JP2021138661A - Method for producing cyclic carbonates - Google Patents
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- 150000005676 cyclic carbonates Chemical class 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 21
- 229920005862 polyol Polymers 0.000 claims abstract description 14
- 150000003077 polyols Chemical class 0.000 claims abstract description 14
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims abstract description 6
- YISPIDBWTUCKKH-UHFFFAOYSA-L zinc;4-methylbenzenesulfonate Chemical compound [Zn+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 YISPIDBWTUCKKH-UHFFFAOYSA-L 0.000 claims abstract description 4
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims abstract description 3
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims abstract description 3
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims description 11
- 239000005997 Calcium carbide Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract 4
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract 2
- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical compound OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 description 24
- 239000011701 zinc Substances 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- RJTZQPTVNWCDBI-UHFFFAOYSA-N C(CNCc1ncccc1)NCc1ncccc1 Chemical compound C(CNCc1ncccc1)NCc1ncccc1 RJTZQPTVNWCDBI-UHFFFAOYSA-N 0.000 description 2
- 0 C1*=Cc(ccc2c3nccc2)c3N=C1 Chemical compound C1*=Cc(ccc2c3nccc2)c3N=C1 0.000 description 2
- UJAQYOZROIFQHO-UHFFFAOYSA-N Cc1cc2cccnc2c2ncccc12 Chemical compound Cc1cc2cccnc2c2ncccc12 UJAQYOZROIFQHO-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- PDDBTWXLNJNICS-UHFFFAOYSA-N [O-][N+](c(c1c2nccc1)cc1c2nccc1)=O Chemical compound [O-][N+](c(c1c2nccc1)cc1c2nccc1)=O PDDBTWXLNJNICS-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N c1ccnc(-c2ccccn2)c1 Chemical compound c1ccnc(-c2ccccn2)c1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- UMFJHYOWLZYOJK-UHFFFAOYSA-N 1,1-dihydroxybutyl hydrogen carbonate Chemical compound CCCC(O)(O)OC(O)=O UMFJHYOWLZYOJK-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- QBPPRVHXOZRESW-UHFFFAOYSA-N C1NCCNCCNCCNC1 Chemical compound C1NCCNCCNCCNC1 QBPPRVHXOZRESW-UHFFFAOYSA-N 0.000 description 1
- IYRGXJIJGHOCFS-UHFFFAOYSA-N Cc1ccc(ccc2ccc(C)nc22)c2n1 Chemical compound Cc1ccc(ccc2ccc(C)nc22)c2n1 IYRGXJIJGHOCFS-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- NJTGANWAUPEOAX-UHFFFAOYSA-N molport-023-220-454 Chemical compound OCC(O)CO.OCC(O)CO NJTGANWAUPEOAX-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 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
- 238000003756 stirring Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
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Abstract
Description
本願は、亜鉛化合物と炭化カルシウムの存在下で、ポリオール類と二酸化炭素を反応させて、環状カーボネートを製造する方法に関する。 The present application relates to a method for producing a cyclic carbonate by reacting polyols with carbon dioxide in the presence of a zinc compound and calcium carbide.
スズ化合物の存在下で、グリセロールと二酸化炭素を反応させて、環状カーボネートを製造する方法が知られている（非特許文献１）。この環状カーボネートの製造方法では、副生する水の影響で、生成物の収率（約０．４％）が極めて低かった。この副生する水を除去するために、モレキュラーシーブを脱水剤として用いても、生成物の収率は約６％であり、余り改善されなかった。 A method for producing a cyclic carbonate by reacting glycerol with carbon dioxide in the presence of a tin compound is known (Non-Patent Document 1). In this method for producing cyclic carbonate, the yield of the product (about 0.4%) was extremely low due to the influence of water produced as a by-product. Even if a molecular sieve was used as a dehydrating agent to remove this by-product water, the yield of the product was about 6%, which was not improved so much.
本願の課題は、安価な炭化カルシウムを用いて副生する水を除去することにより、経済性に優れ、かつ高収率で環状カーボネートが製造できる方法を提供することである。 An object of the present application is to provide a method capable of producing cyclic carbonate with excellent economy and high yield by removing water produced as a by-product using inexpensive calcium carbide.
本願の環状カーボネートの製造方法は、亜鉛化合物と炭化カルシウムの存在下で、ポリオール類と二酸化炭素を反応させる反応工程を有する。 The method for producing cyclic carbonate of the present application includes a reaction step of reacting polyols with carbon dioxide in the presence of a zinc compound and calcium carbide.
