JP2012224494A - Method for producing carbonyl sulfide - Google Patents
Method for producing carbonyl sulfide Download PDFInfo
- Publication number
- JP2012224494A JP2012224494A JP2011092439A JP2011092439A JP2012224494A JP 2012224494 A JP2012224494 A JP 2012224494A JP 2011092439 A JP2011092439 A JP 2011092439A JP 2011092439 A JP2011092439 A JP 2011092439A JP 2012224494 A JP2012224494 A JP 2012224494A
- Authority
- JP
- Japan
- Prior art keywords
- ene
- carbonyl sulfide
- sulfur
- triazabicyclo
- carbon monoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011593 sulfur Substances 0.000 claims abstract description 28
- -1 cyclic secondary amine Chemical class 0.000 claims abstract description 26
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 15
- 150000001409 amidines Chemical class 0.000 claims abstract description 14
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 10
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 34
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 20
- OEBXWWBYZJNKRK-UHFFFAOYSA-N 1-methyl-2,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine Chemical compound C1CCN=C2N(C)CCCN21 OEBXWWBYZJNKRK-UHFFFAOYSA-N 0.000 claims description 16
- UURSXESKOOOTOV-UHFFFAOYSA-N dec-5-ene Chemical compound CCCCC=CCCCC UURSXESKOOOTOV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 6
- WWLBWFDOHOYGIL-UHFFFAOYSA-N CN(C)[PH4] Chemical compound CN(C)[PH4] WWLBWFDOHOYGIL-UHFFFAOYSA-N 0.000 claims description 3
- YYYXREXEAQIJTR-UHFFFAOYSA-N N1(CCCC1)[PH4] Chemical compound N1(CCCC1)[PH4] YYYXREXEAQIJTR-UHFFFAOYSA-N 0.000 claims description 3
- 125000005277 alkyl imino group Chemical group 0.000 claims 1
- 238000005530 etching Methods 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000002585 base Substances 0.000 description 16
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 12
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Inorganic materials S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- VSCBATMPTLKTOV-UHFFFAOYSA-N 2-tert-butylimino-n,n-diethyl-1,3-dimethyl-1,3,2$l^{5}-diazaphosphinan-2-amine Chemical compound CCN(CC)P1(=NC(C)(C)C)N(C)CCCN1C VSCBATMPTLKTOV-UHFFFAOYSA-N 0.000 description 1
- HFKVKGYQGDZBTJ-UHFFFAOYSA-N 3-[4-[[bis[(1-tert-butyltriazol-4-yl)methyl]amino]methyl]triazol-1-yl]propan-1-ol Chemical compound N1=NN(C(C)(C)C)C=C1CN(CC=1N=NN(C=1)C(C)(C)C)CC1=CN(CCCO)N=N1 HFKVKGYQGDZBTJ-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XIYLJKDSPVXWSV-UHFFFAOYSA-N CN(C)P(N(C)C)(N(C)C)=NC Chemical compound CN(C)P(N(C)C)(N(C)C)=NC XIYLJKDSPVXWSV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YRNOSHBJMBLOSL-UHFFFAOYSA-N n-[tert-butylimino-bis(dimethylamino)-$l^{5}-phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(N(C)C)(N(C)C)=NC(C)(C)C YRNOSHBJMBLOSL-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JEUZJMXPVCUAMW-UHFFFAOYSA-N o-methyl n,n-diethylcarbamothioate Chemical compound CCN(CC)C(=S)OC JEUZJMXPVCUAMW-UHFFFAOYSA-N 0.000 description 1
- BMGULSOUUKULAV-UHFFFAOYSA-N o-methyl n,n-dipropylcarbamothioate Chemical compound CCCN(CCC)C(=S)OC BMGULSOUUKULAV-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000019086 sulfide ion homeostasis Effects 0.000 description 1
- PVNUIRUAPVSSOK-UHFFFAOYSA-N tert-butylimino(tripyrrolidin-1-yl)-$l^{5}-phosphane Chemical compound C1CCCN1P(N1CCCC1)(=NC(C)(C)C)N1CCCC1 PVNUIRUAPVSSOK-UHFFFAOYSA-N 0.000 description 1
- 150000003510 tertiary aliphatic amines Chemical class 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 230000002463 transducing effect Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、硫化カルボニルの製造方法に関する。特に、硫黄と一酸化炭素を液相で反応させて硫化カルボニルを製造する方法に関する。 The present invention relates to a method for producing carbonyl sulfide. In particular, the present invention relates to a method for producing carbonyl sulfide by reacting sulfur and carbon monoxide in a liquid phase.
硫化カルボニルは、有機系反射防止膜のプラズマによる高異方性および高選択性エッチング用のエッチングガスとして注目される重要な化合物である。従来、この硫化カルボニルの製造方法としては、炭酸ガスと二硫化炭素とを反応させる方法と、硫黄と一酸化炭素とを反応させる方法が知られている。 Carbonyl sulfide is an important compound that is attracting attention as an etching gas for high anisotropy and high selectivity etching of organic antireflection films by plasma. Conventionally, as a method for producing this carbonyl sulfide, a method of reacting carbon dioxide with carbon disulfide and a method of reacting sulfur with carbon monoxide are known.
