JP4789892B2 - Method for producing fluorocyclic carbonate - Google Patents
Method for producing fluorocyclic carbonate Download PDFInfo
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- JP4789892B2 JP4789892B2 JP2007236041A JP2007236041A JP4789892B2 JP 4789892 B2 JP4789892 B2 JP 4789892B2 JP 2007236041 A JP2007236041 A JP 2007236041A JP 2007236041 A JP2007236041 A JP 2007236041A JP 4789892 B2 JP4789892 B2 JP 4789892B2
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 claims description 19
- 150000001340 alkali metals Chemical class 0.000 claims description 16
- 229910001515 alkali metal fluoride Inorganic materials 0.000 claims description 14
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- -1 fluoro cyclic carbonate Chemical class 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000011541 reaction mixture Substances 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- 150000003983 crown ethers Chemical class 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000003444 phase transfer catalyst Substances 0.000 claims description 4
- UDHFKPDSMSBLMN-UHFFFAOYSA-N C(O)(O)=O.CCCCC(C)C=C Chemical compound C(O)(O)=O.CCCCC(C)C=C UDHFKPDSMSBLMN-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 claims description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 2
- 229910016036 BaF 2 Inorganic materials 0.000 claims description 2
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000005586 carbonic acid group Chemical group 0.000 claims description 2
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 description 9
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- 150000003990 18-crown-6 derivatives Chemical group 0.000 description 1
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical group ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/42—Halogen atoms or nitro radicals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0204—Ethers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
本発明は、フルオロ環状炭酸エステルを製造する方法に関するものである。 The present invention relates to a method for producing a fluorocyclic carbonate.
フルオロ環状炭酸エステルは主に高出力リチウム電池のリチウムイオン電解液に用いられ、有効にその耐低温性を改善するとその難燃性を向上させることなどができる。従来のフルオロ環状炭酸エステルの合成の研究において、炭酸エチレンを原料とし、単体フッ素をフッ化試薬とし、窒素雰囲気で反応させてフルオロ炭酸エチレンを生成する方法が既に報告されている。他の方法は、炭酸エチレンとフッ化テトラエチルアンモニウムフッ酸塩とで、遷移金属のコバルトなどの触媒の作用で直接フルオロ炭酸エチレンを合成するものである。この２つの方法には、原材料が稀で、かつ高価であると共に、単体フッ素ガスのような原料には劇毒及び爆発しやすいという危険があるため、研究又は生産にいろいろな不便をもたらすという問題がある。 Fluorocyclic carbonates are mainly used in lithium ion electrolytes for high-power lithium batteries, and their flame retardancy can be improved by effectively improving their low temperature resistance. In research on the synthesis of conventional fluorocyclic carbonates, a method has already been reported in which ethylene carbonate is used as a raw material, simple fluorine is used as a fluorination reagent, and reaction is performed in a nitrogen atmosphere to produce fluoroethylene carbonate. Another method is to directly synthesize fluoroethylene carbonate with ethylene carbonate and tetraethylammonium fluoride hydrofluorate by the action of a catalyst such as cobalt as a transition metal. These two methods have the problem that they cause various inconveniences in research or production because raw materials are rare and expensive, and there is a risk that raw materials such as simple fluorine gas are easily poisoned and explosive. is there.
本発明は、合成工程が簡単で、原料が低価で、入手が容易で、かつ収率が高いフルオロ環状炭酸エステルの製造方法を提供することを目的とする。 An object of the present invention is to provide a method for producing a fluorocyclic carbonate having a simple synthesis process, low cost raw materials, easy availability, and high yield.
