 1.66 (with preliminary phase than worsening+0.02).
Embodiment 1-6
The above-mentioned catalyzer 3 of 80g is filled into thermopnore circulation treatment unit, with the flow circulation nitrogen of 1.6L/min.After being heated to 140 ℃, except circulation nitrogen, also with the flow of 23mg/min with the gaseous phase diethylmethyl silane (below the water cut 10ppm) that goes into circulation, and kept 5 hours.Stop the circulation of diethylmethyl silane after 5 hours, be heated to 200 ℃, the nitrogen that only circulates kept 4 hours.Behind the naturally cooling, under nitrogen atmosphere, be kept in the encloses container, process to estimate and use catalyzer.
It is 2.0 μ mol/m that the surface hydroxyl amount of catalyzer is used in this evaluation
2, the acid amount below the pKa-5.6 is 100 μ mol/g.
Use 22g to estimate and use catalyzer, likewise carry out polyethers with embodiment 1-1 and make reaction evaluating.
The transformation efficiency at initial stage is 33.1%, the Mn at initial stage is 2090, the Mw/Mn at initial stage is 1.66, the transformation efficiency behind the reaction 161.7h be 27.4% (with respect to the initial stage, transformation efficiency is 83% relatively), Mn=2108, Mw/Mn be 1.68 (with preliminary phase than worsening+0.02).
Comparative example 1-3
Directly use the above-mentioned catalyzer 3 of 22g, likewise carry out polyethers with embodiment 1-1 and make reaction evaluating.
The transformation efficiency at initial stage is 29.6%, the Mn at initial stage is 1582, the Mw/Mn at initial stage is 1.68, the transformation efficiency behind the reaction 139.5h be 23.0% (with respect to the initial stage, transformation efficiency is 78% relatively), Mn=1567, Mw/Mn be 1.74 (with preliminary phase than worsening+0.06).
Embodiment 1-7
The above-mentioned catalyzer 4 of 80g is filled into thermopnore circulation treatment unit, with the flow circulation nitrogen of 1.6L/min.Then, except circulation nitrogen, also with the flow of 88mg/min with the gaseous phase trimethylsilyl acetate that goes into circulation, be heated to 100 ℃ and kept 5 hours.Stop the circulation of trimethylsilyl acetate after 5 hours, be heated to 200 ℃, the nitrogen that only circulates kept 4 hours.Behind the naturally cooling, under nitrogen atmosphere, be kept in the encloses container, process to estimate and use catalyzer.
It is 2.4 μ mol/m that the surface hydroxyl amount of catalyzer is used in this evaluation
2, the acid amount below the pKa-5.6 is 190 μ mol/g.
Use 22g to estimate and use catalyzer, likewise carry out polyethers with embodiment 1-1 and make reaction evaluating.
The transformation efficiency at initial stage is 29.0%, the Mn at initial stage is 3500, the Mw/Mn at initial stage is 1.84, the transformation efficiency behind the reaction 165.4h be 12.2% (with respect to the initial stage, transformation efficiency is 42% relatively), Mn=3470, Mw/Mn be 1.85 (with preliminary phase than worsening+0.01).
Comparative example 1-4
Directly use the above-mentioned catalyzer 4 of 22g, likewise carry out polyethers with embodiment 1-1 and make reaction evaluating.
The transformation efficiency at initial stage is 28.1%, the Mn at initial stage is 2668, the Mw/Mn at initial stage is 1.85, the transformation efficiency behind the reaction 165.4h be 10.1% (with respect to the initial stage, transformation efficiency is 36% relatively), Mn=2794, Mw/Mn be 2.00 (with preliminary phase than worsening+0.15).
Above-mentioned evaluation result provides with showing to gather among the 1-2 in below table 1-1.
[table 1-1]
[table 1-2]
Can know by table 1-1, table 1-2; Through handling solid acid catalyst with organic cpds and/or mineral compound in advance; Can obtain the solid acid catalyst of low surface hydroxyl amount and peracid amount, through use this solid acid catalyst can prevent transformation efficiency through the time reduce, and; Can also prevent resulting polyethers MWD (Mw/Mn) through the time worsen, can obtain the polyethers of narrow molecular weight distribution.
[explanation of the 3rd aspect]
The inventor finds; Through in the pore of carrier, carrying out sluggish precipitation (it is from uniform solution, to generate sedimentary reaction); Can metal hydroxides and/or MOX be loaded in the carrier with even and trickle dispersion state, thereby accomplish the 3rd aspect of the present invention.
According to thinking; Under the situation of sluggish precipitation; The precipitation agent (for example alkali) that is used for metallic salt is processed metal hydroxides can generate in carrier pore inside equably, thereby the concentration difference of the metal hydroxides on the different positions of carrier inside becomes minimum, can generate trickle and uniform aggegation and the big aggegation of metal hydroxides can in carrier, not occur; Its result can access more than the soda acid amount and the solid acid catalyst of strength of acid narrowly distributing.
The main points of the 3rd aspect are a kind of method of manufacture of solid acid catalyst; It is the method for manufacture with metal hydroxides and/or the metal oxide supported solid acid catalyst that on carrier, forms; It is characterized in that this method comprises that the sluggish precipitation that utilizes in the carrier pore is in the pore internal burden metal hydroxides of carrier and/or the operation of MOX.
In the 3rd aspect, said sluggish precipitation is to have utilized the sluggish precipitation of precipitation agent precursor comparatively suitable.
This precipitation agent precursor is that the alkali precursor is comparatively suitable.
Metal hydroxides and/or MOX be selected from by the oxyhydroxide and/or the oxide compound of at least a metallic element in the group of periodictable the 3rd family, the 4th family, the 5th family, the 13rd family and the 14th group composition comparatively suitable.
The alkali precursor is that urea is comparatively suitable.
According to the 3rd aspect; Through in the pore of carrier, carrying out sluggish precipitation (it is from uniform solution, to generate sedimentary reaction); Can metal hydroxides and/or MOX be loaded in the carrier with even and trickle dispersion state; Its result can access that the soda acid amount is many, the solid acid catalyst of strength of acid narrowly distributing.
Through utilizing such solid acid catalyst, can be in the ring-opening polymerization of for example THF make the polyethers of narrow molecular weight distribution with high conversion.
Be elaborated in the face of the embodiment of the 3rd aspect down, but the explanation of the constitutive requirements of following record is merely an example (typical example) of the embodiment of the 3rd aspect, only otherwise exceed its main points, the 3rd aspect does not receive the restriction of these contents.
Solid acid catalyst with the method manufacturing of the 3rd aspect is through in the pore of carrier, carrying out sluggish precipitation metal hydroxides and/or MOX to be loaded on the catalyzer that obtains in the pore of carrier with homogeneous and trickle dispersion state.
This sluggish precipitation is implemented as follows, for example, infiltrate metal-salt and the precipitation agent precursor that in solution, produces precipitation agent simultaneously in carrier through chemical reactions such as hydrolysis after, this impregnated carrier is carried out heat treated etc. is generated precipitation agent by the precipitation agent precursor processing.Owing to be sluggish precipitation, therefore importantly metal-salt and precipitation agent precursor form liquid phase, promptly form solution.That is, the dipping solution that will contain metal-salt and precipitation agent precursor is infiltrated up in the carrier, then, carries out being generated by the precipitation agent precursor processing of precipitation agent.
[method of manufacture of solid acid catalyst]
At first; Method of manufacture to based on the solid acid catalyst of the 3rd aspect of sluggish precipitation describes, and as stated, said sluggish precipitation does; The dipping solution that will contain metal-salt and precipitation agent precursor infiltrates in carrier, carries out being generated by the precipitation agent precursor processing of precipitation agent then.
(1) carrier
The carrier that uses for the 3rd aspect does not limit especially; Preferable alloy is oxide-based, complex metal oxides class, zeolites, clay class; More preferably silicon-dioxide, aluminum oxide, zirconium white, titanium oxide, silica-alumina, silicon-dioxide-zirconium white, silica-titania, preferred especially silicon-dioxide, aluminum oxide, zirconium white.
As for particle diameter, fine pore and the pore volume of carrier, can be different because of purposes, use form as solid acid catalyst, cannot treat different things as the same.
These carriers both can use a kind of separately, also can share two or more.
(2) metal hydroxides and/or MOX
Be carried on metal hydroxides and/or the not special restriction of MOX on the carrier for above-mentioned that kind; Be generally the oxyhydroxide and/or the oxide compound of the metallic element of periodictable the 2nd～14 family; Be preferably the oxyhydroxide and/or the oxide compound that are selected from by at least a metallic element in the group of periodictable the 3rd family, the 4th family, the 5th family, the 13rd family and the 14th group composition; More preferably be selected from the oxyhydroxide and/or the oxide compound of at least a metallic element in the group of forming by Ti, Zr, Hf, Nb, Al and Si, be preferably the oxyhydroxide and/or the oxide compound that are selected from least a metallic element in the group of forming by Ti, Zr, Al and Nb especially.
(3) metal-salt
The metal-salt that is used for sluggish precipitation is to generate the above-mentioned metal hydroxides that is carried on the resulting solid acid catalyst and/or the metal-salt of MOX; Therefore; Be generally the salt of the metallic element of above-mentioned periodictable the 2nd～14 family; Be preferably the salt of the metallic element of the 3rd, 4,5,13,14 families, more preferably Ti, Zr, Hf, Nb, Al, Si salt are preferably Ti, Zr, Al, Nb salt especially.
For the not special restriction of the kind of salt, preferably nitrate, acetate, vitriol, oxynitrate, muriate, oxychloride, more preferably oxynitrate, oxychloride, vitriol.