本願によれば、亜鉛系触媒存在下で、ポリオール類と二酸化炭素との反応から副生する水を安価な炭化カルシウムを用いて除去することにより、高収率で環状カーボネートが製造できる。 According to the present application, cyclic carbonate can be produced in high yield by removing water produced as a by-product from the reaction between polyols and carbon dioxide using inexpensive calcium carbide in the presence of a zinc-based catalyst.
本願の実施形態の環状カーボネートの製造方法は、亜鉛化合物と炭化カルシウムの存在下で、ポリオール類と二酸化炭素を反応させる反応工程を備えている。本実施形態の製造方法で得られる環状カーボネートとしては、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、グリセロールカーボネート、およびブタントリオールカーボネートなどが例示される。 The method for producing cyclic carbonate according to the embodiment of the present application includes a reaction step of reacting polyols with carbon dioxide in the presence of a zinc compound and calcium carbide. Examples of the cyclic carbonate obtained by the production method of the present embodiment include ethylene carbonate, propylene carbonate, butylene carbonate, glycerol carbonate, butanetriol carbonate and the like.
亜鉛化合物は触媒として機能する。亜鉛化合物としては、酢酸亜鉛（Ｚｎ（ＣＨ３ＣＯＯ）２）（以下「Ｚｎ（ＯＡｃ）２」と記載することがある）、硫酸亜鉛（ＺｎＳＯ４）、塩化亜鉛（ＺｎＣｌ２）、臭化亜鉛（ＺｎＢｒ２）、ヨウ化亜鉛（ＺｎＩ２）、トリフルオロメタンスルホン酸亜鉛（Ｚｎ（ＣＦ３ＳＯ３）２）（以下「Ｚｎ（ＯＴｆ）２」と記載することがある）、およびｐ−トルエンスルホン酸亜鉛（Ｚｎ（Ｃ７Ｈ７Ｏ３Ｓ）２）（以下「Ｚｎ（Ｔｏｓ）２」と記載することがある）などが例示される。これらの中でもＺｎＩ２、Ｚｎ（ＯＴｆ）２、およびＺｎ（Ｔｏｓ）２が好ましい。高収率で環状カーボネートが得られるからである。 The zinc compound functions as a catalyst. Examples of the zinc compound include zinc acetate (Zn (CH 3 COO) 2 ) (hereinafter sometimes referred to as “Zn (OAc) 2 ”), zinc sulfate (ZnSO 4 ), zinc chloride (ZnCl 2 ), and zinc bromide. (ZnBr 2 ), zinc iodide (ZnI 2 ), zinc trifluoromethanesulfonate (Zn (CF 3 SO 3 ) 2 ) (hereinafter sometimes referred to as "Zn (OTf) 2 "), and p-toluenesulfone. Examples include zinc acid (Zn (C 7 H 7 O 3 S) 2 ) (hereinafter sometimes referred to as “Zn (Tos) 2”). Among these, ZnI 2 , Zn (OTf) 2 , and Zn (Tos) 2 are preferable. This is because the cyclic carbonate can be obtained in high yield.
炭化カルシウムは脱水剤として機能する。ポリオール類と二酸化炭素が反応して環状カーボネートが生成するとき、水が副生する。副生する水を反応系から炭化カルシウムが除くことにより、ポリオール類と二酸化炭素から環状カーボネートが生成する反応が進行する。ポリオール類としては、ジオールおよびトリオールなどが例示される。ジオールとしては、下記の化学式で表されるグリコールなどが例示される。トリオールとしては、１，２，３−プロパントリオール（グリセロール）および１，２，４−ブタントリオールなどが例示される。 Calcium carbide functions as a dehydrating agent. When polyols react with carbon dioxide to form cyclic carbonate, water is by-produced. By removing calcium carbide from the reaction system by removing water as a by-product, the reaction of producing cyclic carbonate from polyols and carbon dioxide proceeds. Examples of polyols include diols and triols. Examples of the diol include glycol represented by the following chemical formula. Examples of triol include 1,2,3-propanetriol (glycerol) and 1,2,4-butanetriol.