本発明の発明者らは、従来技術にある問題に対して、研究を深めたところ、フルオロ環状炭酸エステルの生産に適する新規な方法を見出した。
本発明は、次の構造式（ｉ）で示されるクロロ環状炭酸エステルと、アルカリ金属又はアルカリ土類金属のフッ化物とを原料とし、
The present invention uses, as a raw material, a chlorocyclic carbonate represented by the following structural formula (i) and an alkali metal or alkaline earth metal fluoride,
この方法には、さらに前記フルオロ環状炭酸エステルを含む反応混合物を減圧で精留し、精製のフルオロ環状炭酸エステルを得ることが含まれることが好ましい。
前記溶媒は、炭酸二炭化水素基エステル或は環状炭酸エステルであることが好ましい。前記炭酸二炭化水素基エステルは次の構造式：
This method preferably further includes rectifying the reaction mixture containing the fluorocyclic carbonate under reduced pressure to obtain a purified fluorocyclic carbonate.
The solvent is preferably a carbonic acid dihydrocarbon ester or a cyclic carbonate. The carbonate dihydrocarbon group ester has the following structural formula:
の構成を持つことがより好ましい。式中Ｒ２とＲ２’は相同或は相異のもので、それぞれ独立にＣ１−Ｃ８アルキル基又はＣ６−Ｃ８アリール基から選ばれる。前記環状炭酸エステルは次の構造式： It is more preferable to have the following structure. In the formula, R 2 and R 2 ′ are homologous or different and are each independently selected from a C 1 -C 8 alkyl group or a C 6 -C 8 aryl group. The cyclic ester carbonate has the following structural formula:
を持つことがより好ましい。式中、Ｒ３とＲ３’は相同或は相異のもので、それぞれ独立にＣ１−Ｃ８アルキル基又はＣ６−Ｃ８アリール基から選ばれる。 It is more preferable to have Wherein, R 3 and R 3 'are intended homologous or differences, Ru are independently selected from C 1 -C 8 alkyl group or a C 6 -C 8 aryl group.
前記クラウンエーテル系相間移動触媒は、１８−クラウン−６、ジベンゾ−１８−クラウン−６、ジシクロヘキシル−１８−クラウン−６、１５−クラウン−５、或は１２−クラウン−４であることが好ましく、これらの構造式はそれぞれ以下のようである。 The crown ether phase transfer catalyst is preferably 18-crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown-6, 15-crown-5, or 12-crown-4. These structural formulas are as follows.
前記アルカリ金属又はアルカリ土類金属のフッ化物は、ＫＦ、ＬｉＦ、ＮａＦ、ＭｇＦ２、ＣａＦ２或はＢａＦ２から選ばれることが好ましい。
前記溶媒は、炭酸ジメチル、炭酸ジエチル、炭酸ジプロピル、炭酸メチルエチル、炭酸メチルプロピル、炭酸エチルプロピル、５−ヘキシル炭酸エチレン、炭酸エチレン、炭酸ジフェニル、５−フェニル炭酸エチレン、炭酸プロピレン及び炭酸フェニル（メチル）フェニルから選ばれる一種或は多種であることが好ましい。
The alkali metal or alkaline earth metal fluoride is preferably selected from KF, LiF, NaF, MgF 2 , CaF 2 or BaF 2 .
The solvent is dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, 5-hexyl ethylene carbonate, ethylene carbonate, diphenyl carbonate, 5-phenyl ethylene carbonate, propylene carbonate and phenyl carbonate (methyl ) It is preferably one or more selected from phenyl.
好ましくは、前記反応は、９０〜１２０℃の温度範囲で行う。
好ましくは、前記減圧精留の温度範囲は４０〜１５０℃で、減圧精留の真空度範囲は０．１〜２００ｋＰａである。
Preferably, the reaction is carried out in the temperature range of 90-120 ° C.
Preferably, the temperature range of the vacuum rectification is 40 to 150 ° C., and the vacuum range of the vacuum rectification is 0.1 to 200 kPa.