That is, as nitrate salt, acetate, vitriol, oxynitrate, muriate, the oxychloride of metal-salt preferred cycle table the 2～14 family's metals, more preferably Zircosol ZN, basic zirconium chloride, zirconium sulfate, titanium chloride, Tai-Ace S 150, niobium oxychloride.
These metal-salts both can use a kind of separately, also can share two or more.
(4) precipitation agent precursor
Precipitation agent precursor of the present invention is meant, causes that through processing such as in dipping solution, heating hydrolysis or other chemical reactions are to generate the material of precipitation agent.Precipitation agent be meant with dipping solution in reacting metal salt generate the sedimentary material of metal hydroxides and/or MOX.In the precipitation agent precursor; With producing alkali (promptly as the material of precipitation agent; In dipping solution, produce alkali, the pH of solution risen, make metal-salt with the sedimentary material of the form of oxyhydroxide and/or oxide compound through hydrolysis or other chemical reaction) be called " alkali precursor ".
For the not special restriction of precipitation agent precursor that is used to carry out sluggish precipitation, use the alkali precursor usually.
As the alkali precursor, amide compound that generally use urea, tricyanic acid, alkyl substituted ureas, thiocarbamide, alkyl substituting thioureido, constitutes by amine and carboxylic acid etc.Preferred urea, tricyanic acid, the alkyl substituted ureas of using is from being easy to obtain and the consideration of cost aspect preferred especially urea, tricyanic acid.These alkali precursors can use a kind of separately, also can share two or more.
(5) alkaline matter
In dipping solution, not only can add above-mentioned alkali precursor, and the alkaline matter that can in not generating sedimentary scope, add predetermined amount in advance is to improve pH.Through using alkaline matter, consumption, the minimizing that can reduce the alkali precursor generate the deposition time necessary.
For the not special restriction of alkaline matter; Can enumerate oxyhydroxide, carbonate, supercarbonate, phosphoric acid salt, the acetate of basic metal, earth alkali metal and ammonium; Ammonia; Organic amine etc., preferred ammonia, organic amine, the carbonate of ammonium, supercarbonate, phosphoric acid salt, more preferably volatile salt, bicarbonate of ammonia.
These alkaline matters both can use a kind of separately, also can share two or more.
(6) dipping solution
Dipping solution prepares through above-mentioned metal-salt, precipitation agent precursor and the alkaline matter that uses as required are dissolved in the water usually.
To the not special restriction of the concentration of metal-salt in the dipping solution and precipitation agent precursor; As long as can keep dissolved state and can realize to after state the charge capacity that is fit to of carrier; Usually metal salt concentrations is 0.01 weight %～50 weight %, is preferably 0.1 weight %～40 weight %, is preferably 0.5 weight %～30 weight % especially; For the precipitation agent precursor as after state; With respect to being enough to make the whole sedimentary theoretical amount of this metal-salt is 0.1～10 times, is preferably 0.2～8 times, is preferably 0.3～5 times especially.
Can suitably use alkaline matter to obtain required pH condition.That is, owing to generate the necessary pH condition of deposition according to the kind of employed metal-salt and precipitation agent precursor or concentration and different, so can use the alkaline matter of necessary amount according to these conditions.
In addition; Among the present invention, in order in carrier, to implement sluggish precipitation, make before the precipitation agent precursor converts the processing of precipitation agent into; Needing at least a metal-salt and precipitation agent precursor is liquid phase in dipping solution; Be dissolved state, for except this at least a metal-salt and the material the precipitation agent precursor, in dipping solution, exist and all can with random order.
(7) sluggish precipitation
< dipping solution is to the infiltration method of carrier >
For making above-mentioned dipping solution be infiltrated up to the not special restriction of method in the carrier, load to equably on the carrier in order to make metal-salt, preferably implement with the hole completion method.In this case, the volume that is infiltrated up to the dipping solution in the carrier is preferably 60%～120% of carrier pore volume, and more preferably 70%～110%, be preferably 80%～105% especially.If this hypovolia, then dipping solution can not get in the carrier pore equably, and causes uneven homogenize.Conversely, if this hypervolia, then steeping fluid still can cause uneven homogenize attached to the carrier outside surface.
In addition; The charge capacity that loads on the metal-salt on the carrier through infiltration can be selected to measure arbitrarily; But be 0.01 weight %～50 weight % with respect to vehicle weight usually, be preferably 0.05 weight %～40 weight %, further be preferably 0.1 weight %～30 weight %.Charge capacity for the precipitation agent precursor; If being enough to make the whole sedimentary theoretical amount of the metal-salt that is carried on the carrier is,, in 0.1～10 scope, use the precipitation agent precursor usually at 1 o'clock with molar ratio computing; Be preferably 0.2～8 scope, further be preferably 0.3～5 scope.
< sedimentary generation and post-treating method >
In the 3rd aspect; Dipping solution is infiltrated up in the carrier; The state that makes the metal-salt that is carried on the carrier and precipitation agent precursor in the carrier pore, keep solution thus; Implement heating in this state and wait the processing that the precipitation agent precursor is converted into precipitation agent, be utilized in the even precipitation agent that produces of carrier inside and convert metal-salt into corresponding metal hydroxides.
Usually use the alkali precursor as the precipitation agent precursor, in the processing that the alkali precursor is converted into alkali, utilize the hydrolysis of the alkali precursor that causes by heating.
As stated; In the 3rd aspect; In order in the carrier pore, to implement sluggish precipitation; Need be before carrying out converting the precipitation agent precursor processing of precipitation agent into, make at least a metal-salt and precipitation agent precursor be solution state, be liquid phase, and except this at least a metal-salt, material the precipitation agent precursor be that any state all can.
In based on the hydrolysis reaction that adds thermal initiation, the alkali precursor is converted under the situation of alkali,, adopt 50 ℃～300 ℃ scope usually, preferably adopt 60 ℃～200 ℃ scope as Heating temperature.Heating temperature is changed in time.If Heating temperature is low excessively, the reaction of precipitation agent then might not take place to be generated by the precipitation agent precursor, or need expend the very long time; If Heating temperature is too high, then the necessary moisture of hydrolysis sometimes may all be removed before the reaction that is generated precipitation agent by the precipitation agent precursor finishes.In order to implement good and stable sluggish precipitation, preferably when the sedimentary reaction of generation finished, the moisture entrapment in the dipping solution of infiltration in carrier is more than 5%, and was more preferably residual more than 10%.
As the fixed bed heating unit; Can there be the carrier of dipping solution to heat to infiltration at the immobilising state of load carriers; But especially under the situation of a large amount of catalyzer of preparation, more preferably the thermopnore device of working load carrier flow, revolving heating unit etc.According to thinking, when heating, occur under the situation of moisture evaporation, make load carriers mobile method that the water evaporation quantity of every particle loading carrier is changed, thereby further increase uniformity.
In addition; If the moisture evaporation during heating is too fast; Then moisture was all removed before the hydrolysis of alkali precursor finishes fully, can not fully carry out the supply of precipitation agent sometimes, therefore it is desirable to usually; By begin to be heated to through deposition after formation reaction finishes, till removing moisture fully, with more than 1 hour, preferred more than 3 hours, further preferred time more than 6 hours carries out removing fully of moisture.
Thereafter; Water, alkaline aqueous solution, aqueous acid, organic solvent etc. clean resulting catalyzer as required; After the drying; Under inert gas atmospheres such as nitrogen, argon gas or oxidizing gas atmosphere such as air or dilution oxygen, fire, thus the solid acid catalyst that can obtain having desired performance.Heating firing temperature as this moment is generally 100 ℃～1200 ℃, is preferably 300 ℃～1100 ℃, further is preferably 500 ℃～1000 ℃.Fire through carrying out such heating, the catalyst activity of resulting solid acid catalyst and stability are improved.
(8) solid acid catalyst
On the solid acid catalyst that obtains by above-mentioned operation the crystallite dimension of the MOX of load and/or metal hydroxides because of the kind of the kind of metallic element, charge capacity, carrier, to fire condition etc. different; Use same metal-salt same charge capacity, identical carrier, same firing under the situation about preparing under the condition; This crystallite dimension is below 90% of crystallite dimension during with prior art for preparing; Be preferably below 80%, further be preferably below 75%.In addition, this crystallite dimension utilizes the peak width at half at XRD determining peak to calculate.
In addition, be 0.05 weight %～40 weight % with respect to the metal hydroxides of carrier and/or the charge capacity of metal acidulants in the solid acid catalyst that obtains with the method for the 3rd aspect, be preferably 0.1 weight %～30 weight % especially.
[method of manufacture of polyethers]
The solid acid catalyst of making according to the method for the 3rd aspect can be well as the catalyst for polymerization in the manufacturing of polyethers (particularly utilizing the manufacturing of polyethers of the ring-opening polymerization of ring-type ethers).
Down in the face of using solid acid catalyst of the present invention to describe as the method for manufacture of the polyethers of catalyst for polymerization.
Make under the situation of polyethers with the ring-opening polymerization of ring-type ethers, as the cyclic ether as reaction raw materials, the formation carbonatoms that can enumerate ring is 3～10 cyclic ether, and, can use with substituted cyclic ethers such as alkyl, halogen radical, acyl groups.Specifically, can use THF, trimethylene oxide, oxepane, 1,4-dioxane, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran etc.And, any polymerization in the homopolymerization that can only use a kind of ring-type ethers and the copolymerization of using two or more ring-type ethers.
Consider that from the aspect of control molecular weight the ring-opening polymerization of cyclic ether preferably carries out in the presence of carboxylic acid anhydride and/or carboxylic acid.As carboxylic acid anhydride and/or carboxylic acid, generally use aliphatics or aromatic carboxylic acid anhydride and/or carboxylic acid, preferred carboxylic acid anhydride and/or the carboxylic acid that use with 2～8 carbon atoms with 2～12 carbon atoms.These carboxylic acid anhydride and/or carboxylic acid both can use a kind of separately, also can share two or more.Carboxylic acid anhydride and/or carboxylic acid are comparatively suitable with respect to cyclic ether to be that 0.01～1.0 (mol ratio) added usually.
