JPH024737A - Production of carbonic acid ester - Google Patents
Production of carbonic acid esterInfo
- Publication number
- JPH024737A JPH024737A JP63156172A JP15617288A JPH024737A JP H024737 A JPH024737 A JP H024737A JP 63156172 A JP63156172 A JP 63156172A JP 15617288 A JP15617288 A JP 15617288A JP H024737 A JPH024737 A JP H024737A
- Authority
- JP
- Japan
- Prior art keywords
- oxidizing agent
- amount
- chloride
- catalyst
- oxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 150000004651 carbonic acid esters Chemical class 0.000 title abstract 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 imidazole) Chemical class 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 150000001879 copper Chemical class 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 150000002460 imidazoles Chemical class 0.000 claims abstract description 5
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 5
- 150000003222 pyridines Chemical class 0.000 claims abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 11
- 150000003230 pyrimidines Chemical class 0.000 claims description 5
- 229910001361 White metal Inorganic materials 0.000 claims description 3
- 239000010969 white metal Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 12
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 6
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 abstract description 4
- 229960003280 cupric chloride Drugs 0.000 abstract description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 abstract description 3
- 150000002978 peroxides Chemical class 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 abstract description 2
- 229960001927 cetylpyridinium chloride Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229920006351 engineering plastic Polymers 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 229910002090 carbon oxide Inorganic materials 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 229940045803 cuprous chloride Drugs 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001242 acetic acid derivatives Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- YNBADRVTZLEFNH-UHFFFAOYSA-N methyl nicotinate Chemical compound COC(=O)C1=CC=CN=C1 YNBADRVTZLEFNH-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical group [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- SBPIDKODQVLBGV-UHFFFAOYSA-N 1h-imidazole;pyridine Chemical class C1=CNC=N1.C1=CC=NC=C1 SBPIDKODQVLBGV-UHFFFAOYSA-N 0.000 description 1
- OKDGRDCXVWSXDC-UHFFFAOYSA-N 2-chloropyridine Chemical compound ClC1=CC=CC=N1 OKDGRDCXVWSXDC-UHFFFAOYSA-N 0.000 description 1
- KIFPIAKBYOIOCS-UHFFFAOYSA-N 2-methyl-2-(trioxidanyl)propane Chemical compound CC(C)(C)OOO KIFPIAKBYOIOCS-UHFFFAOYSA-N 0.000 description 1
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 1
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005752 Copper oxychloride Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HKMOPYJWSFRURD-UHFFFAOYSA-N chloro hypochlorite;copper Chemical compound [Cu].ClOCl HKMOPYJWSFRURD-UHFFFAOYSA-N 0.000 description 1
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 1
- 229960001238 methylnicotinate Drugs 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は触媒の存在下に、脂肪族アルコールを一酸化炭
素及び酸素と反応させて炭酸エステルを製造する方法に
関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a carbonic ester by reacting an aliphatic alcohol with carbon monoxide and oxygen in the presence of a catalyst.
〔従来の技術及び発明が解決しようとする課題〕炭酸エ
ステルは医農薬製造用中間体やエンジニアリングプラス
チックス製造用中間体及び溶媒として工業上有用な物質
である。炭酸エステルの製造法としては、■ホスゲンと
アルコールを反応させて製造する方法、■銅塩触媒の存
在下にアルコールを一酸化炭素及び酸素と反応させて製
造する方法（特公昭６０−５８７３９＞、■パラジウム
と銅塩と第三級アルキルアミン又は複素架橋環式第三級
アミンよりなる触媒の存在下、アルコールを一酸化炭素
及び酸素と反応させて製造する方法（特公昭６１−８８
１６、特公昭６ｌ−４３３３８）が知られている。[Prior Art and Problems to be Solved by the Invention] Carbonic esters are industrially useful substances as intermediates and solvents for the production of pharmaceuticals and agricultural chemicals and engineering plastics. Methods for producing carbonic esters include: (1) a method in which phosgene is reacted with an alcohol; (2) a method in which an alcohol is reacted with carbon monoxide and oxygen in the presence of a copper salt catalyst (Japanese Patent Publication No. 60-58739); ■Production method by reacting alcohol with carbon monoxide and oxygen in the presence of a catalyst consisting of palladium, copper salt, tertiary alkyl amine or hetero-bridged cyclic tertiary amine (Japanese Patent Publication No. 61-88
16, Special Publication Sho 6l-43338) is known.