好ましくは、反応原料であるクロロ環状炭酸エステルとアルカリ金属又はアルカリ土類金属のフッ化物とのモル比は１：１０〜１０：１の範囲にあり、ここで、アルカリ金属又はアルカリ土類金属のフッ化物はフッ素原子のモル数で計算する。より好ましくは、反応原料であるクロロ環状炭酸エステルとアルカリ金属又はアルカリ土類金属のフッ化物とのモル比は１：４〜４：１の範囲にあり、ここで、アルカリ金属又はアルカリ土類金属のフッ化物はフッ素原子のモル数で計算する。とくに好ましくは、反応原料であるクロロ環状炭酸エステルとアルカリ金属又はアルカリ土類金属のフッ化物とのモル比は１：１〜１：４の範囲にあり、ここで、アルカリ金属又はアルカリ土類金属のフッ化物はフッ素原子のモル数で計算する。 Preferably, the molar ratio of the reaction raw material chloro cyclic carbonate to the alkali metal or alkaline earth metal fluoride is in the range of 1:10 to 10: 1, where the alkali metal or alkaline earth metal Fluoride is calculated by the number of moles of fluorine atoms. More preferably, the molar ratio of the reaction raw material chloro cyclic carbonate to the alkali metal or alkaline earth metal fluoride is in the range of 1: 4 to 4: 1, where alkali metal or alkaline earth metal. Is calculated by the number of moles of fluorine atoms. Particularly preferably, the molar ratio of the reaction raw material chloro cyclic carbonate to the alkali metal or alkaline earth metal fluoride is in the range of 1: 1 to 1: 4, where alkali metal or alkaline earth metal. Is calculated by the number of moles of fluorine atoms.
本発明は主に以下の利点がある：
１．合成工程経路が簡単であること、
２．原料が低価で、入手が容易であること、
３．原料には劇毒及び爆発しやすいという危険がなく、固体と液体の廃棄残渣が形成し
、基本的に環境には汚染がないこと、
４．減圧精留により、フルオロ環状炭酸エステル製品の純度が９９．９％を超え、収率が９０％以上であること。
The present invention mainly has the following advantages:
1. The synthesis process route is simple,
2. The raw materials are low in price and easy to obtain,
3. There is no danger of toxic poison or explosion in raw materials, solid and liquid waste residues are formed, and basically there is no pollution in the environment.
4). The purity of the fluorocyclic carbonate product exceeds 99.9% by vacuum rectification, and the yield is 90% or more.
本発明で用いられる用語の「フルオロ環状炭酸エステル」とは、５位で置換又は無置換の４−フルオロ−１，３−ジオキサシクロペンタン−２−オンのことである。本発明で用いられる用語の「クロロ環状炭酸エステル」とは、５位で置換又は無置換の４−クロロ−１，３−ジオキサシクロペンタン−２−オンのことである。 The term “fluoro cyclic carbonate” used in the present invention refers to 4-fluoro-1,3-dioxacyclopentan-2-one substituted or unsubstituted at the 5-position. The term “chlorocyclic carbonate” used in the present invention refers to 4-chloro-1,3-dioxacyclopentan-2-one substituted or unsubstituted at the 5-position.
以下、本発明について具体的に説明する。その内容は説明のためのものだけで、決して本発明の保護範囲の限定にはならないと理解されるべきである。
一つの好ましい具体的な実施形態において、アルカリ金属又はアルカリ土類金属のフッ化物（特に好ましくはフッ化カリウム）と溶媒（好ましくは炭酸二炭化水素基エステル或は環状炭酸エステル）とを反応容器に入れ、攪拌しながらクラウンエーテル系相間移動触媒を加え、一定の温度（好ましくは７０〜１５０℃）でクロロ環状炭酸エステルを加えて化学反応をさせ、化学反応終了後、冷却してろ過し、ろ液が得られ、このろ液はフルオロ環状炭酸エステル含有反応混合物である。
Hereinafter, the present invention will be specifically described. It should be understood that the contents are for illustrative purposes only and do not in any way limit the scope of protection of the present invention.