本実施形態の反応工程は、例えば、亜鉛化合物、炭化カルシウム、ポリオール類、および溶媒が入っている反応容器に二酸化炭素を充填させることによって行えるが、反応工程の実施態様には特に制限がない。反応工程における温度（反応温度）は、反応を十分に進行させる観点から、１００〜２００℃が好ましく、１５０〜１８０℃がより好ましく、１６５〜１８０℃がさらに好ましいが、特に制限がない。反応温度１６５〜１８０℃で反応工程を行うと、高収率で環状カーボネートが得られる。 The reaction step of the present embodiment can be carried out, for example, by filling a reaction vessel containing a zinc compound, calcium carbide, polyols, and a solvent with carbon dioxide, but the embodiment of the reaction step is not particularly limited. The temperature (reaction temperature) in the reaction step is preferably 100 to 200 ° C., more preferably 150 to 180 ° C., still more preferably 165 to 180 ° C., but is not particularly limited, from the viewpoint of sufficiently advancing the reaction. When the reaction step is carried out at a reaction temperature of 165 to 180 ° C., a cyclic carbonate is obtained in a high yield.
反応工程における二酸化炭素の圧力は、０．５〜３０ＭＰａが好ましく、１〜１０ＭＰａがより好ましく、３〜５ＭＰａがさらに好ましいが、特に制限がない。二酸化炭素の圧力を３〜５ＭＰａとして反応工程を行うと、高収率で環状カーボネートが得られる。反応工程の時間（反応時間）は、ポリオール類の種類、反応温度、および二酸化炭素の圧力などの条件により異なるが、４〜２４時間が好ましい。 The pressure of carbon dioxide in the reaction step is preferably 0.5 to 30 MPa, more preferably 1 to 10 MPa, still more preferably 3 to 5 MPa, but there is no particular limitation. When the reaction step is carried out at a carbon dioxide pressure of 3 to 5 MPa, a cyclic carbonate is obtained in high yield. The reaction step time (reaction time) varies depending on conditions such as the type of polyol, the reaction temperature, and the pressure of carbon dioxide, but is preferably 4 to 24 hours.
反応工程における溶媒は、環状カーボネートの生成を妨げなければ特に制限がなく、無溶媒であってもよい。反応工程における溶媒としては、炭化水素類やエーテル類などが挙げられる。具体的には、アセトニトリル（ＭｅＣＮ）、テトラヒドロフラン（ＴＨＦ）、トルエン、Ｎ，Ｎ′−ジメチルホルムアミド（ＤＭＦ）、Ｎ，Ｎ′−ジメチルアセトアミド（ＤＭＡｃ）、メチルエチルケトン（ＭＥＫ）、およびＮ−メチル−２−ピロリドン（ＮＭＰ）などが例示される。これらの中でもＤＭＡｃおよびＮＭＰが好ましく、ＮＭＰが特に好ましい。高収率で環状カーボネートが得られるからである。 The solvent in the reaction step is not particularly limited as long as it does not interfere with the formation of cyclic carbonate, and may be solvent-free. Examples of the solvent in the reaction step include hydrocarbons and ethers. Specifically, acetonitrile (MeCN), tetrahydrofuran (THF), toluene, N, N'-dimethylformamide (DMF), N, N'-dimethylacetamide (DMAc), methylethylketone (MEK), and N-methyl-2. -Pyrrolidone (NMP) and the like are exemplified. Among these, DMAc and NMP are preferable, and NMP is particularly preferable. This is because the cyclic carbonate can be obtained in high yield.
反応工程では、さらに下記の化学式で表される少なくとも一種の配位子の存在下で、ポリオール類と二酸化炭素を反応させてもよい。環状カーボネートの収率が向上するからである。 In the reaction step, the polyols and carbon dioxide may be further reacted in the presence of at least one ligand represented by the following chemical formula. This is because the yield of cyclic carbonate is improved.