Can in reaction, use inert solvent during polyreaction.As this solvent, use the divided ring polyreaction to be in inert aliphatic hydrocarbon, the aromatic hydrocarbon etc. one or more usually.
Reaction formation uses the general form of using such as grooved, tower, can be any of batch mode, continuous mode.Following method etc. is for example arranged: cyclic ether, catalyzer, carboxylic acid anhydride and/or carboxylic acid are under agitation fed intake carry out polymeric method (batch mode); In containing the reactor drum of catalyzer, supply with cyclic ether, carboxylic acid anhydride and/or carboxylic acid and continuous method (continuous mode) of extracting reaction solution out etc. continuously.Consider preferred continuous mode from the aspect of productivity.
The consumption of solid acid catalyst depends on its kind, not special the qualification, but for example in the batch-type reactor drum, if catalytic amount is very few, then polymerization velocity is slack-off, conversely if too much, then be difficult to remove heat of polymerization.And, because the slurry concentration of reaction system uprises, cause stirring difficulty, and be easy to go wrong in the separatory of catalyzer and reaction solution after polyreaction finishes.Therefore,, can consider under the condition of reaction form of batch reactions, circulation reaction, be generally 0.001～50 times of weight with respect to liquid phase, be preferably in the scope of 0.01～20 times of weight and select for catalyst consumption.Wherein, under the situation of circulation reaction, catalyst consumption is represented the amount with respect to the catalyzer of liquid phase feed rate of time per unit.
Temperature of reaction is generally 0 ℃～200 ℃, is preferably 10 ℃～80 ℃.
Reaction pressure is that reaction system can keep the pressure of liquid phase to get final product, usually from normal pressure～10MPa, preferably select from the pressure range of normal pressure～5MPa.
To not special qualification of reaction times, consider itself and catalytic amount the two, consider yield, economy, the reaction times is 0.1 hour～20 hours scope, is preferably 0.5 hour～15 hours scope.The said here reaction times is meant, in batch mode, plays the time till reaction finishes to begin to cool down when rising to temperature of reaction by temperature; In continuous mode, the residence time of liquid in reactor drum formed in reaction.
Use is carried out according to the solid acid catalyst of the 3rd aspect manufacturing under the situation of ring-opening polymerization of THF (THF), and can obtain number-average molecular weight (Mn) is 200～80,000, particularly 200～40, the polyethers of low～middle molecular weight of about 000.And then the polyethers that can easily produce narrow molecular weight distribution also is one of characteristic.Promptly; The Mw/Mn of the polyethers that industrial requirement is bigger is 1.3～2.5; Through utilizing solid acid catalyst of the present invention; Can access Mw/Mn less than 3, for example Mw/Mn is 1.1～3.0 polytetramethylene ether diol (PTMG), particularly through selecting optimum condition of the present invention for use, can also obtain Mw/Mn and be about 1.5～1.8 the very narrow polyethers of MWD.And according to the present invention, the yield that can make product is more than 25%, is preferably more than 30%, further is more than 35%.
[embodiment and comparative example]
Enumerate embodiment and comparative example below to the further explanation particularly of the 3rd aspect, but following embodiment not delimit the scope of the invention.
In addition, in the content below, the GPC (GPC) below the yield of polytetramethylene ether diol acetic ester (PTME), number-average molecular weight (Mn), MWD (Mw/Mn) are utilized obtains.
The GPC device: Tosoh society makes GPC 8220
Post: TSK-GELH 30cm * 2 piece
Detection method: RI
Column temperature: 40 ℃
Mobile phase: THF
Flow velocity: 1ml/min
Sample IR: 100 μ L
Sample concentration: the concentration that is adjusted to polyethers is about 0.1 weight %
Embodiment 2-1
< preparation of solid acid catalyst >
[dipping of dipping solution]
(new Japanese metallochemistry society makes ZrO at the 89.66g Zircosol ZN aqueous solution
2Conversion concentration 18.12 weight %) add 18.72g de-salted water and uniform mixing in.To wherein adding 11.84g urea uniform mixing, the preparation dipping solution.In this solution, add 80g SiO
2(Silysia of Fuji makes, CARiACT Q15, particle diameter 75 μ m～500 μ m; Median size 200 μ m, pore volume 1.16ml/g, average fine pore 15nm); Vibrate and mixed in about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).
[heat treated]
Have the carrier of above-mentioned dipping solution to pack in the 500ml pyriform flask infiltration, jointing and the bend pipe that is plugged with glass wool connect TM in measurement section on flask top.With anchor clamps flask be fixed on the turning axle of rotating dryer on thereafter.Speed rotation turning axle with 10rpm is set at 105 ℃ with the drying machine temperature, carries out 6 hours heating.At this moment, confirm the moisture entrapment 90% in the dipping solution through weight change.Then, unload the bend pipe that is plugged with glass wool on top after, the drying machine temperature is set at 120 ℃, carry out 16 hours heating.
Then, unload the joint on top after, the drying machine temperature is set at 140 ℃, carry out 4 hours heating, moisture is almost completely removed.After 4 hours, stop heating, rotation, take out catalyzer.
Catalyzer is transferred in the beaker of 500ml and naturally cools to room temperature, add the de-salted water of about 300ml then, carry out about 10 minutes suspension cleaning.Behind the filtering catalyst, be transferred to once more in the beaker of 500ml, the suspension that amounts to 3 times is cleaned.Next, behind the air-dry catalyzer, under airiness, implement 2 hours fire in 900 ℃ then a dry night in 120 ℃ drying machine, obtain solid acid catalyst.Obtain the zirconic average crystallite footpath that is carried on this solid acid catalyst through XRD determining; The result is
and, be 16.9 weight % through calculating by the zirconic charge capacity of obtaining forming of steeping fluid with respect to the catalyzer total amount.
< manufacturing of polyethers >
In the four-hole boiling flask of 500ml, add 133.5g THF, 6.85g diacetyl oxide under the condition of nitrogen gas and mix.The solid acid catalyst that weighing 4.68g obtains in the preparation of above-mentioned solid acid catalyst under condition of nitrogen gas is after stirring is added to it in above-mentioned mixed solution down, in 40 ℃ of reactions 5 hours.With the gpc analysis reaction solution, number-average molecular weight (Mn), the MWD (Mw/Mn) of transformation efficiency and the PTME of THF are measured, transformation efficiency is 56.3% as a result, and Mn is 2563, and Mw/Mn is 1.88.
Embodiment 2-2
42.46g basic zirconium chloride 8 hydrates are dissolved in the 59.48g de-salted water, and to wherein adding 11.84g urea and uniform mixing, the preparation dipping solution likewise carries out Preparation of catalysts with embodiment 2-1 in addition, utilizes this catalyzer to carry out the manufacturing of polyethers.The zirconic average crystallite that draws through XRD determining is directly for detecting below the lower limit
, is 16.9 weight % with respect to the zirconic charge capacity of catalyzer total amount.Transformation efficiency is 55.1%, and Mn is 2520, and Mw/Mn is 1.87.
Embodiment 2-3
(Japanese light metal society makes, ZrO with the 46.95g zirconium sulfate aqueous solution
2Conversion concentration is 15.1 weight %) be dissolved in the 56.95g de-salted water, to wherein adding 23.78g urea and uniform mixing, the preparation dipping solution likewise carries out Preparation of catalysts with embodiment 2-1 in addition, utilizes this catalyzer to carry out the manufacturing of polyethers.Directly the zirconic charge capacity with respect to the catalyzer total amount is 16.9 weight % to the zirconic average crystallite that draws through XRD determining for
.Transformation efficiency is 51.2%, and Mn is 2252, and Mw/Mn is 1.87.
Embodiment 2-4
(new Japanese metallochemistry society makes ZrO to the 86.80g Zircosol ZN aqueous solution
2Conversion concentration is 18.72 weight %) middle 17.84g de-salted water and the uniform mixing of adding, to wherein little by little adding 10.84g Ammonium Bicarbonate, Food Grade and uniform mixing, to wherein adding 7.92g urea and uniform mixing, the preparation dipping solution.In this solution, add 80g SiO
2(Silysia of Fuji make, CARiACT Q15), vibration mixed about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).
It is added in the 500ml pyriform flask; To change 1.5 hours into by 6 hours in the heat-up time in temperature is 105 ℃ drying machine; Likewise operate with embodiment 2-1 in addition, carry out a series of heating, clean, fire processing, obtain solid acid catalyst.Directly the zirconic charge capacity with respect to the catalyzer total amount is 16.9 weight % to the zirconic average crystallite that obtains through XRD determining for
.
Use this solid acid catalyst, likewise carry out the manufacturing of polyethers with embodiment 2-1.Transformation efficiency is 55.4%, and Mn is 2626, and Mw/Mn is 1.87.
Comparative example 2-1
(new Japanese metallochemistry society makes ZrO to the 89.66g Zircosol ZN aqueous solution
2Conversion concentration 18.12 weight %) add 18.72g de-salted water and uniform mixing in.To wherein adding 11.84g urea and uniform mixing, the preparation dipping solution.In this solution, add 80g SiO
2(Silysia of Fuji make, CARiACT Q15), vibration mixed about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).Remove the moisture of steeping fluid more than 97% through it being carried out drying under reduced pressure, obtain thus through exsiccant metal-salt and precipitation agent precursor load carriers with the solid state shape load.
It is added in the 500ml pyriform flask, likewise operate, carry out a series of heating, clean, fire processing, obtain solid acid catalyst with embodiment 2-1.Directly the zirconic charge capacity with respect to the catalyzer total amount is 16.9 weight % to the zirconic average crystallite that obtains through XRD determining for
.