In one preferred specific embodiment, an alkali metal or alkaline earth metal fluoride (particularly preferably potassium fluoride) and a solvent (preferably a dicarbonic acid carbonate ester or a cyclic carbonate ester) are added to a reaction vessel. Add a crown ether phase transfer catalyst while stirring, add a chloro cyclic carbonate at a certain temperature (preferably 70 to 150 ° C.) to cause a chemical reaction, and after completion of the chemical reaction, cool and filter. A liquid is obtained, and the filtrate is a fluorocyclic carbonate-containing reaction mixture.
得られた反応混合物は、主にフルオロ環状炭酸エステル生成物と溶媒を含有する。実用的には、フルオロ環状炭酸エステルと溶媒を含有する混合物がそのまま用いられる場合もある。例えば、リチウム電池の固形電解質界面膜（ＳＥＩ膜）の成膜効果或は電解液の溶媒の低温流動性を改善しようとする場合、１０〜５０重量％のフルオロ環状炭酸エステルと５０〜９０重量％の溶媒（例えば炭酸エチレン）を含有する混合物を使用することができる。 The resulting reaction mixture mainly contains a fluorocyclic carbonate product and a solvent. In practice, a mixture containing a fluorocyclic carbonate and a solvent may be used as it is. For example, in order to improve the film forming effect of a solid electrolyte interface film (SEI film) of a lithium battery or the low temperature fluidity of a solvent of an electrolytic solution, 10 to 50% by weight of a fluorocyclic carbonate and 50 to 90% by weight A mixture containing a solvent such as ethylene carbonate can be used.
もう一つの好ましい実施形態において、前記反応混合物に対して減圧精留を行うが、減圧精留の温度範囲は４０〜１５０℃が好ましく、減圧精留の真空度範囲は０．１〜２００ｋＰａが好ましい。留分は収集するが、この留分は精製のフルオロ環状炭酸エステルである。減圧精留により、フルオロ環状炭酸エステル製品の純度は９９．９％、ひいてはそれ以上になることが可能である。 In another preferred embodiment, the reaction mixture is subjected to vacuum rectification. The temperature range of the vacuum rectification is preferably 40 to 150 ° C., and the vacuum range of the vacuum rectification is preferably 0.1 to 200 kPa. . The fraction is collected, but this fraction is a purified fluorocyclic carbonate. By vacuum rectification, the purity of the fluorocyclic carbonate product can be 99.9% and thus even higher.
本発明の方法において、使用できる溶媒は、炭酸ジメチル、炭酸ジエチル、炭酸ジプロピル、炭酸メチルエチル、炭酸メチルプロピル、炭酸エチルプロピル、５−ヘキシル炭酸エチレン、炭酸エチレン、炭酸ジフェニル、５−フェニル炭酸エチレン、炭酸プロピレン及び炭酸フェニル（メチル）フェニルから選ばれる一種或は多種であることが好ましい。 In the method of the present invention, usable solvents are dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, 5-hexyl ethylene carbonate, ethylene carbonate, diphenyl carbonate, 5-phenyl ethylene carbonate, One kind or various kinds selected from propylene carbonate and phenyl (methyl) phenyl carbonate are preferable.
本発明の方法において、溶媒の用量は特に限定がないが、反応原料を十分に反応させることができればよい。好ましくは、溶媒の用量は反応物の総重量の０．５〜１０倍で、かかる反応物の総重量とは、「クロロ環状炭酸エステルとアルカリ金属又はアルカリ土類金属のフッ化物、並びにクラウンエーテル系相間移動触媒の総重量」のことである。 In the method of the present invention, the dose of the solvent is not particularly limited as long as the reaction raw materials can be sufficiently reacted. Preferably, the solvent dosage is 0.5 to 10 times the total weight of the reactants, such as “chloro cyclic carbonate and alkali metal or alkaline earth metal fluoride, and crown ether. It is the total weight of the system phase transfer catalyst.