（実施例１）
撹拌装置を備える容量１０ｍＬのオートクレーブに、ポリオール類であるグリセロール０．５ｍｍｏｌ、炭化カルシウム２．５ｍｍｏｌ、ｐ−トルエンスルホン酸亜鉛０．０２５ｍｍｏｌ、１，１０−フェナントロリン（以下「ｐｈｅｎ」と記載することがある）０．０７５ｍｍｏｌ、および溶媒であるＮＭＰ３ｍＬを入れ、二酸化炭素ボンベを接続して密封した。オートクレーブ内を撹拌しながら、オートクレーブ内に二酸化炭素を充填し、１８０℃に昇温して、オートクレーブ内の圧力が５ＭＰａになるように調整し、２４時間反応させて環状カーボネートであるグリセロールカーボネートを合成した（下記化学反応式）。なお、オートクレーブ内の圧力を二酸化炭素の圧力とみなした。
(Example 1)
In a 10 mL autoclave equipped with a stirrer, the polyols glycerol 0.5 mmol, calcium carbide 2.5 mmol, zinc p-toluenesulfonate 0.025 mmol, 1,10-phenanthroline (hereinafter referred to as “phen”) may be described. 0.075 mmol (is) and 3 mL of NMP as a solvent were added, and a carbon dioxide bomb was connected and sealed. While stirring the inside of the autoclave, the autoclave is filled with carbon dioxide, the temperature is raised to 180 ° C., the pressure inside the autoclave is adjusted to 5 MPa, and the reaction is carried out for 24 hours to synthesize glycerol carbonate which is a cyclic carbonate. (Chemical reaction formula below). The pressure in the autoclave was regarded as the pressure of carbon dioxide.
反応終了後、オートクレーブ内を冷却し、残存する二酸化炭素を放出した。つぎに、ジメチルスルホキシド−ｄ６（ＤＭＳＯ−ｄ６）を用いて、グリセロールカーボネートを１Ｈ−ＮＭＲで分析し、収率を算出した。グリセロールカーボネートの収率は９２％であった。 After completion of the reaction, the inside of the autoclave was cooled to release the remaining carbon dioxide. Next, glycerol carbonate was analyzed by 1 H-NMR using dimethyl sulfoxide-d 6 (DMSO-d 6 ), and the yield was calculated. The yield of glycerol carbonate was 92%.
（実施例２および比較例１）
ｐ−トルエンスルホン酸亜鉛に代えて、下記の表１に示した亜鉛化合物を用い、実施例１と同様にしてグリセロールカーボネートを合成した。比較例として、亜鉛化合物を用いなかった点を除いて、実施例１と同様にしてグリセロールカーボネートを合成した。グリセロールカーボネートの収率を表１に示す。表１に示すように、様々な亜鉛化合物を用いて、高収率でグリセロールカーボネートが合成できることがわかった。
(Example 2 and Comparative Example 1)
Instead of zinc p-toluenesulfonate, the zinc compounds shown in Table 1 below were used, and glycerol carbonate was synthesized in the same manner as in Example 1. As a comparative example, a glycerol carbonate was synthesized in the same manner as in Example 1 except that a zinc compound was not used. The yield of glycerol carbonate is shown in Table 1. As shown in Table 1, it was found that glycerol carbonate can be synthesized in high yield using various zinc compounds.
（実施例３）
ｐｈｅｎの量を変えて、またはｐｈｅｎに代えて、下記の表２に示した配位子を用い、もしくは配位子を用いずに、実施例１と同様にしてグリセロールカーボネートを合成した。ただし、実施例３−６から３−９までは、反応時間を１６時間とした。なお、表２に示す配位子の略称は、上記の配位子の化学式の下方に記載した略称と一致する。グリセロールカーボネートの収率を表２に示す。
(Example 3)
Glycerol carbonate was synthesized in the same manner as in Example 1 with or without the ligands shown in Table 2 below, with varying amounts of phen or instead of phen. However, in Examples 3-6 to 3-9, the reaction time was 16 hours. The abbreviations of the ligands shown in Table 2 correspond to the abbreviations described below the chemical formulas of the above-mentioned ligands. The yield of glycerol carbonate is shown in Table 2.
表２に示すに示すように、様々な配位子を用いて、または配位子を用いなくても、高収率でグリセロールカーボネートが合成できることがわかった。また、Ｚｎ（ＯＴｆ）２の物質量（０．０２５ｍｍｏｌ）の２倍〜３倍の物質量のｐｈｅｎを用いたときに、より高収率でグリセロールカーボネートが合成できることがわかった。 As shown in Table 2, it was found that glycerol carbonate can be synthesized in high yield with or without various ligands. It was also found that glycerol carbonate can be synthesized in a higher yield when phen having a substance amount of 2 to 3 times the substance amount of Zn (OTf) 2 (0.025 mmol) is used.
（実施例４）
ＮＭＰに代えて、下記の表３に示した溶媒を用い、実施例１と同様にしてグリセロールカーボネートを合成した。グリセロールカーボネートの収率を表３に示す。表３に示すように、様々な溶媒を用いて、高収率でグリセロールカーボネートが合成できることがわかった。
(Example 4)
Glycerol carbonate was synthesized in the same manner as in Example 1 using the solvents shown in Table 3 below instead of NMP. The yield of glycerol carbonate is shown in Table 3. As shown in Table 3, it was found that glycerol carbonate can be synthesized in high yield using various solvents.