Use this solid acid catalyst, likewise carry out the manufacturing of polyethers with embodiment 2-1.Transformation efficiency is 29.8%, and Mn is 3019, and Mw/Mn is 2.01.
Comparative example 2-2
(new Japanese metallochemistry society makes ZrO to the 89.66g Zircosol ZN aqueous solution
2Conversion concentration 18.12 weight %) add 27.72g de-salted water and uniform mixing in.In this solution, add 80g SiO
2(Silysia of Fuji make, CARiACT Q15), vibration mixed about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).
In its 500ml pyriform flask of packing into, jointing and the bend pipe that is plugged with glass wool connect TM in measurement section on flask top.With anchor clamps flask be fixed on the turning axle of rotating dryer on thereafter.Speed rotation turning axle with 10rpm is set at 105 ℃ with the drying machine temperature, carries out 6 hours heating.Then, unload the bend pipe that is plugged with glass wool on top after, the drying machine temperature is set at 120 ℃, carry out 16 hours heating.
Then, unload the joint on top after, the drying machine temperature is set at 140 ℃, carry out 4 hours heating.After 4 hours, stop heating, rotation, take out catalyzer.
Catalyzer is transferred to naturally cool to room temperature in the beaker of 500ml after, be added on the solution that dissolving 35g Ammonium Bicarbonate, Food Grade obtains in the 350ml de-salted water, stir about 10 minutes.Behind the filtering catalyst, add the de-salted water of about 300ml, carry out about 10 minutes suspension and clean.Behind the filtering catalyst, be transferred to once more in the beaker of 500ml, the suspension that amounts to 3 times is cleaned.Next, behind the air-dry catalyzer, under airiness, implement 2 hours fire in 900 ℃ then a dry night in 120 ℃ drying machine, obtain solid acid catalyst.Directly the zirconic charge capacity with respect to the catalyzer total amount is 16.9 weight % for
to obtain zirconic average crystallite through XRD determining.
Use this solid acid catalyst, likewise carry out the manufacturing of polyethers with embodiment 2-1.Transformation efficiency is 45.7%, and Mn is 2947, and Mw/Mn is 2.03.
Embodiment 2-5
(new Japanese metallochemistry society makes ZrO to the 89.66g Zircosol ZN aqueous solution
2Conversion concentration is 18.12 weight %) middle 20.65g de-salted water and the uniform mixing of adding.To wherein little by little adding 6.74g volatile salt and uniform mixing.To wherein adding 11.84g urea and uniform mixing, the preparation dipping solution.In this solution, add 80g SiO
2(Silysia of Fuji makes, CARiACT Q30, particle diameter 75 μ m～500 μ m; Median size 200 μ m, pore volume 1.21ml/g, average fine pore 30nm); Vibration mixed about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).
It is added in the 500ml pyriform flask, likewise operate, carry out a series of heating, clean, fire processing, obtain solid acid catalyst with embodiment 2-2.Directly the zirconic charge capacity with respect to the catalyzer total amount is 16.9 weight % to the zirconic average crystallite that obtains through XRD determining for
.
Use this solid acid catalyst, likewise carry out the manufacturing of polyethers with embodiment 2-1.Transformation efficiency is 52.7%, and Mn is 2875, and Mw/Mn is 1.85.
Embodiment 2-6
(new Japanese metallochemistry society makes ZrO to the 88.01g Zircosol ZN aqueous solution
2Conversion concentration is 18.46 weight %) middle 26.83g de-salted water and the uniform mixing of adding.To wherein adding 11.84g urea and uniform mixing, the preparation dipping solution.In this solution, add 80g SiO
2(Silysia of Fuji make, CARiACT Q30), vibration mixed about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).
It is added in the 500ml pyriform flask, will change 2 hours into by 6 hours, likewise operate with embodiment 2-1 in addition, carry out a series of heating, clean, fire processing, obtain solid acid catalyst in the heat-up time in temperature is 105 ℃ drying machine.Directly the zirconic charge capacity with respect to the catalyzer total amount is 16.9 weight % to the zirconic average crystallite that obtains through XRD determining for
.
Use this solid acid catalyst, likewise carry out the manufacturing of polyethers with embodiment 2-1.Transformation efficiency is 41.9%, and Mn is 2436, and Mw/Mn is 1.73.
Comparative example 2-3
(new Japanese metallochemistry society makes ZrO to the 89.66g Zircosol ZN aqueous solution
2Conversion concentration 18.12 weight %) add 22.72g de-salted water and uniform mixing in.To wherein adding 11.84g urea and uniform mixing, the preparation dipping solution.In this solution, add 80g SiO
2(Silysia of Fuji make, CARiACT Q30), vibration mixed about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).Remove the moisture of steeping fluid more than 97% through it being carried out drying under reduced pressure, obtain to have the load carriers of the metal-salt and the precipitation agent precursor of solid state shape thus through the exsiccant load.
It is added in the 500ml pyriform flask, likewise operate, carry out a series of heating, clean, fire processing, obtain solid acid catalyst with embodiment 2-1.Directly the zirconic charge capacity with respect to the catalyzer total amount is 16.9 weight % to the zirconic average crystallite that obtains through XRD determining for
.
Use this solid acid catalyst, likewise carry out the manufacturing of polyethers with embodiment 2-1.Transformation efficiency is 13.0%, and Mn is 3167, and Mw/Mn is 2.13.
Comparative example 2-4
(new Japanese metallochemistry society makes ZrO to the 89.66g Zircosol ZN aqueous solution
2Conversion concentration 18.12 weight %) add 31.72g de-salted water and uniform mixing in.In this solution, add 80g SiO
2(Silysia of Fuji make, CARiACT Q30), vibration mixed about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).In its 500ml pyriform flask of packing into, 2-2 likewise heats with comparative example, likewise handle and carry out with Ammonium Bicarbonate, Food Grade catalyzer filtration, cleaning, drying, fire, obtain solid acid catalyst.Directly the zirconic charge capacity with respect to the catalyzer total amount is 16.9 weight % for
to obtain zirconic average crystallite through XRD determining.
Use this solid acid catalyst, likewise carry out the manufacturing of polyethers with embodiment 2-1.Transformation efficiency is 35.9%, and Mn is 3943, and Mw/Mn is 1.97.
The result of the foregoing description 2-1～2-6 and comparative example 2-1～2-4 gathers among the 2-1 in table and provides.
[table 2-1]
2-1 can know following content by table.
Contrast by embodiment 2-1～2-3 and comparative example 2-1 can be known; Do not utilize the sluggish precipitation in the carrier pore; But, dry impregnated carrier begins heat treated again, the poor-performing of the catalyzer that obtains thus after processing solid state shape with impregnating metal salt and precipitation agent precursor.
In addition, can be known by the contrast of embodiment 2-1～2-3 and comparative example 2-2, not utilize the sluggish precipitation in the carrier pore, supply with alkali but have the carrier of metal-salt to put in the alkaline solution infiltration by the outside, the performance of the catalyzer that obtains thus is also relatively poor.
In addition; Contrast by embodiment 2-5～2-6 and comparative example 2-3～2-4 can be known; Also identical result can be obtained under the situation of use different carriers,, just high performance solid acid catalyst can be made so long as implement method based on the sluggish precipitation in the carrier pore of the 3rd aspect.
[explanation of the 4th aspect]
The inventor finds; Through in the presence of catalyzer, the cyclic ether ring-opening polymerization being made in the method for polyethers; Use to contain as catalyzer and be selected from by one or more elements in the group of periodictable the 1st, 2,4,6,8,9,12,13,14,15,16,17 group compositions and can be with itself solid acid catalyst with the cyclic ether ring-opening polymerization; When carrying out the manufacturing of polyethers; Can be simply and effectively the molecular-weight average of resulting polyethers be controlled at desired value and can produce detrimentally affect to other performances, thereby accomplish the invention of the 4th aspect.
Promptly; The main points of the 4th aspect are a kind of method of manufacture of polyethers; It is through in the presence of catalyzer, the cyclic ether ring-opening polymerization being made the method for polyethers; It is characterized in that; Use the catalyzer obtain as follows as catalyzer: be selected from by at least a element in the group of periodictable the 1st, 2,4,6,8,9,12,13,14,15,16,17 group compositions and can make it contain being selected from of not comprising in this solid acid catalyst containing with in itself solid acid catalyst with the cyclic ether ring-opening polymerization by at least a metallic element in the group of periodictable the 3rd, 5,10,11 group compositions.
In the 4th aspect; As can be with itself solid acid catalyst with the cyclic ether ring-opening polymerization, preferred one or more the solid acid catalyst that is selected from the group of forming by catalyzer, O composite metallic oxide catalyst, clay catalyst and the zeolite catalyst of MOX by load that uses.
Be selected from by the metallic element in the group of periodictable the 3rd, 5,10,11 group compositions as what do not comprise in the said solid acid catalyst, preferably use copper and/or nickel.
As can be with the solid acid catalyst of cyclic ether ring-opening polymerization, preferred one or more the solid acid catalyst that is selected from the group of forming by clay catalyst, silica-alumina, silica-titania and silicon-dioxide-zirconium white that uses.
Said catalyzer is preferably through utilizing the sluggish precipitation in the carrier pore to make at the pore internal burden metal hydroxides and/or the MOX of carrier.
Method of manufacture according to the polyethers of the 4th aspect need not change reaction conditions, only changes the composition and the composition thereof of employed catalyzer, just can change the molecular-weight average of resulting polyethers, and can not produce detrimentally affect to the performance beyond the molecular-weight average.
Therefore, according to the 4th aspect, can produce the polyethers with desired molecular-weight average of the purposes that meets polyethers simply and effectively.