本発明の方法において、触媒の用量は特に限定がないが、クロロ環状炭酸エステルとアルカリ金属又はアルカリ土類金属のフッ化物の間の化学反応に有効的に触媒作用をすることができればよいが、触媒の用量が多すぎると勿論コストを向上させることになる。好ましくは、触媒の用量は反応物の総重量の０．１〜１０重量％で、より好ましくは０．５〜５重量％である。ここで、かかる反応物の総重量とは、「クロロ環状炭酸エステルとアルカリ金属又はアルカリ土類金属のフッ化物の総重量」のことである。 In the method of the present invention, the dose of the catalyst is not particularly limited as long as it can effectively catalyze the chemical reaction between the chlorocyclic carbonate and the alkali metal or alkaline earth metal fluoride. If the amount of the catalyst is too large, the cost will of course be improved. Preferably, the catalyst dosage is 0.1 to 10% by weight of the total weight of the reactants, more preferably 0.5 to 5% by weight. Here, the total weight of the reactant is “total weight of chloro cyclic carbonate and alkali metal or alkaline earth metal fluoride”.
以下、具体的な実施例で、本発明をさらに説明する。これらの実施例は本発明を説明するためだけで、本発明の範囲を限定するものではないと理解されるべきである。以下の実施例において、具体的な条件が説明されていない実験方法は通常一般の条件、或はメーカーが薦める条件に従う。付加の説明がない限り、すべての「部」は「重量部」で、すべての「％」は「重量％」である。 Hereinafter, the present invention will be further described with specific examples. It should be understood that these examples are merely illustrative of the invention and are not intended to limit the scope of the invention. In the following examples, experimental methods whose specific conditions are not explained generally follow general conditions or conditions recommended by the manufacturer. Unless otherwise stated, all “parts” are “parts by weight” and all “%” are “% by weight” .
＜実施例１＞
炭酸ジメチル３５０ｇとフッ化カリウム２５０ｇ（４．３１モル）が入った３口フラスコに、攪拌しながら触媒の１８−クラウン−６を３ｇ加え、９０℃で４−クロロ−１，３−ジオキサシクロペンタン−２−オン１８０ｇ（１．４７モル）を１時間かけて滴下し、３時間保温した。冷却して、ろ過し、ろ液５２８ｇが得られた。ろ液の成分についてガスクロマトグラフ（ＧＣ−２０１４、株式会社島津製作社から入手）で分析したところ、このろ液は２８．４重量％４−フルオロ−１，３−ジオキサシクロペンタン−２−オンと６８．５６重量％炭酸ジメチルの混合物であることがわかった。
<Example 1>
While stirring, 3 g of catalyst 18-crown-6 was added to a three-necked flask containing 350 g of dimethyl carbonate and 250 g (4.31 mol) of potassium fluoride, and 4-chloro-1,3-dioxacyclo was added at 90 ° C. Pentan-2-one (180 g, 1.47 mol) was added dropwise over 1 hour, and the mixture was kept warm for 3 hours. Cooled and filtered to obtain 528 g of filtrate. When the components of the filtrate were analyzed by gas chromatograph (GC-2014, obtained from Shimadzu Corporation), this filtrate was found to be 28.4% by weight 4-fluoro-1,3-dioxacyclopentan-2-one. And 68.56% by weight dimethyl carbonate.
以上のように得られたろ液に対して減圧精留を行い、９０〜１００℃／２〜５ｋＰａで留分１４５ｇを収集し、ＧＣ／ＭＳ質量分析による結果はｍ／ｚ：１０６、８５で、次の構造式のイオン特徴フラグメントであることが証明された。 The filtrate obtained as described above was subjected to reduced-pressure rectification, and 145 g of a fraction was collected at 90 to 100 ° C./2 to 5 kPa. The result of GC / MS mass spectrometry was m / z: 106, 85, It was proved to be an ionic feature fragment of the following structural formula:
ガスクロマトグラフ（ＧＣ−２０１４、株式会社島津製作社から入手）で測定した結果、留分における４−フルオロ−１，３−ジオキサシクロペンタン−２−オンの純度が９９．９２６５重量％で、４−フルオロ−１，３−ジオキサシクロペンタン−２−オン製品の収率が９３．０６％であった。 As a result of measuring with a gas chromatograph (GC-2014, obtained from Shimadzu Corporation), the purity of 4-fluoro-1,3-dioxacyclopentan-2-one in the fraction was 99.9265% by weight, 4 The yield of -fluoro-1,3-dioxacyclopentan-2-one product was 93.06% .