（実施例５）
炭化カルシウムの物質量を１．２５ｍｍｏｌとした点を除き、実施例１と同様にしてグリセロールカーボネートを合成した。グリセロールカーボネートの収率は６９％であった。
(Example 5)
Glycerol carbonate was synthesized in the same manner as in Example 1 except that the amount of substance of calcium carbide was 1.25 mmol. The yield of glycerol carbonate was 69%.
（実施例６）
反応温度を１５０℃（実施例１６−１）または１６５℃（実施例１６−２）とした点を除き、実施例１と同様にしてグリセロールカーボネートを合成した。反応時間とグリセロールカーボネートの収率の関係を、実施例１（反応温度１８０℃）とともに図１に示す。実施例１では、グリセロールカーボネートの収率は、反応時間１６時間で７２％に、反応時間２４時間で９２％にそれぞれ達した。反応時間２４時間のグリセロールカーボネートの収率は、実施例１６−１で３６％、実施例１６−２で５７％であった。反応温度が高いとグリセロールカーボネートの収率も高かった。
(Example 6)
Glycerol carbonate was synthesized in the same manner as in Example 1 except that the reaction temperature was 150 ° C. (Example 16-1) or 165 ° C. (Example 16-2). The relationship between the reaction time and the yield of glycerol carbonate is shown in FIG. 1 together with Example 1 (reaction temperature 180 ° C.). In Example 1, the yield of glycerol carbonate reached 72% at a reaction time of 16 hours and 92% at a reaction time of 24 hours. The yield of glycerol carbonate for a reaction time of 24 hours was 36% in Example 16-1 and 57% in Example 16-2. The higher the reaction temperature, the higher the yield of glycerol carbonate.
（実施例７）
グリセロールに代えて、下記の表４に示した原料を用い、実施例１と同様にして環状カーボネートを合成した。環状カーボネートの収率を表４に示す。表４に示すように、トリオールだけはなく、様々なジオールを原料として、高収率で環状カーボネートが合成できることがわかった。
(Example 7)
Cyclic carbonate was synthesized in the same manner as in Example 1 using the raw materials shown in Table 4 below instead of glycerol. The yield of cyclic carbonate is shown in Table 4. As shown in Table 4, it was found that cyclic carbonate can be synthesized in high yield using not only triol but also various diols as raw materials.
Claims (6)
前記亜鉛化合物が、ヨウ化亜鉛、トリフルオロメタンスルホン酸亜鉛、およびｐ−トルエンスルホン酸亜鉛の少なくとも一種である環状カーボネートの製造方法。 In claim 1,
A method for producing a cyclic carbonate in which the zinc compound is at least one of zinc iodide, zinc trifluoromethanesulfonate, and zinc p-toluenesulfonate.
前記反応工程では、さらに下記の化学式で表される少なくとも一種の配位子の存在下で、ポリオール類と二酸化炭素を反応させる環状カーボネートの製造方法。
In the reaction step, a method for producing a cyclic carbonate in which polyols and carbon dioxide are reacted in the presence of at least one ligand represented by the following chemical formula.
Ｎ−メチル−２−ピロリドン溶媒を用いて前記反応工程を行う環状カーボネートの製造方法。 In any of claims 1 to 3,
A method for producing a cyclic carbonate in which the reaction step is carried out using an N-methyl-2-pyrrolidone solvent.
温度１６５〜１８０℃で前記反応工程を行う環状カーボネートの製造方法。 In any of claims 1 to 4,
A method for producing a cyclic carbonate in which the reaction step is carried out at a temperature of 165 to 180 ° C.
二酸化炭素の圧力が３〜５ＭＰａで前記反応工程を行う環状カーボネートの製造方法。 In any of claims 1 to 5,
A method for producing a cyclic carbonate in which the reaction step is carried out at a carbon dioxide pressure of 3 to 5 MPa.
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| WO2018224737A1 (en) * | 2017-06-09 | 2018-12-13 | Maston Oy | A method for preventing hardener compounds to be formed from hardener precursors and extending shelf life of the dispersion |
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| WO2018224737A1 (en) * | 2017-06-09 | 2018-12-13 | Maston Oy | A method for preventing hardener compounds to be formed from hardener precursors and extending shelf life of the dispersion |
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