Be elaborated in the face of the embodiment of the 4th aspect down, but the explanation of the constitutive requirements of following record is merely an example (typical example) of the embodiment of the 4th aspect, only otherwise exceed its main points, the 4th aspect does not receive the restriction of these contents.
[catalyzer]
At first the catalyzer that uses in the 4th aspect is described.The catalyzer that uses among the present invention is the catalyzer that in solid acid catalyst, contains the metallic element of specific (periodictable the 3rd, 5,10,11 families).
< solid acid catalyst >
Among the present invention,, can enumerate the zeolites of crystalline structure such as for example having MFI, X, Y as solid acid catalyst; Metal oxide-type such as silicon-dioxide, aluminum oxide, titanium oxide, zirconium white; The complex metal oxides class that two or more oxide-metal combinations such as silica-titania, silica-alumina, silicon-dioxide-zirconium white, aluminum oxide-titanium oxide form; With MOX, clay, zeolite is that carrier and load have the MOX that is different from this carrier or have the loading type acid catalyst class of the compound of acid matter; Clay classes such as atlapulgite; Or the like.
Wherein, preferred complex metal oxides class, loading type acid catalyst class, clay class, preferred especially silicon-dioxide-zirconium white, silica-alumina, silica-titania, clay class.
< method of manufacture of solid acid catalyst >
As the method for manufacture of solid acid catalyst, can use technique known and not special restriction, specifically, can adopt the method for manufacture of record in above-mentioned patent documentation 1, the patent documentation 2 etc.
As the catalyzer that the 4th aspect is used, preferably utilize the interior sluggish precipitation of carrier pore at the pore internal burden metal hydroxides of carrier and/or the catalyzer of MOX.
< making the method that contains specific metallic element in the solid acid catalyst >
Contain the method that is selected from that is not comprised in this solid acid catalyst in the solid acid catalyst as making, can adopt as follows any method in (1), (2), (3) by at least a metallic element in the group of periodictable the 3rd, 5,10,11 group compositions (hereinafter being sometimes referred to as " adding metallic element (additive element) "):
When (1) preparing solid acid catalyst, make employed carrier contain the method for this interpolation metallic element in advance;
Make it contain the method for this interpolation metallic element when (2) preparing solid acid catalyst simultaneously;
(3) prepare the method for adding this interpolation metallic element after the solid acid catalyst;
But the method for preferred (2) makes it contain the method for this interpolation metallic element simultaneously when promptly preparing solid acid catalyst.
<utilizing sluggish precipitation to carry out the manufacturing of catalyzer >
Down in the face of the method for making the employed catalyzer in the 4th aspect describes, in the preparation solid acid catalyst, make it contain the interpolation metallic element during precipitation from homogeneous solution manufactured catalyzer in this method in utilizing the carrier pore.
Under the situation of the catalyzer that uses in the 4th aspect as the loading type acid catalyst, with respect to whole content of metal of its carrier, as the content of metal of solid acid catalyst, add the metallic element charge capacity be preferably by after the metal-salt stated or the metal oxide supported amount amount that converts and obtain.
Sluggish precipitation is implemented as follows, for example, infiltrate metal-salt and the precipitation agent precursor that in solution, produces precipitation agent simultaneously in carrier through chemical reactions such as hydrolysis after, this impregnated carrier is carried out heat treated etc. is generated precipitation agent by the precipitation agent precursor processing.Owing to be sluggish precipitation, therefore importantly metal-salt and precipitation agent precursor form the liquid phase ie in solution.That is, the dipping solution that will contain metal-salt and precipitation agent precursor is infiltrated up in the carrier, then, carries out being generated by the precipitation agent precursor processing of precipitation agent.
As the metal-salt that is dissolved in this immersion solvent, will be used to generate the metal-salt (hereinafter being sometimes referred to as " acid generates metal-salt ") of solid acid catalyst and be used to generate the metal-salt (hereinafter being sometimes referred to as " salt that adds metallic element ") that adds metallic element and share.
(1) carrier
For the not special restriction of the carrier of catalyzer; Preferable alloy is oxide-based, complex metal oxides class, zeolites, clay class; More preferably silicon-dioxide, aluminum oxide, zirconium white, titanium oxide, silica-alumina, silicon-dioxide-zirconium white, silica-titania, clay class, preferred especially silicon-dioxide, aluminum oxide, zirconium white, clay class.
These carriers both can use a kind of separately, also can share two or more.
(2) be dissolved in metal-salt in the dipping solution
(2-1) acid generates metal-salt
As being carried on the carrier and showing the metallic element of the metal-salt of solid acid, more than one in can life cycle table the 1,2,4,6,8,9,12,13,14,15,16,17 family's metallic elements.The metallic element of preferred life cycle table the 4 families, the 13rd family, the 14th family more preferably uses Ti, Zr, Hf, Al, Si metallic element, especially preferably uses Ti, Zr, Al.
For the not special restriction of the kind of salt, preferably nitrate, acetate, vitriol, oxynitrate, muriate, oxychloride, more preferably oxynitrate, oxychloride, vitriol.
Promptly; Generate metal-salt as acid; Nitrate salt, acetate, vitriol, oxynitrate, muriate, the oxychloride of preferred cycle table the 1,2,4,6,8,9,12,13,14,15,16,17 families, more preferably Zircosol ZN, basic zirconium chloride, zirconium sulfate, titanium chloride, Tai-Ace S 150.
These acid generation metal-salts both can use a kind of separately, also can share two or more.
(2-2) salt of interpolation metallic element
On the other hand; Be selected from by at least a metallic element in the group of periodictable the 3rd, 5,10,11 group compositions (interpolation metallic element) for what do not contain in this solid acid catalyst that will in solid acid catalyst, add; The metallic element of life cycle table the 3 families, the 5th family, the 10th family, the 11st family; The metallic element of preferred Ni, Cu, Ce, preferred especially Ni, Cu.
Add the not special restriction of salt of metallic element, preferably nitrate, acetate, vitriol, oxynitrate, muriate, oxychloride, more preferably oxynitrate, oxychloride, vitriol for these.
That is, as the salt that adds metallic element, preferred cycle table the 3 families, the 5th family, the 10th family, the nitrate salt of the 11st family's metal, acetate, vitriol, oxynitrate, muriate, oxychloride, more preferably nickelous nitrate, nickelous chloride, cupric nitrate, cupric chloride.
These salt that add metallic element both can use a kind of separately, also can share two or more.
(3) precipitation agent precursor
The precipitation agent precursor is meant, causes that through processing such as in dipping solution, heating hydrolysis or other chemical reactions are to generate the material of precipitation agent.Precipitation agent be meant with dipping solution in reacting metal salt generate the material of precipitate metal hydroxides.In the precipitation agent precursor; With producing (promptly as the material of the alkali of precipitation agent; In dipping solution, produce alkali, the pH of solution risen, make metal-salt with the sedimentary material of the form of oxyhydroxide or oxide compound through hydrolysis or other chemical reaction) be called " alkali precursor ".
For the not special restriction of precipitation agent precursor that is used to carry out sluggish precipitation, use the alkali precursor usually.
As the alkali precursor, amide compound that generally use urea, tricyanic acid, alkyl substituted ureas, thiocarbamide, alkyl substituting thioureido, constitutes by amine and carboxylic acid etc.Preferred urea, tricyanic acid, the alkyl substituted ureas of using is from being easy to obtain and the consideration of cost aspect preferred especially urea, tricyanic acid.These alkali precursors can use a kind of separately, also can share two or more.
(4) alkaline matter
In dipping solution, not only can add above-mentioned alkali precursor, and the alkaline matter that can in not generating sedimentary scope, add predetermined amount in advance is to improve pH.Through using alkaline matter, consumption, the minimizing that can reduce the alkali precursor generate the deposition time necessary.
For the not special restriction of alkaline matter; Can enumerate oxyhydroxide, carbonate, supercarbonate, phosphoric acid salt, the acetate of basic metal, earth alkali metal and ammonium; Ammonia; Organic amine etc., preferred ammonia, organic amine, the carbonate of ammonium, supercarbonate, phosphoric acid salt, more preferably volatile salt, bicarbonate of ammonia.
These alkaline matters both can use a kind of separately, also can share two or more.
(5) dipping solution
Dipping solution usually through the salt that above-mentioned acid generated metal-salt and add metallic element and precipitation agent precursor and as required the alkaline matter of use be dissolved in the water and prepare.
To the not special restriction of the concentration of metal-salt in the dipping solution and precipitation agent precursor; As long as can keep dissolved state and can realize to after state the charge capacity that is fit to of carrier; Usually metal salt concentrations is expressed as 0.01 weight %～50 weight % with the total concentration that acid generates metal-salt and the salt that adds metallic element, is preferably 0.1 weight %～40 weight %, is preferably 0.5 weight %～30 weight % especially; For the precipitation agent precursor as after state; With respect to being enough to make the whole sedimentary theoretical amount of this metal-salt is 0.1～10 times, is preferably 0.2～8 times, is preferably 0.3～5 times especially.
Can suitably use alkaline matter to obtain required pH condition.That is, owing to generate the necessary pH condition of deposition according to the kind of employed metal-salt and precipitation agent precursor or concentration and different, so can use the alkaline matter of necessary amount according to these conditions.
In order in carrier, to implement sluggish precipitation; Before carrying out converting the precipitation agent precursor processing of precipitation agent into; At least two kinds of metal-salts and the precipitation agent precursor that need acid to generate metal-salt and the salt that adds metallic element are liquid phase in dipping solution; Be dissolved state,, in dipping solution, exist and all can with random order for the material beyond these at least two kinds of metal-salts and the precipitation agent precursor.