炭酸ガスと二硫化炭素とを触媒の存在下、気相で反応する方法が、例えば、米国特許第４１２０９４４号明細書（特許文献１）、米国特許第３４０９３９９号明細書（特許文献２）、特公昭４７−４０６３２号公報（特許文献３）に記載されているが、触媒活性低下が課題である。硫黄と一酸化炭素とを反応させる硫化カルボニルの製造方法は、気相での反応と液相での反応が知られている。気相での反応は、例えば、特公昭５６−４５８４７号公報（特許文献４）、特公昭６１−５４０９号公報（特許文献５）には、触媒の存在下または無触媒で硫黄と一酸化炭素を反応させる方法が記載されているが、過剰に用いる硫黄の分離が必要であり、さらに、いったん生成した硫化カルボニルが高温のため、分解する恐れがある。無触媒の場合、きわめて高い反応温度が必要であり、高価な耐食材料を用いる必要がある。 A method of reacting carbon dioxide gas and carbon disulfide in the gas phase in the presence of a catalyst is disclosed in, for example, US Pat. No. 4,120,944 (Patent Document 1), US Pat. No. 3,409,399 (Patent Document 2), Although described in Japanese Examined Patent Publication No. 47-40632 (Patent Document 3), reduction of catalyst activity is a problem. As a method for producing carbonyl sulfide in which sulfur and carbon monoxide are reacted, a reaction in a gas phase and a reaction in a liquid phase are known. For example, Japanese Patent Publication No. 56-45847 (Patent Document 4) and Japanese Patent Publication No. 61-5409 (Patent Document 5) describe reactions in the gas phase in the presence or absence of a catalyst and sulfur and carbon monoxide. However, it is necessary to separate excess sulfur, and the carbonyl sulfide once formed may be decomposed due to high temperature. In the case of non-catalyst, a very high reaction temperature is required, and it is necessary to use an expensive corrosion-resistant material.
硫黄と一酸化炭素とを反応させる硫化カルボニルの製造方法のうち、液相での反応は、以下の特許文献に記載されている方法が知られている。
（１）米国特許第２９９２８９６号明細書（特許文献６）には、脂肪族アルコール溶媒中、脂肪族３級アミンと硫化水素を懸濁させ、硫黄と一酸化炭素とを反応させて硫化カルボニルを製造する方法が記載されている。
（２）米国特許第２９９２８９７号明細書（特許文献７）には、脂肪族アルコール溶媒を用い、アルカリあるいはアルカリ土類金属のサルファイド、バイサルファイドを触媒に用い、硫黄と一酸化炭素を反応させて硫化カルボニルを製造する方法が記載されている。
（３）米国特許第２９９２８９８号明細書（特許文献８）には、水酸基を有する３級脂肪族アミン溶液中で硫黄と一酸化炭素を反応させて硫化カルボニルを製造する方法が記載されている。
（４）米国特許第３２３５３３３号明細書（特許文献９）には、触媒として、アルカリ金属のカルボン酸塩、アルカリ金属の蟻酸塩、アルカリ金属の酢酸塩、Ｉ、ＩＩあるいはＩＩＩ族金属のアルコキシド、テトラメチルグアニジン、蟻酸カリウムのいずれかを用い、５０℃から１５０℃の温度、一酸化炭素の圧力が２００ｐｓｉｇ（１．３８ＭＰａ）から５０００ｐｓｉｇ（３４．４ＭＰａ）で硫黄と一酸化炭素を反応させて硫化カルボニルを製造する方法が記載されている。
（５）特開昭６１−１９７４１４号公報（特許文献１０）には、２級脂肪族アミンを、セレン（Ｓｅ）を触媒として、一酸化炭素と硫黄とを反応させることによりチオカルバミン酸アミン塩を製造し、生成したチオカルバミン酸アミン塩を加熱することにより、硫化カルボニルと２級アミンに分解し、得られた２級アミン反応液を再度一酸化炭素と硫黄と反応させる、連続的に硫化カルボニルを製造する方法が記載されている。
（６）国際公開第２００４／０８９８２４号（特許文献１１）には、二硫化炭素に溶解した硫黄と一酸化炭素とを反応させる硫化カルボニルの製造プロセスが記載されている。
Among the methods for producing carbonyl sulfide in which sulfur and carbon monoxide are reacted, the methods described in the following patent documents are known for the reaction in the liquid phase.
(1) In U.S. Pat. No. 2,992,896 (Patent Document 6), an aliphatic tertiary amine and hydrogen sulfide are suspended in an aliphatic alcohol solvent, and sulfur and carbon monoxide are reacted to form carbonyl sulfide. A method of manufacturing is described.
(2) In US Pat. No. 2,992,897 (Patent Document 7), an aliphatic alcohol solvent is used, and an alkali or alkaline earth metal sulfide or bisulfide is used as a catalyst to react sulfur with carbon monoxide. A method for producing carbonyl sulfide is described.
(3) U.S. Pat. No. 2,992,898 (Patent Document 8) describes a method for producing carbonyl sulfide by reacting sulfur and carbon monoxide in a tertiary aliphatic amine solution having a hydroxyl group.