しかし、これら三種類の製造方法にはそれぞれ次の様な
問題点が残されている。即ち、上記■の方法はホスゲン
の毒性が強いこと及びホスゲンを製造するのに必要な電
解塩素が高価なこと、上記■の方法は一酸化炭素の燃焼
損失が大きいこと及び反応速度が遅いこと、あるいは高
い一酸化炭素分圧及び酸素分圧が必要であること、上記
■の方法は一酸化炭素の燃焼損失が大きいこと及び炭酸
エステルの生成里が少ないこと、などである。However, these three types of manufacturing methods each have the following problems. That is, the above method (①) has the drawbacks that phosgene is highly toxic and the electrolytic chlorine necessary to produce phosgene is expensive, and the above method (③) has a large combustion loss of carbon monoxide and a slow reaction rate. Alternatively, high carbon monoxide partial pressure and oxygen partial pressure are required, and method (2) above has a large combustion loss of carbon monoxide and a small amount of carbonate ester formation.
本発明はこの様な先行技術をふまえて、アルコール、−
酸化炭素、酸素から炭酸エステルを製造する方法におい
て、燃焼損失等による一酸化炭素の選択率の低下を低減
し、かつ高反応速度で炭酸エステルを得る方法を提供す
ることを目的とする。The present invention is based on such prior art, alcohol, -
An object of the present invention is to provide a method for producing a carbonate ester from carbon oxide and oxygen, which reduces decrease in selectivity of carbon monoxide due to combustion loss, etc., and obtains a carbonate ester at a high reaction rate.
本発明者等はパラジウム・銅レドックス触媒系を用いて
アルコール、−酸化炭素、酸素から炭酸エステルを製造
する方法について鋭意努力して助触媒の探索を行ったと
ころ、芳香族第三級アミン、イミダゾール類、ピリジン
類、ピリミジン類及び第三級ピリジニウム塩が助触媒と
して、炭酸エステルの生成量を増加させる点、並びに−
酸化炭素の燃焼損失等による選択率の低下を低減させる
点で優れていることを見出して本発明に到ったものであ
る。The present inventors have made extensive efforts to search for cocatalysts for the production of carbonic esters from alcohol, -carbon oxide, and oxygen using a palladium/copper redox catalyst system, and found that aromatic tertiary amines, imidazole pyridines, pyrimidines and tertiary pyridinium salts act as promoters to increase the amount of carbonate ester produced, and -
The present invention was developed based on the discovery that this method is excellent in reducing the decrease in selectivity due to combustion loss of carbon oxide, etc.