(6) sluggish precipitation
(6-1) dipping solution is to the infiltration method of carrier
The not special restriction of method for above-mentioned dipping solution being infiltrated up in the carrier loads on the carrier with the salt that adds metallic element in order acid to be generated metal-salt equably, preferably implements with the hole completion method.In this case, the volume that is infiltrated up to the dipping solution in the carrier is preferably 60%～120% of carrier pore volume, and more preferably 70%～110%, be preferably 80%～105% especially.If this hypovolia, then dipping solution can not get in the carrier pore equably, and causes uneven homogenize.Conversely, if this hypervolia, then steeping fluid still can cause uneven homogenize attached to the carrier outside surface.
In addition; The charge capacity that loads on the metal-salt on the carrier through infiltration can be selected to measure arbitrarily; But with respect to vehicle weight; Be generally 0.01 weight %～50 weight % when representing with the total of adding metal-salt, be preferably 0.05 weight %～40 weight %, further be preferably 0.1 weight %～30 weight % with acid generation metal-salt.Charge capacity for the precipitation agent precursor; If being enough to make the whole sedimentary theoretical amount of the metal-salt that is carried on the carrier is,, in 0.1～10 scope, use the precipitation agent precursor usually at 1 o'clock with molar ratio computing; Be preferably 0.2～8 scope, further be preferably 0.3～5 scope.
(6-2) sedimentary generation and post-treating method
Dipping solution is infiltrated up in the carrier; The state that makes the metal-salt that is carried on the carrier and precipitation agent precursor in the carrier pore, keep solution thus; Implement heating in this state and wait the processing that the precipitation agent precursor is converted into precipitation agent, be utilized in the even precipitation agent that produces of carrier inside and convert metal-salt into corresponding metal hydroxides.
Usually use the alkali precursor as the precipitation agent precursor, in the processing that the alkali precursor is converted into alkali, utilize hydrolysis based on the alkali precursor of heating.
As stated; In order in the carrier pore, to implement sluggish precipitation; Need be before carrying out converting the precipitation agent precursor processing of precipitation agent into; Make at least two kinds of metal-salts and precipitation agent precursor be solution state, be liquid phase, and except these at least two kinds of metal-salts, material the precipitation agent precursor be that any state all can.
In based on the hydrolysis reaction that adds thermal initiation, the alkali precursor is converted under the situation of alkali,, adopt 50 ℃～300 ℃ scope usually, preferably adopt 60 ℃～200 ℃ scope as Heating temperature.Heating temperature is changed in time.If Heating temperature is low excessively, then might not take place to generate the reaction of precipitation agent or need expend the very long time by the precipitation agent precursor; If Heating temperature is too high, then the necessary moisture of hydrolysis sometimes may all be removed before the reaction that is generated precipitation agent by the precipitation agent precursor finishes.In order to implement good and stable sluggish precipitation, preferably when the deposition formation reaction finished, the moisture entrapment in the dipping solution of infiltration in carrier is more than 5%, and was more preferably residual more than 10%.
As the fixed bed heating unit; Can there be the carrier of dipping solution to heat to infiltration at the immobilising state of load carriers; But especially under the situation of a large amount of catalyzer of preparation, more preferably the thermopnore device of working load carrier flow, revolving heating unit etc.According to thinking, when heating, occur under the situation of moisture evaporation, make load carriers mobile method that the water evaporation quantity of every particle loading carrier is changed, thereby further increase uniformity.
In addition; If the moisture evaporation during heating is too fast; Then moisture was all removed before the hydrolysis of alkali precursor finishes fully, can not fully carry out the supply of precipitation agent sometimes, therefore it is desirable to usually; By beginning to be heated to through deposition after formation reaction finishes till removing moisture fully, with more than 1 hour, preferred more than 3 hours, further preferred time more than 6 hours carries out removing fully of moisture.
Thereafter; Water, alkaline aqueous solution, aqueous acid, organic solvent etc. clean resulting catalyzer as required; After the drying; Under inert gas atmospheres such as nitrogen, argon gas or oxidizing gas atmosphere such as air or dilution oxygen, fire, thus the catalyzer that can obtain having desired performance.Heating firing temperature as this moment is generally 100 ℃～1200 ℃, is preferably 300 ℃～1100 ℃, further is preferably 500 ℃～1000 ℃.Fire through carrying out such heating, can make resulting catalyzer, promptly be added with the catalyst activity and the improved stability of the solid acid catalyst of specific metallic element.
Wherein, Above-mentioned operation not all is essential operation; As long as can obtain in solid acid catalyst, being added with the catalyzer that is selected from that this solid acid catalyst do not contain, to the restriction especially of its manufacturing process by at least a metallic element in the group of periodictable the 3rd, 5,10,11 group compositions.
< content of metal >
The catalyzer that obtains with aforesaid method normally in solid acid catalyst the form with oxide compound be added with the catalyzer that adds metallic element.
The catalyzer that uses among the present invention is under the situation of the metal oxide supported catalyzer that on carriers such as silicon-dioxide, adds interpolation metallic elements such as Ni, Cu, Ce in the formed solid acid catalyst and obtain such as zirconium white; With respect to carrier; The content of metal of solid acid catalyst is preferably 0.1 mole of %～15 mole %, is preferably 0.5 mole of %～10 mole % especially.If charge capacity is more than this scope, then metal is difficult to the state load with even and high dispersing, if charge capacity is less than this scope, then can not generate enough acid amounts.And; With respect to carrier, the charge capacity of special metal element is preferably 0.01 mole of %～10 mole %, is preferably 0.05 mole of %～5 mole % especially; Adding metallic element/solid acid catalyst metal molar ratio is preferably 0.01～5, is preferably 0.05～3 especially.
If add the metallic element charge capacity more than this scope, then possibly produce detrimentally affect to the catalyst performance beyond the molecular-weight average, if be less than this scope, then can't fully obtain the change effect of molecular-weight average.
In addition; The catalyzer that uses among the present invention is in as the clay catalyst of solid acid catalyst, add metallic element and under the situation of the catalyzer that forms; With respect to clay catalyst; The addition that adds metallic element is preferably 0.01 weight %～20 weight %, is preferably 0.05 weight %～15 weight % especially.If the charge capacity of adding metallic element more than this scope, then possibly produce detrimentally affect to the catalyst performance beyond the molecular-weight average,, then can not fully obtain the change effect of molecular-weight average if be less than this scope.
[method of manufacture of polyethers]
Down in the face of using solid acid catalyst that containing of as above making add metallic element to describe as the method for manufacture of the polyethers of the present invention of catalyst for polymerization.
The method of manufacture of this polyethers through the ring-opening polymerization of ring-type ethers, promptly be that reaction raw materials carries out ring-opening polymerization to it and carries out with the ring-type ethers.
Make under the situation of polyethers with the ring-opening polymerization of ring-type ethers, as the cyclic ether as reaction raw materials, the formation carbonatoms that can enumerate ring is 3～10 cyclic ether, and, can use with substituted cyclic ethers such as alkyl, halogen radical, acyl groups.Specifically, can use THF, trimethylene oxide, oxepane, 1,4-dioxane, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran etc.And, any polymerization in the homopolymerization that can only use a kind of ring-type ethers and the copolymerization of using two or more ring-type ethers.
Use one or more that as above contain the solid acid catalyst that adds metallic element as catalyzer.
Consider that from the aspect of control molecular weight the ring-opening polymerization of cyclic ether preferably carries out in the presence of carboxylic acid anhydride and/or carboxylic acid.As carboxylic acid anhydride and/or carboxylic acid, generally use aliphatics or aromatic carboxylic acid anhydride and/or carboxylic acid, preferred carboxylic acid anhydride and/or the carboxylic acid that use with 2～8 carbon atoms with 2～12 carbon atoms.These carboxylic acid anhydride and/or carboxylic acid both can use a kind of separately, also can share two or more.It is comparatively suitable that carboxylic acid anhydride and/or carboxylic acid add in the scope that with respect to cyclic ether is 0.01～1.0 (mol ratio) usually.
Can in reaction, use inert solvent during polyreaction.As this solvent, use the divided ring polyreaction to be in inert aliphatic hydrocarbon, the aromatic hydrocarbon etc. one or more usually.
Reaction formation uses the general form of using such as grooved, tower, can be any of batch mode, continuous mode.Following method etc. is for example arranged: cyclic ether, catalyzer, carboxylic acid anhydride and/or carboxylic acid are under agitation fed intake carry out polymeric method (batch mode); In containing the reactor drum of catalyzer, supply with cyclic ether, carboxylic acid anhydride and/or carboxylic acid and continuous method (continuous mode) of extracting reaction solution out etc. continuously.Consider preferred continuous mode from the aspect of productivity.
Catalyst consumption depends on its kind, not special the qualification, but for example in the batch-type reactor drum, if catalytic amount is very few, then polymerization velocity is slack-off, conversely if too much, then be difficult to remove heat of polymerization.And, because the slurry concentration of reaction system uprises, cause stirring difficulty, and be easy to go wrong in the separatory of catalyzer and reaction solution after polyreaction finishes.Therefore, for catalyst consumption, can be generally 0.001～50 times of weight with respect to liquid phase under the condition of the reaction form of considering batch reactions, circulation reaction, be preferably in the scope of 0.01～20 times of weight and select.Wherein, under the situation of circulation reaction, catalyst consumption is represented the amount with respect to the catalyzer of the feed rate of liquid phase of time per unit.
Temperature of reaction is generally 0 ℃～200 ℃, is preferably 10 ℃～80 ℃.
Reaction pressure is that reaction system can keep the pressure of liquid phase to get final product, usually from normal pressure～10MPa, preferably select from the pressure range of normal pressure～5MPa.