(4) In U.S. Pat. No. 3,235,333 (Patent Document 9), as a catalyst, an alkali metal carboxylate, an alkali metal formate, an alkali metal acetate, an I, II or III group alkoxide, Using either tetramethylguanidine or potassium formate, sulfur and carbon monoxide are reacted by reacting sulfur and carbon monoxide at a temperature of 50 ° C. to 150 ° C. and a pressure of carbon monoxide of 200 psig (1.38 MPa) to 5000 psig (34.4 MPa). A method for producing carbonyl is described.
(5) JP-A 61-197414 (Patent Document 10) discloses a thiocarbamic acid amine salt obtained by reacting a secondary aliphatic amine with carbon monoxide and sulfur using selenium (Se) as a catalyst. The resulting thiocarbamic acid amine salt is heated to decompose into carbonyl sulfide and secondary amine, and the resulting secondary amine reaction solution is reacted again with carbon monoxide and sulfur. A method for producing carbonyl is described.
(6) International Publication No. 2004/088984 (Patent Document 11) describes a process for producing carbonyl sulfide in which sulfur dissolved in carbon disulfide is reacted with carbon monoxide.
しかしながら、上記の（１）〜（６）の硫化カルボニルの製造方法は、以下の点で依然として改善の余地がある。
（１）、（２）、（３）の製造方法は、液相で、比較的低温でも硫黄と一酸化炭素から硫化カルボニルが生成することを示しているが、選択性、品質についてはなんら述べられていない。（１）や（２）の方法は、溶媒に脂肪族アルコールやグリコール類を用いることから、副生成物の生成は避けられない。
（４）の製造方法は、触媒量のアルカリの存在で、比較的低温で、望ましくは８０℃から１５０℃で、硫黄と一酸化炭素を反応させるが、一酸化炭素の圧力が、１．３８ＭＰａ（２００ｐｓｉｇ）以上、望ましくは３．４４ＭＰａ（５００ｐｓｉｇ）以上の圧力が開示されており、比較的高い圧力が必要である。さらに、実施例は、大部分メタノールを溶媒に用いて行われており、溶媒は、メタノールが最適と思えるが、アルカリ条件では、生成した硫化カルボニルがアルカリ条件下で反応するおそれがあり、副生成物を伴うおそれがある。
（５）の製造方法は、まず、一酸化炭素と、硫黄と２当量の２級アミンからチオカルバミン酸アミン塩を作り、これを熱分解する、という２段反応であり、しかも、有害性の高いセレンを用いる必要があり、有利な工業生産の方法とはいえない。
（６）の製造方法は、二硫化炭素に溶解した硫黄が一酸化炭素と反応して硫化カルボニルが生成することを前提に、製造プロセスの組み立て方法が開示されているが、反応条件、触媒の有無については何も記載されていない。
However, the above-mentioned carbonyl sulfide production methods (1) to (6) still have room for improvement in the following points.
The production methods (1), (2), and (3) show that carbonyl sulfide is produced from sulfur and carbon monoxide even in a liquid phase even at a relatively low temperature. It is not done. In the methods (1) and (2), the production of by-products is inevitable because aliphatic alcohols and glycols are used as the solvent.
In the production method (4), sulfur and carbon monoxide are reacted at a relatively low temperature, preferably at 80 ° C. to 150 ° C., in the presence of a catalytic amount of alkali. The pressure of carbon monoxide is 1.38 MPa. A pressure of (200 psig) or higher, desirably 3.44 MPa (500 psig) or higher is disclosed, and a relatively high pressure is required. Furthermore, the examples are mostly carried out using methanol as the solvent, and methanol seems to be optimal as the solvent. However, under alkaline conditions, the produced carbonyl sulfide may react under alkaline conditions. There is a risk of accompanying things.
The production method (5) is a two-stage reaction in which a thiocarbamic acid amine salt is first made from carbon monoxide, sulfur and 2 equivalents of a secondary amine and then thermally decomposed. It is necessary to use high selenium, which is not an advantageous industrial production method.
The production method (6) discloses a method for assembling the production process on the assumption that sulfur dissolved in carbon disulfide reacts with carbon monoxide to produce carbonyl sulfide. Nothing is stated about the presence or absence.
本発明は、上記のような従来技術に伴う問題を解決しようとするものであって、有機系反射防止膜のプラズマによる高異方性、高選択性エッチング用のエッチングガスとして注目される重要な化合物である硫化カルボニル（ＣＯＳ）を効率よく簡便に、かつ安価に製造する方法を提供することを目的としている。 The present invention is intended to solve the problems associated with the prior art as described above, and is important as an etching gas for high anisotropy and high selectivity etching by plasma of an organic antireflection film. An object of the present invention is to provide a method for efficiently and easily producing carbonyl sulfide (COS), which is a compound, at low cost.