即ち本発明は、■金属銅もしくは銅塩と白金属化合物と
、■芳香族第三級アミン、イミダゾール類、ピリジン類
、ピリミジン類及び第三級ピリジニウム塩よりなる群か
ら選ばれる少なくとも一種の化合物とからなる触媒の存
在下に、脂肪族アルコールを一酸化炭素及び酸化剤と反
応させることを特徴とする炭酸エステルの製造法を提供
するものである。That is, the present invention provides at least one compound selected from the group consisting of: (1) metallic copper or a copper salt and a white metal compound; and (2) at least one compound selected from the group consisting of aromatic tertiary amines, imidazoles, pyridines, pyrimidines, and tertiary pyridinium salts. The present invention provides a method for producing a carbonic ester, which comprises reacting an aliphatic alcohol with carbon monoxide and an oxidizing agent in the presence of a catalyst comprising:
以下に本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明においては、通常−酸化炭素分圧０．５〜２０ｋ
ｇ／ｃｍ２の条件下、一定量の一酸化炭素、酸化剤及び
不活性な希釈ガスをオートクレーブ内に挿入した回分式
あるいは液相連続式反応系において、脂肪族アルコール
を金属銅もしくは銅塩と白金属化合物、及び芳香族第三
級アミン、イミダゾール類、ピリジン類、ピリミジン類
及び第三級ピリジニウム塩よりなる群から選ばれる少な
くとも一種の化合物からなる触媒の存在下に酸化剤及び
−酸化炭素と反応させることにより炭酸エステルが製造
される。In the present invention, usually - carbon oxide partial pressure 0.5 to 20k
g/cm2, aliphatic alcohol is reacted with metallic copper or copper salt in a batch or liquid-phase continuous reaction system in which a fixed amount of carbon monoxide, an oxidizing agent, and an inert diluent gas are inserted into an autoclave. Reaction with an oxidizing agent and carbon oxide in the presence of a catalyst consisting of a metal compound and at least one compound selected from the group consisting of aromatic tertiary amines, imidazoles, pyridines, pyrimidines, and tertiary pyridinium salts. Carbonic ester is produced by this process.
脂肪族アルコールとしては、飽和脂肪族アルコール、例
エハメタノーノペプロパノール、エタノール、ブタノー
ル、エチレンクリコール、プロピレングリコーノペ １
，４−ブタンジオールなどが使用され、通常は溶媒を兼
ねて過剰量使用される。Examples of aliphatic alcohols include saturated aliphatic alcohols, such as ethanol, butanol, ethylene glycol, propylene glycol, etc.
, 4-butanediol, etc. are used, and are usually used in an excess amount to also serve as a solvent.
銅は金属又は塩化第一銅、塩化第二銅等のハロゲン化物
のほか、オキシ塩化銅や硝酸塩、硫酸塩、スルホン酸塩
、酢酸塩、安息香酸塩、蓚酸塩、燐酸塩などの銅塩が使
用される。Copper is a metal or halides such as cuprous chloride and cupric chloride, as well as copper salts such as copper oxychloride, nitrates, sulfates, sulfonates, acetates, benzoates, oxalates, and phosphates. used.
白金属化合物としては、ルテニウム、ロジウム、パラジ
ウムなどの金属又はそれらのハロゲン化物、硝酸塩、硫
酸塩、燐酸塩、酢酸塩、スルホン酸塩あるいはこれらを
活性炭、グラファイト、アルミナ、シリカ−アルミナ、
珪藻土、アスベスト、イオン交換樹脂、珪酸塩、ポリビ
ニールピリジン、マグネシア、カルシア等の担体に担持
したものが使用される。なかでもパラジウムの化合物が
好ましい。Examples of white metal compounds include metals such as ruthenium, rhodium, and palladium, their halides, nitrates, sulfates, phosphates, acetates, and sulfonates, or activated carbon, graphite, alumina, silica-alumina,
Those supported on carriers such as diatomaceous earth, asbestos, ion exchange resins, silicates, polyvinylpyridine, magnesia, and calcia are used. Among these, palladium compounds are preferred.
芳香族第三級アミンとしては、Ｎ、Ｎ−ジメチルアニリ
ン、Ｎ、Ｎ−ジエチルアニリン、４−ジメチルアミノピ
リジンなどが使用され、イミダゾール類としては、イミ
ダゾール、Ｎ−メチルイミダゾール、ベンゾイミダゾー
ルなどが使用され、ピリジン類としてはピリジン、１−
りロロピリジン、２−クロロピリジン、１−ピコリン、
２−ピコリン、２．６−ルチジン、４−ジメチルアミノ
ピリジン、１．１’−ビピリジン、コリジン、ニコチン
酸メチル、イソニコチン酸メチルなどが使用され、ピリ
ミジン類としてはピリミジン、キナゾリンなどが使用さ
れ、第三級ピリジニウム塩としては塩化セチルピリジニ
ウム、塩化ラウリルピリジニウムなどが使用される。As aromatic tertiary amines, N,N-dimethylaniline, N,N-diethylaniline, 4-dimethylaminopyridine, etc. are used, and as imidazoles, imidazole, N-methylimidazole, benzimidazole, etc. are used. The pyridines include pyridine, 1-
lylolopyridine, 2-chloropyridine, 1-picoline,
2-picoline, 2,6-lutidine, 4-dimethylaminopyridine, 1,1'-bipyridine, collidine, methyl nicotinate, methyl isonicotinate, etc. are used, and as pyrimidines, pyrimidine, quinazoline, etc. are used, As the tertiary pyridinium salt, cetylpyridinium chloride, laurylpyridinium chloride, etc. are used.