To not special qualification of reaction times, consider itself and catalytic amount the two, consider yield, economy, the reaction times is 0.1 hour～20 hours scope, is preferably 0.5 hour～15 hours scope.The said here reaction times is meant, in batch mode, plays the time till reaction finishes to begin to cool down when rising to temperature of reaction by temperature; In continuous mode, the residence time of liquid in reactor drum formed in reaction.
The MWD of the polyethers that generates depends on the kind of starting compound; Carry out under the situation of ring-opening polymerization of THF (THF); Can obtain number-average molecular weight (Mn) is 200～80,000, particularly 200～40, the polyethers of low～middle molecular weight of about 000.And then the polyethers that can easily produce narrow molecular weight distribution also is one of characteristic.Promptly; The Mw/Mn of the polyethers that industrial requirement is bigger is 1.3～2.5; Through utilizing solid acid catalyst of the present invention; Can access Mw/Mn less than 3, for example Mw/Mn is 1.1～3.0 polyethers, particularly through selecting optimum condition of the present invention for use, can also obtain Mw/Mn and be about 1.3～2.0 the very narrow polyethers of MWD.
In addition; Cannot treat different things as the same with respect to the relation between the molecular-weight average of the addition of solid acid catalyst and gained polyethers for adding metallic element in the catalyst system therefor; According to the different polyethers that obtain various molecular-weight average of the kind of adding metallic element, but in general, same interpolation metallic element is added under the situation of same solid acid catalyst into; The addition that adds metallic element is many more, trends towards obtaining the big polyethers of molecular-weight average more.
Polyethers constructed in accordance can be used for purposes such as spandex fiber, thermoplastic polyester elastomer, TPUE, coating material.
[embodiment and comparative example]
Enumerate embodiment and comparative example below to the further explanation particularly of the 4th aspect, but following embodiment does not limit the scope of the 4th aspect.
In addition, in the content below, the GPC (GPC) below the number-average molecular weight (Mn) of the transformation efficiency of THF (THF), polytetramethylene ether diol acetic ester (PTME), MWD (Mw/Mn) are utilized obtains.
The GPC device: Tosoh society makes GPC 8220
Post: TSK-GEL H (30cm) * 2
Detection method: RI
Column temperature: 40 ℃
Mobile phase: THF
Flow velocity: 1ml/min
Sample IR: 500 μ L
Sample concentration: the concentration that is adjusted to polyethers is about 0.1 weight %
[comparative example 3-1]
< preparation of solid acid catalyst >
With 2.84g ZrO (NO
3)
22H
2O and 0.957g urea are dissolved in the homogeneous solution of processing 12.1ml in the de-salted water.(Silysia of Fuji makes, CARiACT Q30, particle diameter 75 μ m～500 μ m in this steeping fluid, to add the 10.0g silica supports under the room temperature; Median size 200 μ m, pore volume 1.21ml/g, average fine pore 30nm); Vibrating mixing held 1 hour every now and then, make its infiltration.Impregnated carrier is packed in the 100ml Erlenmeyer flask, and cover lid carries out 6 hours processing to it in 110 ℃ drying machine.Open the lid of flask after 6 hours, keep this state in 110 ℃ drying machine dry 16 hours.With it in 140 ℃ of further naturally cooling after dry 4 hours.Under the room temperature product that so obtains added and in the 72ml de-salted water, be dissolved with in the 7.2g bicarbonate of ammonia solution of (containing ammonia 20 weight %) in ammonia; Stir 1 hour after-filtration; And then with after the 84ml de-salted water suspension cleaning 3 times; In 120 ℃ of dryings, under airiness, fire in 900 ℃ then, obtain catalyzer.
< polyreaction >
Under nitrogen atmosphere, in the 500ml four-hole boiling flask, add 133.5g THF and 6.85g diacetyl oxide and mix.The above-mentioned catalyzer of weighing 4.68g under nitrogen atmosphere, and after under agitation adding in the said mixed solution, in 40 ℃ of reactions 5 hours.With GPC reaction solution is analyzed, measured transformation efficiency, the molecular-weight average (Mn) of PTME, the MWD (Mw/Mn) of THF, transformation efficiency is 32% as a result, and Mn is 3002, and Mw/Mn is 1.84.
[embodiment 3-1]
With 2.86g ZrO (NO
3)
22H
2O, 0.464g Ce (NO
3)
36H
2O and 1.108g urea are dissolved in the de-salted water; Form the homogeneous solution of 12.1ml, thereby prepare steeping fluid, in addition; Use the method preparation identical to contain the solid acid catalyst that adds metallic element, use this catalyzer likewise to implement polyreaction with comparative example 3-1.
Its result, transformation efficiency is 28%, and Mn is 2664, and Mw/Mn is 1.84.
[embodiment 3-2]
With 2.86g ZrO (NO
3)
22H
2O, 0.432g Fe (NO
3)
39H
2O and 1.108g urea are dissolved in the de-salted water; Form the homogeneous solution of 12.1ml, thereby prepare steeping fluid, in addition; Use the method preparation identical to contain the solid acid catalyst that adds metallic element, use this catalyzer likewise to implement polyreaction with comparative example 3-1.
Its result, transformation efficiency is 36%, and Mn is 3241, and Mw/Mn is 1.82.
[embodiment 3-3]
With 2.86g ZrO (NO
3)
22H
2O, 0.311g Ni (NO
3)
26H
2O and 1.06g urea are dissolved in the de-salted water; Process the homogeneous solution of 12.1ml, thereby prepare steeping fluid, in addition; Use the method preparation identical to contain the solid acid catalyst that adds metallic element, use this catalyzer likewise to implement polyreaction with comparative example 3-1.
Its result, transformation efficiency is 34%, and Mn is 4137, and Mw/Mn is 1.83.
[embodiment 3-4]
With 2.86g ZrO (NO
3)
22H
2O, 0.258g Cu (NO
3)
23H
2O and 1.059g urea are dissolved in the de-salted water; Process the homogeneous solution of 12.1ml, thereby prepare steeping fluid, in addition; Use the method preparation identical to contain the solid acid catalyst that adds metallic element, use this catalyzer likewise to implement polyreaction with comparative example 3-1.
Its result, transformation efficiency is 30%, and Mn is 4059, and Mw/Mn is 1.76.
[comparative example 3-2]
< preparation of solid acid catalyst >
The zirconyl nitrate solution of making in the new Japanese metallochemistry of 88.01g society is (with ZrO
2Meter is 18.46 weight %) middle 22.35g de-salted water, the uniform mixing of adding.To wherein adding 11.89g urea, uniform mixing is processed dipping solution.(Silysia of Fuji makes in this solution, to add the 80g silica supports; CARiACT Q15, particle diameter 75 μ m～500 μ m, median size 200 μ m; Pore volume 116ml/g; Average fine pore 15nm), vibrates and mixed in about 1 hour, with the mode that hole is filled infiltrate (dipping solution amount be carrier pore volume 100%).
In its 500ml pyriform flask of packing into, jointing and the bend pipe that is plugged with glass wool on flask top.With anchor clamps flask be fixed on the turning axle of rotating dryer on thereafter.Speed rotation turning axle with 10rpm is set at 105 ℃ with the drying machine temperature, carries out 2 hours heating.Then, unload the bend pipe that is plugged with glass wool on top after, the drying machine temperature is set at 120 ℃, carry out 16 hours heating.Then, unload the joint on top after, the drying machine temperature is set at 140 ℃, carry out 4 hours heating.After 4 hours, stop heating, rotation, take out catalyzer.Catalyzer is transferred to naturally cool to room temperature in the beaker of 500ml after, add the de-salted water of about 300ml, after the cleaning that suspends was carried out 3 times in about 10 minutes; Air-dry catalyzer; A dry night in 120 ℃ drying machine, under airiness, fire in 900 ℃ then, obtain catalyzer.
< polyreaction >
Use the above-mentioned solid acid catalyst that obtains likewise to implement polyreaction as catalyzer and comparative example 3-1, transformation efficiency is 43% as a result, and Mn is 2116, and Mw/Mn is 1.75.
[embodiment 3-5]
The zirconyl nitrate solution of making in the new Japanese metallochemistry of 77.52g society is (with ZrO
2Meter is 18.46 weight %) middle 23.22g de-salted water and the uniform mixing of adding.To wherein adding 1.03g Ca (NO
3)
24H
2O and uniform mixing.And then add 10.92g urea and uniform mixing, thereby the preparation dipping solution uses the method preparation identical with comparative example 3-2 to contain the solid acid catalyst that adds metallic element in addition, uses this catalyzer likewise to implement polyreaction.
Its result, transformation efficiency is 46%, and Mn is 2279, and Mw/Mn is 1.75.
[embodiment 3-6]
The zirconyl nitrate solution of making in the new Japanese metallochemistry of 77.69g society is (with ZrO
2Meter is 18.46 weight %) middle 20.31g de-salted water and the uniform mixing of adding.To wherein adding 2.12g Ni (NO
3)
26H
2O and uniform mixing.And then add 11.81g urea and uniform mixing, thereby the preparation dipping solution uses the method preparation identical with comparative example 3-2 to contain the solid acid catalyst that adds metallic element in addition, uses this catalyzer likewise to implement polyreaction.
Its result, transformation efficiency is 47%, and Mn is 2687, and Mw/Mn is 1.76.
[embodiment 3-7]
The zirconyl nitrate solution of making in the new Japanese metallochemistry of 77.52g society is (with ZrO
2Meter is 18.46 weight %) middle 23.22g de-salted water and the uniform mixing of adding.To wherein adding 1.05g Cu (NO
3)
23H
2O and uniform mixing.And then add 10.92g urea and uniform mixing, thereby the preparation dipping solution uses the method preparation identical with comparative example 3-2 to contain the solid acid catalyst that adds metallic element in addition, uses this catalyzer likewise to implement polyreaction.
Its result, transformation efficiency is 47%, and Mn is 2983, and Mw/Mn is 1.74.