高純度の硫化カルボニルを製造する際、選択性と熱的安定性を考慮して、より低温での反応を実現すべく、鋭意検討を重ねた結果、塩基性有機化合物を触媒として用い、硫黄と一酸化炭素とを適当な有機溶媒を用いて反応することにより、穏やかな条件で、高選択率で硫化カルボニルを製造しうることを見出し、本発明に至った。 In the production of high-purity carbonyl sulfide, considering the selectivity and thermal stability, as a result of intensive studies to realize a reaction at a lower temperature, a basic organic compound was used as a catalyst, and sulfur and It has been found that by reacting carbon monoxide with an appropriate organic solvent, carbonyl sulfide can be produced with high selectivity under mild conditions, and the present invention has been achieved.
すなわち、本発明は、有機溶媒中で一酸化炭素と硫黄を反応させて硫化カルボニルを製造する方法であって、触媒としてアミジン塩基、フォスファゼン塩基、１，５，７−トリアザビシクロ［４．４．０］デカ−５−エン、７−メチル−１，５，７−トリアザビシクロ［４．４．０］デカ−５−エン、アルキル基またはアラルキル基で置換された４級アンモニウムハイドロオキサイド、脂肪族環状２級アミンおよび脂肪族２級アミンからなる群から選択される少なくとも１種の塩基性有機化合物を用いることを特徴とする。 That is, the present invention is a method for producing carbonyl sulfide by reacting carbon monoxide and sulfur in an organic solvent, and as a catalyst, amidine base, phosphazene base, 1,5,7-triazabicyclo [4.4. .0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, a quaternary ammonium hydroxide substituted with an alkyl group or an aralkyl group, It is characterized by using at least one basic organic compound selected from the group consisting of an aliphatic cyclic secondary amine and an aliphatic secondary amine.
さらに具体的には、本発明は、以下の［１］〜［３］項に関する。
［１］ 有機溶媒中で一酸化炭素と硫黄を反応させて硫化カルボニルを製造する方法であって、触媒としてアミジン塩基、フォスファゼン塩基、１，５，７−トリアザビシクロ［４．４．０］デカ−５−エン、７−メチル−１，５，７−トリアザビシクロ［４．４．０］デカ−５−エン、アルキル基またはアラルキル基で置換された４級アンモニウムハイドロオキサイド、脂肪族環状２級アミンおよび脂肪族２級アミンからなる群から選択される少なくとも１種の塩基性有機化合物を用いることを特徴とする方法。
［２］ 塩基性有機化合物がアミジン塩基、フォスファゼン塩基、１，５，７−トリアザビシクロ［４．４．０］デカ−５−エンおよび７−メチル−１，５，７−トリアザビシクロ［４．４．０］デカ−５−エンから選ばれる、［１］に記載の硫化カルボニルの製造方法。
［３］ アミジン塩基が１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エンおよび１，５−ジアザビシクロ［４．３．０］ノナ−５−エンからなる群から選ばれ、フォスファゼン塩基がアルキルイミノ−トリス（ジメチルアミノ）ホスホラン（ただし、アルキルは炭素数１〜８個のアルキル基である。）およびアルキルイミノ−トリス（ピロリジノ）ホスホラン（ただし、アルキルは炭素数１〜８個のアルキル基である。）からなる群から選ばれる、［１］または［２］に記載の硫化カルボニルの製造方法。
More specifically, the present invention relates to the following items [1] to [3].
[1] A method for producing carbonyl sulfide by reacting carbon monoxide and sulfur in an organic solvent, wherein an amidine base, phosphazene base, 1,5,7-triazabicyclo [4.4.0] is used as a catalyst. Deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, quaternary ammonium hydroxide substituted with alkyl group or aralkyl group, aliphatic cyclic A method using at least one basic organic compound selected from the group consisting of secondary amines and aliphatic secondary amines.
[2] The basic organic compound is an amidine base, phosphazene base, 1,5,7-triazabicyclo [4.4.0] dec-5-ene and 7-methyl-1,5,7-triazabicyclo [ 4.4.0] The method for producing carbonyl sulfide according to [1], selected from deca-5-ene.
[3] A phosphazene base wherein the amidine base is selected from the group consisting of 1,8-diazabicyclo [5.4.0] undec-7-ene and 1,5-diazabicyclo [4.3.0] non-5-ene. Are alkylimino-tris (dimethylamino) phosphorane (wherein alkyl is an alkyl group having 1 to 8 carbon atoms) and alkylimino-tris (pyrrolidino) phosphorane (wherein alkyl is alkyl having 1 to 8 carbon atoms) The method for producing carbonyl sulfide according to [1] or [2], which is selected from the group consisting of:
本発明の製造方法によれば、硫化カルボニル（ＣＯＳ）を、効率よく簡便に、かつ安価に製造することができる。 According to the production method of the present invention, carbonyl sulfide (COS) can be produced efficiently and simply at low cost.
本発明は、有機溶媒中、塩基性有機化合物を触媒として用いて、一酸化炭素と硫黄とを反応することを特徴とする硫化カルボニルの製造方法である。 The present invention is a method for producing carbonyl sulfide, which comprises reacting carbon monoxide and sulfur in an organic solvent using a basic organic compound as a catalyst.