尚本発明の触媒には、塩化テトラメチルアンモニウム、
塩化ベンジルトリエチルアンモニウム、塩化テトラエチ
ルアンモニウム、臭化テトラエチルアンモニウムなどの
第四級アンモニウム塩；臭化テトラブチルホスホニウム
、塩化テトラフェニルホスホニウムなどの第四級ホスホ
ニウム塩を併用することができる。The catalyst of the present invention includes tetramethylammonium chloride,
Quaternary ammonium salts such as benzyltriethylammonium chloride, tetraethylammonium chloride, and tetraethylammonium bromide; quaternary phosphonium salts such as tetrabutylphosphonium bromide and tetraphenylphosphonium chloride can be used in combination.
酸化剤としては、純酸素ガス、あるいは水・硫黄などの
触媒反応を阻害する成分を除いた空気等の分子状酸素の
他に、ｔｅｒｔ−ブチルヒドロキシパーオキシド、メタ
クロロ過安息香酸、過酢酸、ジーｔｅｒｔ−ブチルパー
オキシドなどの過酸化物等が使用される。As an oxidizing agent, in addition to pure oxygen gas or molecular oxygen such as air excluding components that inhibit the catalytic reaction such as water and sulfur, tert-butyl hydroxyperoxide, metachloroperbenzoic acid, peracetic acid, and Peroxides such as tert-butyl peroxide are used.
本発明の実施に当っては、通常は過剰量の原料の脂肪族
アルコールや、反応によって生成する炭酸エステルが溶
媒を兼ねて使用されるが、別に溶媒を使用することもで
きる。かかる溶媒トシては、ベンゼン、トルエン、キシ
レン等の芳香族炭化水素、オクタン、デカン等の脂肪族
炭化水素、ジブチルエーテル、テトラヒドロフラン、エ
チレングリコールジメチルエーテノヘテトラエチレング
リコールジメチルエーテル等のエーテル、酢酸エチル、
安息香酸メチル等のエステル、アセトニトリル、ベンゾ
ニトリル等のニトリル、Ｎ−メチルピロリドン、Ｎ、Ｎ
’／メチルアセトアミド等のアミド、エチレンジメ
チルウレア等の尿素などが用いられる。In carrying out the present invention, an excess amount of aliphatic alcohol as a raw material or a carbonate ester produced by the reaction is usually used as a solvent, but a separate solvent can also be used. Such solvents include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as octane and decane, ethers such as dibutyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethyl acetate,
Esters such as methyl benzoate, nitriles such as acetonitrile and benzonitrile, N-methylpyrrolidone, N,N
Amides such as '/methylacetamide, ureas such as ethylenedimethylurea, etc. are used.