[embodiment 3-8]
The zirconyl nitrate solution of making in the new Japanese metallochemistry of 77.56g society is (with ZrO
2Meter is 18.46 weight %) middle 20.95g de-salted water and the uniform mixing of adding.To wherein adding 0.35g Cu (NO
3)
23H
2O and 1.70gNi (NO
3)
26H
2O and uniform mixing.And then add 11.13g urea and uniform mixing, thereby the preparation dipping solution uses the method preparation identical with comparative example 3-2 to contain the solid acid catalyst that adds metallic element in addition, uses this catalyzer likewise to implement polyreaction.
Its result, transformation efficiency is 46%, and Mn is 2667, and Mw/Mn is 1.74.
[comparative example 3-3]
Under airiness, 20g was fired 1 hour as the Tonsil OptimumFF of the Sued Chemie society of clay (atlapulgite) catalyzer in 400 ℃; The product that use obtains is as catalyzer; In addition, 3-1 likewise operates with comparative example, implements polyreaction.
Its result, transformation efficiency is 42%, and Mn is 3497, and Mw/Mn is 2.01.
[embodiment 3-9]
With 0.35g Cu (NO
3)
23H
2O is dissolved in the 10g de-salted water and uniform mixing.It is infiltrated up among the Tonsil OptimumFF of 20g as the Sued Chemie society manufacturing of clay catalyst, placed 1 hour.Then, likewise under airiness, carry out 1 hour fire in 400 ℃, prepare and contain the solid acid catalyst that adds metallic element, use this catalyzer, likewise implement polyreaction with comparative example 3-3.
Its result, transformation efficiency is 42%, and Mn is 4002, and Mw/Mn is 2.00.
[embodiment 3-10]
With 0.78g Ni (NO
3)
26H
2O is dissolved in the 10g de-salted water and uniform mixing.It is infiltrated up among the Tonsil OptimumFF of 20g as the Sued Chemie society manufacturing of clay catalyst, placed 1 hour.Then, likewise under airiness, carry out 1 hour fire in 400 ℃, prepare and contain the solid acid catalyst that adds metallic element, use this catalyzer, likewise implement polyreaction with comparative example 3-3.
Its result, transformation efficiency is 39%, and Mn is 4380, and Mw/Mn is 2.01.
The above embodiment and the result of comparative example are summarized in table 3-1～3-3.
[table 3-1]
[table 3-2]
[table 3-3]
Can know by comparative example 3-1 and embodiment 3-1～3-4; Owing to make the interpolation metallic element that contains periodictable 3,5,8,10,11 families in the solid acid catalyst, thereby can under same reaction conditions, only change molecular-weight average and can not produce detrimentally affect other performances.
And, can know that by comparative example 3-2 and embodiment 3-5～3-8 the situation of creating conditions that changes solid acid catalyst also is same with the situation of adding two or more metallic elements.
And then, can know that by comparative example 3-3 and embodiment 3-9,3-10 the situation of in solid acid catalyst, adding metallic element afterwards more also is same.
Use specific mode that the present invention has been carried out detailed explanation, but only it will be apparent to one skilled in the art that otherwise break away from the intent of the present invention and scope, can carry out various changes.
In addition, Japanese patent application that the application proposed based on September 6th, 2005 (the special 2005-258055 of hope) and the Japanese patent application (the special 2005-258056 of hope) that proposed on September 6th, 2005, and quote its full content by reference.
Claims (5)
1. the method for manufacture of a polyethers; It is through in the presence of catalyzer, the cyclic ether ring-opening polymerization being made the method for polyethers; It is characterized in that; Use the catalyzer that obtains as follows as said catalyzer: be selected from by at least a element in the group of periodictable the 1st, 2,4,6,8,9,12,13,14,15,16 and 17 group compositions and can be for containing, make it contain at least a metallic element in the group that the copper, nickel, cerium, iron, the calcium that do not comprise in this solid acid catalyst forms with itself solid acid catalyst with the cyclic ether ring-opening polymerization.
2. the method for manufacture of polyethers as claimed in claim 1; It is characterized in that; As said solid acid catalyst, use one or more the solid acid catalyst be selected from the group of forming by catalyzer, O composite metallic oxide catalyst, clay catalyst and the zeolite catalyst of MOX by load.
3. the method for manufacture of polyethers as claimed in claim 1 is characterized in that, the metallic element that does not comprise in this solid acid catalyst is copper or nickel.
4. according to claim 1 or claim 2 the method for manufacture of polyethers; It is characterized in that; As said solid acid catalyst, use at least a above solid acid catalyst that is selected from the group of forming by clay catalyst, silica-alumina, silica-titania and silicon-dioxide-zirconium white.
5. the method for manufacture of polyethers as claimed in claim 1 is characterized in that, said catalyzer is through utilizing the sluggish precipitation in the carrier pore to make at the pore internal burden metal hydroxides and/or the MOX of carrier.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005258055A JP5050332B2 (en) | 2005-09-06 | 2005-09-06 | Method for producing solid acid catalyst |
| JP2005-258056 | 2005-09-06 | ||
| JP2005258056 | 2005-09-06 | ||
| JP2005-258055 | 2005-09-06 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800327534A Division CN101258181B (en) | 2005-09-06 | 2006-09-05 | Method for manufacturing polyester and solid acid catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102617846A true CN102617846A (en) | 2012-08-01 |
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Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100264941A Pending CN102617846A (en) | 2005-09-06 | 2006-09-05 | Process for production of polyether and process for production of solid acid catalyst |
| CN2012100267155A Pending CN102617847A (en) | 2005-09-06 | 2006-09-05 | Process for production of polyether and process for production of solid acid catalyst |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100267155A Pending CN102617847A (en) | 2005-09-06 | 2006-09-05 | Process for production of polyether and process for production of solid acid catalyst |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR20080041684A (en) |
| CN (2) | CN102617846A (en) |
| TW (1) | TW200714360A (en) |
| WO (1) | WO2007029670A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109311771A (en) * | 2016-06-06 | 2019-02-05 | 揖斐电株式会社 | The manufacturing method of honeycomb structure |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5200350B2 (en) * | 2005-09-06 | 2013-06-05 | 三菱化学株式会社 | Solid acid catalyst for producing polyether and method for producing polyether |
| JP2009235400A (en) * | 2008-03-04 | 2009-10-15 | Mitsubishi Chemicals Corp | Method for producing polyether and catalyst for producing polyether |
| CN113234217B (en) * | 2021-05-27 | 2022-07-12 | 万华化学集团股份有限公司 | Preparation method of solid base catalyst and application of solid base catalyst in continuous production of polyether polyol |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09241374A (en) * | 1996-03-05 | 1997-09-16 | Mitsubishi Chem Corp | Catalyst, its production and process for polymerizing cyclic ether by using this catalyst |
| JPH1053646A (en) * | 1996-08-09 | 1998-02-24 | Mitsubishi Chem Corp | Production of polyoxyalkylene glycol |
| JPH10158386A (en) * | 1996-11-29 | 1998-06-16 | Mitsubishi Chem Corp | Polymerization of cyclic ether |
| US5907054A (en) * | 1996-06-05 | 1999-05-25 | Mitsubishi Chemical Corporation | Process for the polymerization of cyclic ether |
| JP2000327770A (en) * | 1999-05-25 | 2000-11-28 | Mitsubishi Chemicals Corp | Production of polyoxyalkylene glycol or its ester |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3933747B2 (en) * | 1996-06-05 | 2007-06-20 | 三菱化学株式会社 | Polymerization method of cyclic ether |
| FR2769521B1 (en) * | 1997-10-14 | 1999-12-10 | Rhodia Chimie Sa | COMPOSITION BASED ON A GRAFTED METAL OXIDE, ITS PREPARATION AND ITS USE IN AN OPENING POLYMERIZATION PROCESS OF OXYGENIC CYCLES |
| JP3937877B2 (en) * | 2002-03-05 | 2007-06-27 | 日産自動車株式会社 | Fuel reforming catalyst |
| JP2004057869A (en) * | 2002-07-25 | 2004-02-26 | Nissan Motor Co Ltd | Fuel reforming catalyst and manufacturing method of hydrogen enriched gas |
-
2006
- 2006-09-05 KR KR1020087005415A patent/KR20080041684A/en not_active Application Discontinuation
- 2006-09-05 CN CN2012100264941A patent/CN102617846A/en active Pending
- 2006-09-05 CN CN2012100267155A patent/CN102617847A/en active Pending
- 2006-09-05 WO PCT/JP2006/317497 patent/WO2007029670A1/en active Application Filing
- 2006-09-06 TW TW095132815A patent/TW200714360A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09241374A (en) * | 1996-03-05 | 1997-09-16 | Mitsubishi Chem Corp | Catalyst, its production and process for polymerizing cyclic ether by using this catalyst |
| US5907054A (en) * | 1996-06-05 | 1999-05-25 | Mitsubishi Chemical Corporation | Process for the polymerization of cyclic ether |
| JPH1053646A (en) * | 1996-08-09 | 1998-02-24 | Mitsubishi Chem Corp | Production of polyoxyalkylene glycol |
| JPH10158386A (en) * | 1996-11-29 | 1998-06-16 | Mitsubishi Chem Corp | Polymerization of cyclic ether |
| JP2000327770A (en) * | 1999-05-25 | 2000-11-28 | Mitsubishi Chemicals Corp | Production of polyoxyalkylene glycol or its ester |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109311771A (en) * | 2016-06-06 | 2019-02-05 | 揖斐电株式会社 | The manufacturing method of honeycomb structure |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200714360A (en) | 2007-04-16 |
| WO2007029670A1 (en) | 2007-03-15 |
| CN102617847A (en) | 2012-08-01 |
| KR20080041684A (en) | 2008-05-13 |
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