本発明において使用する触媒は、アミジン塩基、フォスファゼン塩基、１，５，７−トリアザビシクロ［４．４．０］デカ−５−エン（ＴＢＤ）、７−メチル−１，５，７−トリアザビシクロ［４．４．０］デカ−５−エン（ＭＴＢＤ）、アルキル基またはアラルキル基で置換された４級アンモニウムハイドロオキサイド、脂肪族環状２級アミンおよび脂肪族２級アミンからなる群から選択される少なくとも１種の塩基性有機化合物である。 The catalyst used in the present invention includes amidine base, phosphazene base, 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), 7-methyl-1,5,7-tria. Selected from the group consisting of xabicyclo [4.4.0] dec-5-ene (MTBD), quaternary ammonium hydroxide substituted with alkyl or aralkyl groups, aliphatic cyclic secondary amines and aliphatic secondary amines At least one basic organic compound.
アミジン塩基とは、アミジン骨格を有する塩基性有機化合物をいう。ここで、アミジン骨格とは式（１）で表される構造をいう。 An amidine base refers to a basic organic compound having an amidine skeleton. Here, the amidine skeleton means a structure represented by the formula (1).
アミジン塩基の具体例としては、１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン（ＤＢＵ）、１，５−ジアザビシクロ［４．３．０］ノナ−５−エン（ＤＢＮ）等が挙げられる。 Specific examples of the amidine base include 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5-diazabicyclo [4.3.0] non-5-ene (DBN) and the like. Is mentioned.
フォスファゼン塩基とは、フォスファゼン骨格を有する塩基性有機化合物をいう。ここで、フォスファゼン骨格とは式（２）で表される構造をいう。 A phosphazene base refers to a basic organic compound having a phosphazene skeleton. Here, the phosphazene skeleton means a structure represented by the formula (2).
フォスファゼン塩基の具体例としては、アルキルイミノ−トリス（ジメチルアミノ）ホスホラン（ただし、アルキルは炭素数１〜８個のアルキル基である。）、アルキルイミノ−トリス（ピロリジノ）ホスホラン（ただし、アルキルは炭素数１〜８個のアルキル基である。）等が挙げられる。 Specific examples of the phosphazene base include alkylimino-tris (dimethylamino) phosphorane (wherein alkyl is an alkyl group having 1 to 8 carbon atoms), alkylimino-tris (pyrrolidino) phosphorane (wherein alkyl is carbon It is an alkyl group of several 1 to 8).
脂肪族２級アミンとしては、ジ−ｎ−プロピルアミン、ジエチルアミン、ジ−ｎ−ブチルアミン等が挙げられる。 Examples of the aliphatic secondary amine include di-n-propylamine, diethylamine, and di-n-butylamine.
脂肪族環状２級アミンとしては、ピロリジン、ピペラジン、ピペリジン、モルフォリン等が挙げられる。 Examples of the aliphatic cyclic secondary amine include pyrrolidine, piperazine, piperidine, morpholine and the like.
アルキル基またはアラルキル基で置換された４級アンモニウムハイドロオキサイドにおけるアルキル基は、好ましくは炭素数１〜４個のアルキル基であり、その具体例としては、メチル、エチル、ｎ−プロピル、ｎ−ブチルが挙げられる。
アルキル基またはアラルキル基で置換された４級アンモニウムハイドロオキサイドにおけるアラルキル基は、好ましくは炭素数７〜１０個のアラルキル基であり、その具体例としては、ベンジル、パラメチルベンジルが挙げられる。
アルキル基またはアラルキル基で置換された４級アンモニウムハイドロオキサイドの具体例としては、テトラメチルアンモニウムハイドロオキサイド、ベンジルトリメチルアンモニウムハイドロオキサイド、テトラ−ｎ−ブチルアンモニウムハイドロオキサイドが挙げられる。
The alkyl group in the quaternary ammonium hydroxide substituted with an alkyl group or an aralkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and specific examples thereof include methyl, ethyl, n-propyl, and n-butyl. Is mentioned.
The aralkyl group in the quaternary ammonium hydroxide substituted with an alkyl group or an aralkyl group is preferably an aralkyl group having 7 to 10 carbon atoms, and specific examples thereof include benzyl and paramethylbenzyl.
Specific examples of the quaternary ammonium hydroxide substituted with an alkyl group or an aralkyl group include tetramethylammonium hydroxide, benzyltrimethylammonium hydroxide, and tetra-n-butylammonium hydroxide.
以上の塩基性有機化合物のなかでも、アミジン塩基、フォスファゼン塩基、１，５，７−トリアザビシクロ［４．４．０］デカ−５−エン（ＴＢＤ）および７−メチル−１，５，７−トリアザビシクロ［４．４．０］デカ−５−エン（ＭＴＢＤ）が好ましい。 Among the above basic organic compounds, amidine base, phosphazene base, 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) and 7-methyl-1,5,7 -Triazabicyclo [4.4.0] dec-5-ene (MTBD) is preferred.