本発明方法は回分式あるいは液相連続式で、通常、以下
の条件で実施される。温度条件は５０〜２００℃であり
、−酸化炭素分圧が０．５〜２０ｋｇ／ｃｍ２、酸化剤
として酸素を使用する場合には酸素分圧が０．０５〜１
０ｋｇ／Ｃｆ１１２で使用され、過酸化物を使用する場
合には前に示した酸素の使用量と等量が使用される。白
金属化合物の使用量は、通常、反応溶液１βにつき０．
１〜１００ｍｍｏｎの範囲で使用される。金属銅又はそ
の塩の使用量は反応溶液１βにつき０．５〜１０００１
００Ｏ０の範囲で使用される。芳香族第三級アミン、イ
ミダゾール類、ピリジン類、ピリミジン類及び第三級ピ
リジニウム塩の使用量は反応溶液１１につき０．５〜２
００００ｍｍＯβの範囲で使用される。The method of the present invention is carried out in a batch manner or in a continuous liquid phase manner, and is usually carried out under the following conditions. The temperature conditions are 50 to 200°C, - carbon oxide partial pressure is 0.5 to 20 kg/cm2, and when oxygen is used as an oxidizing agent, oxygen partial pressure is 0.05 to 1.
0 kg/Cf112, and if peroxide is used, an amount equivalent to the amount of oxygen shown above is used. The amount of the platinum metal compound to be used is usually 0.000000000000000000000000 for 1.300000000000000000000000000001
It is used in the range of 1 to 100 mmon. The amount of metallic copper or its salt used is 0.5 to 10,001 per 1β of the reaction solution.
Used in the range 0000. The amount of aromatic tertiary amine, imidazole, pyridine, pyrimidine, and tertiary pyridinium salt used is 0.5 to 2 per 11 of the reaction solution.
It is used in the range of 0000 mmOβ.
本発明の方法によれば炭酸エステルの生成量を増加させ
、しかも選択率の低下を低減させることが出来る。According to the method of the present invention, it is possible to increase the amount of carbonate ester produced and to reduce the decrease in selectivity.
次に発明の詳細について以下に例示するいくつかの実施
例で説明するが、これらの実施例は本発明を限定するも
のではない。Next, the details of the invention will be explained with reference to some examples illustrated below, but these examples are not intended to limit the invention.
実施例１
テフロン加工した撹拌機付き３８０艷のオートクレーブ
に塩化パラジウム０．０８ｍｍｏβ、塩化第二銅７，５
ｍｍｏＡ 、ピリジン７、５ｍｍｏＡ及びメタノール４
０ｍ１を挿入し、オートクレーブ内を窒素で置換した。Example 1 Palladium chloride 0.08 mmoβ and cupric chloride 7.5 were placed in a 380-bar autoclave equipped with a Teflon-treated stirrer.
mmoA, pyridine 7, 5 mmoA and methanol 4
0ml was inserted, and the inside of the autoclave was purged with nitrogen.
次いで窒素を２．２ｋｇ／ｃｍ２、−酸化炭素を１０．
８ｋｇ／ｃｍ２．１９ｍｏｆｆ％の酸素を含む酸素・ア
ルゴン混合ガスを７．０ｋｇ／ｃｍ２圧大した後、オー
トクレーブを１３０℃に保ち、１時間反応させた後、常
温まで冷却して放圧し、反応ガス及び反応生成液をガス
クロマトグラフィーにより分析し、炭酸ジメチルの生成
量及び−酸化炭素の吸収量を定量した。結果は表−１に
示す通りであった。Then nitrogen at 2.2 kg/cm2 and carbon oxide at 10.
After increasing the pressure of oxygen/argon mixed gas containing 8kg/cm2.19moff% of oxygen to 7.0kg/cm2, the autoclave was kept at 130°C and reacted for 1 hour, then cooled to room temperature and depressurized to release the reaction gas. The reaction product liquid was analyzed by gas chromatography to determine the amount of dimethyl carbonate produced and the amount of carbon oxide absorbed. The results were as shown in Table-1.
実施例２〜５
ピリジンの代わりに表−１に示した添加物を使用したこ
と以外は実施例１と同じ反応条件で同様な反応を行った
。結果は表−１に示す通りであった。Examples 2 to 5 Similar reactions were carried out under the same reaction conditions as in Example 1, except that the additives shown in Table 1 were used instead of pyridine. The results were as shown in Table-1.