＜実施例２＞
炭酸プロピレン３５０ｇとフッ化バリウム２５７ｇ（フッ素原子のモル数では２．９４モル）が入った３口フラスコに、攪拌しながら触媒のジベンゾ−１８−クラウン−６を７ｇ加え、１２０℃で４−クロロ−１，３−ジオキサシクロペンタン−２−オン９０ｇ（０．７３５モル）を１時間かけて滴下し、３時間保温した。冷却して、ろ過し、ろ液４３５ｇが得られた。ろ液の成分についてガスクロマトグラフ（ＧＣ−２０１４、株式会社島津製作社から入手）で分析したところ、このろ液は１７．２３重量％４−フルオロ−１，３−ジオキサシクロペンタン−２−オンと８０．８６重量％炭酸プロピレンの混合物であることがわかった。
<Example 2>
7 g of catalyst dibenzo-18-crown-6 was added to a three-necked flask containing 350 g of propylene carbonate and 257 g of barium fluoride (2.94 mol in terms of fluorine atoms) with stirring. -1,3-Dioxacyclopentan-2-one 90 g (0.735 mol) was added dropwise over 1 hour, and the mixture was kept warm for 3 hours. Cooled and filtered to obtain 435 g of filtrate. The components of the filtrate were analyzed with a gas chromatograph (GC-2014, obtained from Shimadzu Corporation), and the filtrate was found to be 17.23 wt% 4-fluoro-1,3-dioxacyclopentan-2-one. And 80.86% by weight of propylene carbonate.
以上のように得られたろ液に対して減圧精留を行い、９０〜１００℃／２〜５ｋＰａで留分７１．５ｇを収集し、ＧＣ／ＭＳ質量分析による結果はｍ／ｚ：１０６、８５で、次の構造式のイオン特徴フラグメントであることが証明された。 The filtrate obtained as described above was subjected to rectification under reduced pressure, and 71.5 g of a fraction was collected at 90 to 100 ° C./2 to 5 kPa, and the results by GC / MS mass spectrometry were m / z: 106, 85. And proved to be an ionic feature fragment of the following structural formula:
ガスクロマトグラフ（ＧＣ−２０１４、株式会社島津製作社から入手）で測定した結果、留分における４−フルオロ−１，３−ジオキサシクロペンタン−２−オンの純度が９９．９３６０重量％で、４−フルオロ−１，３−ジオキサシクロペンタン−２−オン製品の収率が９１．７７％であった。 As a result of measurement with a gas chromatograph (GC-2014, obtained from Shimadzu Corporation), the purity of 4-fluoro-1,3-dioxacyclopentan-2-one in the fraction was 99.9360% by weight, 4 The yield of -fluoro-1,3-dioxacyclopentan-2-one product was 91.77% .
本発明の上述の説明を読んだあと、当業者が本発明に各種の変更や修飾をすることができるが、これらの等価の形態も同じく本願の特許請求の範囲に属するものと理解されるべきである。 After reading the above description of the invention, those skilled in the art will be able to make various changes and modifications to the invention, but it should be understood that equivalent forms thereof are also within the scope of the claims hereof. It is.
本発明の方法で製造したフルオロ環状炭酸エステルは主に高出力リチウム電池のリチウムイオン電解液に用いられる。 The fluorocyclic carbonate produced by the method of the present invention is mainly used for a lithium ion electrolyte solution of a high-power lithium battery.
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