本発明の方法に用いる有機溶媒としては、トルエン、キシレンのような芳香族炭化水素、ヘキサン、オクタンのような脂肪族飽和炭化水素、ＤＭＦ、アセトニトリル、Ｎ−メチルピロリドンのような非プロトン性極性溶媒、ジエチルエーテル、テトラヒドロフラン、アニソールのようなエーテル類、酢酸エチル、酢酸ブチルのようなエステル類、メタノールのようなアルコール類が適している。ケトン類や脂肪族塩素系溶媒は、塩基性有機化合物触媒により分解、縮合等のおそれがあり、望ましくない。 Examples of the organic solvent used in the method of the present invention include aromatic hydrocarbons such as toluene and xylene, aliphatic saturated hydrocarbons such as hexane and octane, aprotic polar solvents such as DMF, acetonitrile, and N-methylpyrrolidone. Suitable are ethers such as diethyl ether, tetrahydrofuran and anisole, esters such as ethyl acetate and butyl acetate, and alcohols such as methanol. Ketones and aliphatic chlorinated solvents are undesirable because they may be decomposed or condensed by a basic organic compound catalyst.
有機溶媒中の触媒の濃度は、０．００５〜２．０ｍｏｌ／Ｌが好ましく、より好ましくは０．０２〜１ｍｏｌ／Ｌの範囲で用いられる。 The concentration of the catalyst in the organic solvent is preferably 0.005 to 2.0 mol / L, and more preferably 0.02 to 1 mol / L.
反応温度は、通常５０℃以上で進行し、１５０℃未満で行う。 The reaction temperature usually proceeds at 50 ° C. or higher and is performed at less than 150 ° C.
反応圧力は、常圧以上で行い、１０ＭＰａ未満が適当である。 The reaction pressure is not less than normal pressure and is suitably less than 10 MPa.
反応の形態としては、限定するものではないが、たとえば、適当な溶媒に触媒を共存させ、硫黄を懸濁させ、撹拌下、一酸化炭素を反応器に導入することにより反応させる。生成する硫化カルボニルは、気相を冷却し、凝縮することにより、未反応の一酸化炭素、溶媒、副生物と分離される。あるいは、気相を連続的に取り出し、冷却することにより、凝縮し、未反応の一酸化炭素と分離される。反応は、バッチでも連続でも可能であり、連続で行う場合には、消費された硫黄と一酸化炭素を連続的に反応器に供給される。加圧下で反応を行うことにより、生成硫化カルボニルを効率的に分離が可能になる。加圧された反応ガスを冷却することにより、硫化カルボニルを凝縮させ、一酸化炭素と分離し、凝縮硫化カルボニルを更に精留することにより容易に高純度の硫化カルボニルをえることが出来る。水分の存在は極力避けるべきであり、硫化カルボニルが炭酸ガスと硫化水素に分解し、生成物の純度を下げ、触媒の失活を招く恐れがある。 Although it does not limit as a form of reaction, for example, it makes it react by making a catalyst coexist in a suitable solvent, suspending sulfur, and introduce | transducing carbon monoxide into a reactor under stirring. The produced carbonyl sulfide is separated from unreacted carbon monoxide, solvent, and by-products by cooling and condensing the gas phase. Alternatively, the vapor phase is continuously taken out and cooled to be condensed and separated from unreacted carbon monoxide. The reaction can be carried out either batchwise or continuously. When the reaction is performed continuously, consumed sulfur and carbon monoxide are continuously supplied to the reactor. By performing the reaction under pressure, the produced carbonyl sulfide can be efficiently separated. By cooling the pressurized reaction gas, the carbonyl sulfide is condensed, separated from carbon monoxide, and the condensed carbonyl sulfide is further rectified to easily obtain high-purity carbonyl sulfide. The presence of moisture should be avoided as much as possible, and carbonyl sulfide may be decomposed into carbon dioxide and hydrogen sulfide, reducing the purity of the product and deactivating the catalyst.
以下、本発明の硫化カルボニルの製造方法について実施例を示して説明するが、本発明はこれらの実施例によって何ら限定されるものではない。 Hereinafter, although the example is shown and demonstrated about the manufacturing method of the carbonyl sulfide of this invention, this invention is not limited at all by these Examples.
［実施例１］
トルエン２０ｍＬおよび硫黄２．０ｇ（６２ｍｍｏｌ）を２００ｍＬのオートクレーブに入れ、触媒として、１，８−ジアザビシクロ［５，４，０］−ウンデカ−７−エン（ＤＢＵ）１．１４ｇ（７．５ｍｍｏｌ）を加え、撹拌し、反応温度を６４℃に設定し、一酸化炭素を０．８ＭＰａまで圧入し、反応を開始した。２６０分後、圧力は０．６ＭＰａになり、反応が終了した。
反応終了後、常圧に戻しつつ、反応容器のガスをジプロピルアミンのテトラヒドロフラン溶液に吸収させ、ヨウ化メチルを加え生成したジプロピルチオカルバミン酸メチルをＨＰＬＣで定量分析した結果、５４ｍｍｏｌのＣＯＳが生成しており、加えた一酸化炭素量とほぼ一致した。すなわち、ＣＯＳの収率はほぼ１００％であった。
[Example 1]
20 mL of toluene and 2.0 g (62 mmol) of sulfur were placed in a 200 mL autoclave, and 1.14 g (7.5 mmol) of 1,8-diazabicyclo [5,4,0] -undec-7-ene (DBU) was used as a catalyst. In addition, the mixture was stirred, the reaction temperature was set to 64 ° C., carbon monoxide was injected to 0.8 MPa, and the reaction was started. After 260 minutes, the pressure was 0.6 MPa and the reaction was complete.