実施例６
塩化第二銅及びピリジンの代わりに塩化第一銅７．５ｍ
ｍｏＡ 、 ２．６−ルチジン７、５ｍｍｏｌ、塩化
テトラエチルアンモニウム７、５ｍｍｏｊ２を使用した
こと以外は実施例１と同じ反応条件で同様な反応を行っ
た。結果は表−１に示す通りであった。Example 6 Cuprous chloride 7.5m instead of cupric chloride and pyridine
A similar reaction was carried out under the same reaction conditions as in Example 1, except that moA, 2.6-lutidine 7, 5 mmol, and tetraethylammonium chloride 7,5 mmol were used. The results were as shown in Table-1.
比較例１
ピリジンの代わりにトリノルマルブチルアミンを使用し
た以外は、実施例１と同じ反応条件で同様な反応を行っ
た。結果は表′−１に示す通りであった。Comparative Example 1 A similar reaction was carried out under the same reaction conditions as in Example 1, except that tri-n-butylamine was used instead of pyridine. The results were as shown in Table'-1.
表−１
（注）−酸化炭素の炭酸ジメチル（ＤＭＣ）への選択率
（Ｓ Ｃｏ−ＤＭＣ）は、下式に従って示される。Table 1 (Note) - The selectivity of carbon oxide to dimethyl carbonate (DMC) (S Co-DMC) is shown according to the following formula.
実施例７〜１０
ピリジンの代わりに４−ジメチルアミノピリジンを使用
し、表−２に示した一酸化炭素、酸素の条件で、実施例
１と同様な反応を行った。Examples 7 to 10 Reactions similar to those in Example 1 were carried out using 4-dimethylaminopyridine instead of pyridine and using the carbon monoxide and oxygen conditions shown in Table 2.
結果は表−２に示す通りであった。The results were as shown in Table-2.
表−２
実施例１１
実施例１で使用したオートクレーブを用いて、塩化パラ
ジウムＱ、 ｌ＋ｙ＋＋ｒ＋ｏｌ、塩化第一銅０．４ｍ
ｍｏ！！、ピリジンＱ、 ３ｍｍｏｌ及びメタノール７
０−を挿入したオートクレーブ内を窒素で置換した。次
いで窒素を５．７ｋｇ／ｃｍ２、−酸化炭素３．６ｋｇ
／ｃｍ２．３３ｍｏｂ％の酸素を含む酸素・アルゴン混
合ガスを２、７ｋｇ／ｃｍ２圧大した後、実施例１と同
様の操作を行った。Table 2 Example 11 Using the autoclave used in Example 1, palladium chloride Q, l+y++r+ol, cuprous chloride 0.4 m
mo! ! , pyridine Q, 3 mmol and methanol 7
The inside of the autoclave into which 0- was inserted was purged with nitrogen. Then 5.7 kg/cm2 of nitrogen, -3.6 kg of carbon oxide
After increasing the pressure of the oxygen/argon mixed gas containing 33 mob% of oxygen/cm2 to 2.7 kg/cm2, the same operation as in Example 1 was performed.
その結果、炭酸ジメチルの生成量は１４．１ｍｍｏｌで
あり、Ｓ ＣＯ−ＤＭＣは４８％であった。As a result, the amount of dimethyl carbonate produced was 14.1 mmol, and the amount of S CO-DMC was 48%.
実施例１２
ピリジンの代わりにイミダゾールを使用した以外は、実
施例１１と同じ反応条件で同様な反応を行った。Example 12 A similar reaction was carried out under the same reaction conditions as in Example 11, except that imidazole was used instead of pyridine.
その結果、炭酸ジメチルの生成量は５．４ｍｍｏＡであ
り、ＳＣＯ−ＤＭＣは３２％であった。As a result, the amount of dimethyl carbonate produced was 5.4 mmoA, and the amount of SCO-DMC was 32%.
比較例２
テフロン加工した撹拌機付き３３０ｍｊｌ！のオートク
レーブに塩化第一銅Ｑ、 ４ｍｍｏＡとメタノール３８
−を挿入し、オートクレーブ内を窒素で置換した。次い
で窒素を５．７ｋｇ／ｃｍ２ −酸化炭素３．６ｋｇ／
ｃｍ２．３３ｍｏＡ％の酸素を含む酸素・アルゴン混合
ガスを２．７ｋｇ／ｃｍ２を圧入した後、実施例１と同
様な操作を行った。Comparative Example 2 330 mjl with Teflon-treated stirrer! cuprous chloride Q, 4 mmoA and methanol 38 in an autoclave.
- was inserted, and the inside of the autoclave was replaced with nitrogen. Next, nitrogen was added at 5.7 kg/cm2 - carbon oxide 3.6 kg/
After pressurizing 2.7 kg/cm2 of oxygen/argon mixed gas containing oxygen at 2.33 moA%, the same operation as in Example 1 was performed.
その結果、炭酸ジメチルの生成量は３．２ｍｍ’ｏβで
あり、Ｓ Ｃｏ−ＤＭＣは２４％であった。As a result, the amount of dimethyl carbonate produced was 3.2 mm'oβ, and the amount of S Co-DMC was 24%.
Claims (1)
香族第三級アミン、イミダゾール類、ピリジン類、ピリ
ミジン類及び第三級ピリジニウム塩よりなる群から選ば
れる少なくとも一種の化合物とからなる触媒の存在下に
、脂肪族アルコールを一酸化炭素及び酸化剤と反応させ
ることを特徴とする炭酸エステルの製造法。(1) metallic copper or a copper salt and a white metal compound; and (2) at least one compound selected from the group consisting of aromatic tertiary amines, imidazoles, pyridines, pyrimidines, and tertiary pyridinium salts. A method for producing a carbonate ester, which comprises reacting an aliphatic alcohol with carbon monoxide and an oxidizing agent in the presence of a catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63156172A JPH024737A (en) | 1988-06-24 | 1988-06-24 | Production of carbonic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63156172A JPH024737A (en) | 1988-06-24 | 1988-06-24 | Production of carbonic acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH024737A true JPH024737A (en) | 1990-01-09 |
Family
ID=15621925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63156172A Pending JPH024737A (en) | 1988-06-24 | 1988-06-24 | Production of carbonic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH024737A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5251501A (en) * | 1991-09-30 | 1993-10-12 | Nsk Ltd. | Intermediate support device for screw shaft |
| US5370214A (en) * | 1992-10-14 | 1994-12-06 | Nsk Ltd. | Movable member feed device |
| US5531557A (en) * | 1994-07-01 | 1996-07-02 | Rite-Hite Corporation | Drive screw system with nested mobile supports |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5545655A (en) * | 1978-09-28 | 1980-03-31 | Mitsubishi Chem Ind Ltd | Production of carbonate ester |
| JPS56167641A (en) * | 1980-04-26 | 1981-12-23 | Bayer Ag | Manufacture of carbonic acid ester |
| JPS6281356A (en) * | 1985-09-30 | 1987-04-14 | テキサコ・デベロツプメント・コ−ポレ−シヨン | Manufacture of organic carbonic acid ester |
-
1988
- 1988-06-24 JP JP63156172A patent/JPH024737A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5545655A (en) * | 1978-09-28 | 1980-03-31 | Mitsubishi Chem Ind Ltd | Production of carbonate ester |
| JPS56167641A (en) * | 1980-04-26 | 1981-12-23 | Bayer Ag | Manufacture of carbonic acid ester |
| JPS6281356A (en) * | 1985-09-30 | 1987-04-14 | テキサコ・デベロツプメント・コ−ポレ−シヨン | Manufacture of organic carbonic acid ester |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5251501A (en) * | 1991-09-30 | 1993-10-12 | Nsk Ltd. | Intermediate support device for screw shaft |
| US5370214A (en) * | 1992-10-14 | 1994-12-06 | Nsk Ltd. | Movable member feed device |
| US5531557A (en) * | 1994-07-01 | 1996-07-02 | Rite-Hite Corporation | Drive screw system with nested mobile supports |
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