After completion of the reaction, while returning to normal pressure, the gas in the reaction vessel was absorbed into a tetrahydrofuran solution of dipropylamine, and methyl iodide was added and methyl dipropylthiocarbamate was quantitatively analyzed by HPLC. As a result, 54 mmol of COS was obtained. The amount of carbon monoxide was almost the same as the amount of carbon monoxide added. That is, the yield of COS was almost 100%.
［実施例２〜１２］
実施例１と同様の反応を、ＤＢＵの代わりに各種塩基性有機化合物を用いて行った。結果を実施例１とあわせ、表１に示した。
[Examples 2 to 12]
Reaction similar to Example 1 was performed using various basic organic compounds instead of DBU. The results are shown in Table 1 together with Example 1.
表中の略称は次の化合物を表す。
ＤＢＵ：１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン
ＤＰＡ：ジ−ｎ−プロピルアミン
ＤＢＮ：１，５−ジアザビシクロ［４．３．０］ノナ−５−エン
ＭＴＢＤ：７−メチル−１，５，７−トリアザビシクロ［４．４．０］デカ−５−エン
ＴＢＤ：１，５，７−トリアザビシクロ［４．４．０］デカ−５−エン
ＢＥＭＰ：ｔｅｒｔ−ブチルイミノ−トリス（ジメチルアミノ）ホスホラン
ＢＴＴＰ：ｔｅｒｔ−ブチルイミノ−トリス（ピロリジノ）ホスホラン
ＴＭＡＨ：テトラメチルアンモニウムハイドロオキサイド
ＢＴＭＡＨ：ベンジルトリメチルアンモニウムハイドロオキサイド
Abbreviations in the table represent the following compounds.
DBU: 1,8-diazabicyclo [5.4.0] undec-7-ene DPA: di-n-propylamine DBN: 1,5-diazabicyclo [4.3.0] non-5-ene MTBD: 7- Methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene TBD: 1,5,7-triazabicyclo [4.4.0] dec-5-ene BEMP: tert- Butylimino-tris (dimethylamino) phosphorane BTTP: tert-butylimino-tris (pyrrolidino) phosphorane TMAH: tetramethylammonium hydroxide BTMAH: benzyltrimethylammonium hydroxide
［実施例１３］
ジメチルホルムアミド（ＤＭＦ）２０ｍＬおよび硫黄２．０ｇ（６２ｍｍｏｌ）を２００ｍＬのオートクレーブに入れ、触媒として、１，８−ジアザビシクロ［５，４，０］−ウンデカ−７−エン）（ＤＢＵ）７６ｍｇ（０．５ｍｍｏｌ）を加え、撹拌し、反応温度を６８℃に設定し、一酸化炭素を０．８ＭＰａまで圧入し、反応を開始した。１２０分後、圧力は０．６ＭＰａになり、反応が終了した。
反応終了後、常圧にもどしつつ、反応容器のガスをジエチルアミンのテトラヒドロフラン溶液に吸収させ、ヨウ化メチルを加え生成したジエチルチオカルバミン酸メチルをＧＣで定量分析した結果、５４ｍｍｏｌのＣＯＳが生成しており、加えた一酸化炭素量とほぼ一致した。
[Example 13]
20 mL of dimethylformamide (DMF) and 2.0 g (62 mmol) of sulfur were placed in a 200 mL autoclave and 1,8-diazabicyclo [5,4,0] -undec-7-ene) (DBU) 76 mg (. 5 mmol) was added and stirred, the reaction temperature was set to 68 ° C., carbon monoxide was injected to 0.8 MPa, and the reaction was started. After 120 minutes, the pressure was 0.6 MPa and the reaction was complete.
After completion of the reaction, the gas in the reaction vessel was absorbed into a solution of diethylamine in tetrahydrofuran while returning to normal pressure, and methyl iodide was added and methyl diethylthiocarbamate was quantitatively analyzed by GC. As a result, 54 mmol of COS was produced. It almost coincided with the amount of carbon monoxide added.
本発明の方法により製造される硫化カルボニルは、有機系反射防止膜のプラズマによる高異方性および高選択性エッチング用のエッチングガスとして好適に利用できる。 The carbonyl sulfide produced by the method of the present invention can be suitably used as an etching gas for high anisotropy and high selectivity etching by plasma of an organic antireflection film.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011092439A JP5721517B2 (en) | 2011-04-18 | 2011-04-18 | Method for producing carbonyl sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011092439A JP5721517B2 (en) | 2011-04-18 | 2011-04-18 | Method for producing carbonyl sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2012224494A true JP2012224494A (en) | 2012-11-15 |
| JP5721517B2 JP5721517B2 (en) | 2015-05-20 |
Family
ID=47275108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2011092439A Active JP5721517B2 (en) | 2011-04-18 | 2011-04-18 | Method for producing carbonyl sulfide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5721517B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020262319A1 (en) * | 2019-06-27 | 2020-12-30 | 日本ゼオン株式会社 | Method for producing carbonyl sulfide |
| CN114045492A (en) * | 2021-12-28 | 2022-02-15 | 苏州金宏气体股份有限公司 | Interface treatment process for electronic-grade carbonyl sulfide storage container and application |
| WO2024070744A1 (en) * | 2022-09-28 | 2024-04-04 | 日本ゼオン株式会社 | Carbonyl sulfide production method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3235333A (en) * | 1961-03-07 | 1966-02-15 | Standard Oil Co | Process for producing carbonylsulfide |
| JPS52131993A (en) * | 1976-04-28 | 1977-11-05 | Ihara Chem Ind Co Ltd | Production of carbonyl sulfide |
| JPS6078937A (en) * | 1983-10-06 | 1985-05-04 | Mitsubishi Gas Chem Co Inc | Production of carboxylic acid ester |
| JPS6164335A (en) * | 1984-06-09 | 1986-04-02 | ビ−ピ− ケミカルズ リミテツド | Catalytic action using supported strong basic catalyst |
| JPS61197414A (en) * | 1985-02-26 | 1986-09-01 | Nippon Nohyaku Co Ltd | Continuous production of carbonyl sulfide |
-
2011
- 2011-04-18 JP JP2011092439A patent/JP5721517B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3235333A (en) * | 1961-03-07 | 1966-02-15 | Standard Oil Co | Process for producing carbonylsulfide |
| JPS52131993A (en) * | 1976-04-28 | 1977-11-05 | Ihara Chem Ind Co Ltd | Production of carbonyl sulfide |
| JPS6078937A (en) * | 1983-10-06 | 1985-05-04 | Mitsubishi Gas Chem Co Inc | Production of carboxylic acid ester |
| JPS6164335A (en) * | 1984-06-09 | 1986-04-02 | ビ−ピ− ケミカルズ リミテツド | Catalytic action using supported strong basic catalyst |
| JPS61197414A (en) * | 1985-02-26 | 1986-09-01 | Nippon Nohyaku Co Ltd | Continuous production of carbonyl sulfide |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020262319A1 (en) * | 2019-06-27 | 2020-12-30 | 日本ゼオン株式会社 | Method for producing carbonyl sulfide |
| CN114045492A (en) * | 2021-12-28 | 2022-02-15 | 苏州金宏气体股份有限公司 | Interface treatment process for electronic-grade carbonyl sulfide storage container and application |
| CN114045492B (en) * | 2021-12-28 | 2024-02-27 | 金宏气体股份有限公司 | Interface treatment process for electronic grade carbonyl sulfide storage container and application |
| WO2024070744A1 (en) * | 2022-09-28 | 2024-04-04 | 日本ゼオン株式会社 | Carbonyl sulfide production method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5721517B2 (en) | 2015-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5889286B2 (en) | Method for producing carbonyl sulfide | |
| JP5849710B2 (en) | Process for producing β-fluoroalcohols | |
| JP6217653B2 (en) | Method for producing α, α-difluoroacetaldehyde | |
| JP2012250930A (en) | Process for producing carbamate | |
| JP5721517B2 (en) | Method for producing carbonyl sulfide | |
| JP6035918B2 (en) | Method for producing α-fluoroaldehyde | |
| KR20140011937A (en) | Process for preparing n,n'-substituted urea derivatives using cerium dioxide catalyst | |
| JP6871802B2 (en) | A method for obtaining a carbonyl compound by a carbonylation reaction of a halogen compound using an aldehyde as a carbon monoxide source in the presence of a heterogeneous palladium catalyst. | |
| WO2012176930A1 (en) | Process for producing carboxylic acid ester | |
| JP6028606B2 (en) | Method for producing amine compound | |
| TWI433726B (en) | Recyclable catalysts for esterification or acylation of alcohols | |
| US20130072713A1 (en) | Method for producing methionine | |
| US9199950B2 (en) | Method for producing glycidol by successive catalytic reactions | |
| CN108178752B (en) | Method for preparing 3,3, 3-trifluoropropene carbonate and 3,3, 3-trifluoro-1, 2-propylene glycol in co-production mode | |
| JP2011051904A (en) | Method for producing tertiary alcohol | |
| EP1970369B1 (en) | Method for producing purified formylcyclopropane compound and intermediate of such formylcyclopropane compound | |
| CN110878025A (en) | Method for reducing aromatic nitro compound into aromatic amine compound | |
| JP2007523083A (en) | Synthesis of highly sterically hindered secondary amino ether alcohols from ketene and / or carboxylic acid halides and / or carboxylic anhydrides | |
| WO2018200881A1 (en) | Process for the preparation of deuterated ethanol from d2o | |
| CN104370953A (en) | (R)-tert-butyl dimethyl siloxy-glutaric acid monoester preparation method | |
| JP2013028590A (en) | Method for producing amino alcohol compound | |
| EP2888250B1 (en) | Process for the synthesis of substituted gamma lactams | |
| US11155516B2 (en) | Synthesis of 2-(2-aminoethoxy) ethanol | |
| JP2011132072A (en) | Method for producing lithium hexafluorophosphate | |
| JP2001011015A (en) | Production of tartaric acid lower alkyl diester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140217 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140625 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140701 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140819 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150224 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150324 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5721517 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |