TW200710070A - Solvent for reaction and production method using the same - Google Patents

Solvent for reaction and production method using the same Download PDF

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TW200710070A
TW200710070A TW95127198A TW95127198A TW200710070A TW 200710070 A TW200710070 A TW 200710070A TW 95127198 A TW95127198 A TW 95127198A TW 95127198 A TW95127198 A TW 95127198A TW 200710070 A TW200710070 A TW 200710070A
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reaction
solvent
acid
anion
mass
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TW95127198A
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Chinese (zh)
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Keiichiro Mizuta
Hironobu Hashimoto
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Nippon Catalytic Chem Ind
Keiichiro Mizuta
Hironobu Hashimoto
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/04Polymerisation in solution
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/14Preparation of carboxylic acid esters from carboxylic acid halides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/54Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Description

200710070 九、發明說明: • 【發明所屬之技術領域】 - 本發明係關於反應用溶劑及使用其之製造方法。更詳 細言之’係關於使用由陽離子與陰離子構成的液狀化合物 (離子性液體)的反應用溶劑及使用該溶劑之製造方法。 【先前技術】 所謂離子性液體係由陽離子與陰離子構成的液狀化合 物,其中具有離子傳導性者,被廣泛地使用於例如:一次 • 電池、鐘(離子)二次電池或燃料電池等具有充電及放電機 構之電池、電解電容器、電雙層電容器、太陽電池-電致色 變(electrochromic)顯示元件等電化學裝置等方面。又,於 此寺用途之外’基於離子性液體本身所具有之各種特性, 其於各種用途之應用也曾被探討。例如,具有於反應過程 中與原料或生成物之反應性小而有安定性之特性者,曾有 人探討使用其作為各種反應用溶劑。 有關離子性液體,曾揭示於離子性液體中使醇或烴進 行乙酿基化之作法(參照例如’司徒華-佛西斯(Stewart A.200710070 IX. Description of the invention: • Technical field to which the invention pertains - The present invention relates to a solvent for reaction and a method for producing the same. More specifically, it is a solvent for the reaction using a liquid compound (ionic liquid) composed of a cation and an anion, and a production method using the solvent. [Prior Art] The ionic liquid system is a liquid compound composed of a cation and an anion, and has ion conductivity, and is widely used, for example, in a primary battery, a clock (ion) secondary battery, or a fuel cell. And electrochemical devices such as batteries for discharge mechanisms, electrolytic capacitors, electric double layer capacitors, solar cells, electrochromic display elements, and the like. Further, in addition to the use of the temple, the use of various properties of the ionic liquid itself has been discussed for various applications. For example, those having a property of being less reactive with a raw material or a product during the reaction and having stability properties have been discussed as a solvent for various reactions. Regarding ionic liquids, it has been revealed that an alcohol or a hydrocarbon is subjected to acetylation in an ionic liquid (see, for example, 'Stewart A.

Forsyth)荨者作 ’ r 化學交流(chemical Communication)」, (英國)’皇家化學協會(Royal Society of Chemistry),2002 年’頁714-715。)。該文獻中記載:藉由使用為有效的溶 劑且為活性鹼觸媒之雙氰胺系離子性液體,可在溫和的條 件下迅速且高產率地進行乙醯基化反應。然而,欲得到可 有效使用於乙醯基化反應以外的反應且可更加提高反應速 度之離子性液體,仍有檢討之餘地。 5 200710070 又’使特定的離子性化合物作為用以進行化學、光化 學、電化學反應之溶劑使用的作法亦曾被揭示(參照例如, 曰本專利特表2000-508677號公報(申請專利範圍第74項, 第%頁以後之實施例等)),於實施例中記載使用鹽作為觸 媒之形態、。然J,欲作為#充分的安定性且可提高反應效 率、亦可適用於各種反應之溶劑,仍有檢討之餘地。 【發明内容】 本發明乃鑑於上述現狀而提出,目的在於提供於各種 =過程中不會揮發、不會與原料或生成物反應、經時性 安定且可充分提高反應效率之反應心劑及使用該溶劑之 製造方法。 本發明人等就反應用溶劑進行各種探討之結果,著眼 於離子性液體中,在反應過程中不會與原料或生成物反 應、並具有化學安定性與熱安定性的特性者,而發現:若 作成為含有具有特定的陰離子之離子性液體《反應用溶 劑’因具有該陰離子而可發揮此等特性,於各種反應過程 中不會揮發到外部、不會與原料或生成物反應、可充分發 揮於長時間的安定性;又發現:可顯著地提高反應速度、 大幅地提高反應效率’而可完美地解決上述課題。而且發 現:藉由使用此等反應用溶劑作為聚合用溶劑,可更充分 地發揮本發明之作用效果。本發明於焉得以達成。 亦即’本發明為-種反應用溶劑,其特徵在於,係含 有具有以下述通式⑴表示之陰離子之離子性液體。 6 200710070Forsyth) ’ "chemical communication", (UK) 'Royal Society of Chemistry, 2002' p. 714-715. ). This document describes that the acetylation reaction can be carried out rapidly and in high yield under mild conditions by using a dicyandiamide-based ionic liquid which is an effective solvent and is an active alkali catalyst. However, there is still room for review in order to obtain an ionic liquid which can be effectively used in reactions other than the acetylation reaction and which can further increase the reaction rate. 5 200710070 Further, the practice of using a specific ionic compound as a solvent for chemical, photochemical, and electrochemical reactions has also been disclosed (refer to, for example, Japanese Patent Laid-Open Publication No. 2000-508677 (Application No. In the examples, 74, and the following examples, etc.)), in the examples, the form in which a salt is used as a catalyst is described. However, there is still room for review as a solvent that is sufficient for stability and can improve the efficiency of the reaction and can also be applied to various reactions. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a reaction agent which does not volatilize in various processes, does not react with a raw material or a product, is stable over time, and can sufficiently improve reaction efficiency. A method of producing the solvent. The inventors of the present invention have conducted various investigations on the reaction solvent, and have focused on the ionic liquid, and have not reacted with the raw material or the product during the reaction, and have chemical stability and thermal stability characteristics, and found that: When the ionic liquid containing a specific anion is used, the solvent for the reaction exhibits such characteristics because it has such an anion, and does not volatilize to the outside during various reaction processes, and does not react with the raw material or the product. It has been used for a long period of time, and it has been found that it can significantly improve the reaction rate and greatly improve the reaction efficiency, and it can perfectly solve the above problems. Further, it has been found that the effects of the present invention can be more fully exerted by using the solvent for the reaction as a solvent for polymerization. The present invention has been achieved. In other words, the present invention is a solvent for the reaction, which is characterized in that it contains an ionic liquid having an anion represented by the following formula (1). 6 200710070

) (式中,x 表示擇自 B、C、N、〇、A1、Si、p、 及Se所構成的群中之至少}種元辛· τη ^ 几1,八及3表示相同或 不同之有機連結基;Q表示有機美 ^衣不韦钺暴,&為i以上之整數、b、 〇、3及6為0以上之整數。 以下’就本發明詳細地做說明。(where x represents at least one of the groups consisting of B, C, N, 〇, A1, Si, p, and Se). The symplectic symplectic · τη ^ is 1, 1 and 3 are the same or different. The organic linking group; Q represents an organic beauty, and is an integer of i or more, and b, 〇, 3, and 6 are integers of 0 or more. Hereinafter, the present invention will be described in detail.

本發明之反應用溶劑(反應溶劑)係含有具有特定陰 子之離子性液體,「離子性液體」係指由陽離子與陰離子 所構成的化合物中為液體狀者。本發明中,可含有^種或 2種以上之此等離子性液體;於含有離子性液冑2種以上 的%合’則可含有由陽離子與陰離子所構成的化合物2種 以上,陽離子或陰離子亦可為同種。 上述離子性液體,較佳為,於40°C下有-定的體積且 具有流動性之液體,具體而言,較佳為於4(TC下為200mPa· 、下之液體,更佳為於下為^ 〇〇mpa · s以下之液體, 再更佳為於40C下$ 50mPa .s以下之液體。又,黏度之 測定方法可使關如,TV_2G㈣度計錐板式(特其枚克公 司製)測定。 上述離子性液體係具有以上述通式(1)表示之陰離子。 此等陰離子,可為構成本發明之反應用溶劑中所含有的離 子性液體之陰離子,亦可為構成其他化合物之陰離子。藉 由具有此等陰離子,可充分地抑制該反應用溶劑於各反應 過程中揮發到外部、或與原料或生成物反應,可充分發揮 7 200710070 長期間之安定性,並可顯著地提高反應速度,大幅地提高 反應效率。The solvent (reaction solvent) for the reaction of the present invention contains an ionic liquid having a specific anion, and the "ionic liquid" means a liquid which is composed of a compound composed of a cation and an anion. In the present invention, two or more kinds of the ionic liquids may be contained, and two or more kinds of compounds composed of a cation and an anion may be contained in a mixture of two or more kinds of ionic liquid hydrazine, and the cation or anion may also be used. Can be the same species. The ionic liquid is preferably a liquid having a predetermined volume and fluidity at 40 ° C, and specifically, preferably 4 (200 mPa· under TC, liquid underneath, more preferably The liquid below ^ 〇〇mpa · s is more preferably a liquid of less than $50mPa.s at 40C. Further, the method of measuring the viscosity can be used as a TV_2G (four) meter taper plate type (specially made by the company) The ionic liquid system has an anion represented by the above formula (1). These anions may be an anion of the ionic liquid contained in the solvent for the reaction of the present invention, or may constitute other compounds. By having such an anion, the solvent for the reaction can be sufficiently suppressed from volatilizing to the outside during each reaction, or reacted with a raw material or a product, and the stability of the long period of 2007 200770 can be fully exerted, and the stability can be remarkably improved. The reaction rate greatly increases the reaction efficiency.

以上述通式(1)表示之陰離子中,X表示擇自B、C、N、 0、Al、Si、p、s、As及Se中之至少1種元素,以c、N 或S為佳’以c或S為更佳。藉此可充分地提高反應用溶 劑之耐熱性,又尤以C為特佳。A及B表示相同或不同之 有機連結基,以分別獨立地擇自-S-、-0-、-S02-、及-CO-中之至少1種連結基為佳,以-S〇2_、_c〇•為更佳。q表示 有枝基’較佳為:氫原子、鹵原子、CpFpp+yHq、 0CpF(2P+i.q)Hq . S〇2CpF(2p+1.q)Hq ^ C02CpF(2p+1.q)Hq ^ S03C6F5_rHr、N02(式中,i 6、0<q$ 13、〇<r$ 5)等; ^ ^ ^ ^ ^ ^ ^ ^ ^ . CpF(2p+1.q)Hq > S02CpF(2p+,q)Hq 〇 a為1以上之整數,b、c、d及e為〇以上之整數,a、 ^及^係依元素X的價數而決定,例如,於X為硫(s)原子 之場合為:a=hd=〇、e==0;於X為氮原子之場合為:(l)a=2、 ㈣、e=0、(2)a=1、扣1、、或⑺Π、扣〇、e=1 之任 一者。又,b&c以〇為佳。 以上述通式⑴表示之陰離子,較佳為:二氰醯胺陰離 子(DCA)、硫代氰酸根陰離子、I氰甲基化物陰離子 (曰T=M)、四氰硼陰離子、氰氧陰離子(cy〇)等,藉此,可 提高耐熱性等之物性,於可充分發揮電性、化學性及執安 :性之同0夺’可更進一步提高反應效率。其中尤以三氰甲 基化物陰離子為更佳。 上述反應用溶劑 要為作為溶劑之場合可適當地發 8 200710070 揮作用者,亦可含有其他陰離子。其他陰離子,可含有例 如:雙三氟甲烷硫醯亞胺陰離子(TFSI)、四氟硼酸陰離子、 乙酸或苯甲酸等之單羧酸;苯二曱酸、馬來酸、琥珀酸陰 離子等之二叛酸陰離子;硫酸甲酯、硫酸乙酯等之硫酸酯 陰離子。又,可使用:六氟磷酸離子、六氟砷酸離子、六 氟錄酸離子、六氟銳酸離子、六敗组酸離子等之含氧無機 離子;苯二甲酸氫離子、馬來酸氫離子、水揚酸離子、苯 曱酸離子、己二酸離子等之羧酸離子;笨磺酸離子、曱苯 磺酸離子、十二烷苯磺酸離子、三氟甲烷磺酸離子、全氟 丁烧績酸離子等之績酸離子;硼酸離子、填酸離子等之無 機氧酸離子;雙(三氟甲烷磺醯)亞胺離子、雙(五氟乙烷磺 醯)亞胺離子、三(三氟甲烷磺醯)甲基化物離子、全氟烷基 氟棚酸根離子(perfluoroalkyl fluoroborate ion)、全氟烧基 氟鱗酸根離子(perfluoroalkyl fluorophosphate ion)、硼二兒 茶紛根 borodicatecholate)、 硼二乙 醇酸根 (borodi glycol at e)、硼二水揚酸根(borodi salicylate)、硼四(三 氟乙酸根)(borotetrakis(trinuoroacetate))、雙(草酸根合)硼 酸根(bis(oxalato)borate)等之四配位硼酸離子等之1種或2 種以上。 於上述反應用溶劑中之陰離子的存在量(全部陰離子之 存在量),為對反應用溶劑1〇〇質量%,源自陰離子之化合 物含有量的下限值較佳為1質量%,更佳為5重量%,再 更佳為10質量%。又,上限值較佳為99·5質量%,更佳為 95質量%,再更佳為90質量%。 9 200710070 又’反應用溶财所含有之全陰離子中1上述通式⑴ 不之陰離子的質量比例,對陰離子總量1〇〇質量0/,下 限較佳為8〇曾吾。/ 1 I ^ 0 WO g里/。。藉此,可更充分發揮於長期間之安定 可充分地提高反應速度。下限更佳為90質量%。 又’上述反應用溶劑可含有構成離子性液體之陽離子, 亦可含有其他陽離子。此種本發明之反應用溶劑中所含有 之陽離子,只要為作為溶劑之場合可適當地發揮作用者皆In the anion represented by the above formula (1), X represents at least one element selected from the group consisting of B, C, N, 0, Al, Si, p, s, As, and Se, preferably c, N or S. 'It is better to use c or S. Thereby, the heat resistance of the solvent for the reaction can be sufficiently improved, and C is particularly preferable. A and B represent the same or different organic linking groups, and are preferably independently selected from at least one of -S-, -0-, -S02-, and -CO-, and -S〇2_, _c〇• is better. q represents a branch base 'preferably: hydrogen atom, halogen atom, CpFpp+yHq, 0CpF(2P+iq)Hq . S〇2CpF(2p+1.q)Hq ^ C02CpF(2p+1.q)Hq ^ S03C6F5_rHr, N02 (where i 6 , 0 < q$ 13 , 〇 < r$ 5), etc.; ^ ^ ^ ^ ^ ^ ^ ^ ^ . CpF(2p+1.q)Hq > S02CpF(2p+, q) Hq 〇a is an integer of 1 or more, and b, c, d, and e are integers above 〇, and a, ^, and ^ are determined by the valence of the element X, for example, when X is a sulfur (s) atom The occasion is: a = hd = 〇, e = 0; where X is a nitrogen atom: (l) a = 2, (four), e = 0, (2) a = 1, deduction 1, or (7) Π, Any one of deductions and e=1. Also, b&c is better. The anion represented by the above formula (1) is preferably a dicyanamide anion (DCA), a thiocyanate anion, an I cyanomethionate anion (曰T=M), a tetracyanoborate anion, or a cyanide anion ( By cy〇), the physical properties such as heat resistance can be improved, and the reaction efficiency can be further improved by fully exhibiting electrical, chemical, and safety properties. Among them, a tricyanomethylate anion is more preferable. The solvent for the above reaction may suitably be used as a solvent, and may also contain other anions. Other anions may contain, for example, a monocarboxylic acid such as bistrifluoromethanesulfonimide anion (TFSI), tetrafluoroborate anion, acetic acid or benzoic acid; benzoic acid, maleic acid, succinic anion, etc. An acid-reducing anion; a sulfate anion such as methyl sulfate or ethyl sulfate. Further, an oxygen-containing inorganic ion such as a hexafluorophosphate ion, a hexafluoroarsenic acid ion, a hexafluoroantimonic acid ion, a hexafluoroacyl acid ion or a hexa-acid acid ion; a hydrogen phthalate hydrogen ion and a hydrogen maleate can be used. Carboxylic acid ions such as ions, salicylic acid ions, benzoic acid ions, adipic acid ions, etc.; stupid sulfonic acid ions, sulfonium benzene sulfonate ions, dodecane benzene sulfonate ions, trifluoromethanesulfonate ions, perfluoro Acidic ions such as acid ions; inorganic acid ions such as boric acid ions and acid ions; bis(trifluoromethanesulfonate) imine ions, bis(pentafluoroethanesulfonyl)imide ions, three (Trifluoromethanesulfonate) methide ion, perfluoroalkyl fluoroborate ion, perfluoroalkyl fluorophosphate ion, boronic borodicatecholate, boron Borodi glycol at e, borodi salicylate, borotetrakis (trinuoroacetate), bis(oxalato)borate Four-coordinate boron 1 of the foregoing ions or two or. The amount of the anion in the solvent for the reaction (the amount of all the anions present) is 1% by mass of the solvent for the reaction, and the lower limit of the content of the compound derived from the anion is preferably 1% by mass, more preferably It is 5% by weight, and more preferably 10% by mass. Further, the upper limit is preferably 99.5% by mass, more preferably 95% by mass, still more preferably 90% by mass. 9 200710070 Further, in the total anion contained in the reaction, the mass ratio of the anion of the above formula (1) is not more than 1% by mass of the anion, and the lower limit is preferably 8〇. / 1 I ^ 0 in WO g /. . Thereby, the stability of the long period can be more fully exerted, and the reaction rate can be sufficiently increased. The lower limit is more preferably 90% by mass. Further, the solvent for the reaction may contain a cation which constitutes an ionic liquid, and may contain other cations. The cation contained in the solvent for the reaction of the present invention can be suitably used as long as it is a solvent.

可,較佳者例如’由以下述通式⑺表示之鏽陽離子作為必 須成分而構成者。 L——Rs (2) 一(式中,L表示C、Si、N、P、S或〇。R為相同或不 同之有機基,亦可互相鍵結。3為3、4或5,為依l的價 數而定之值。) 又,此等陽離子,以形成本發明之反應用溶劑中所含 有的離子性液體之陽離子為佳。較佳為,上述離子性液體 為由以上述通式(1)表示之陰離子與以上述通式(2)表示之陽 子所構成者。此場合’以上述通式(1)表示之陰離子與以 上述通式(2)表示之陽離子所構成之離子性液體,係能於常 溫下安定地保持熔融狀態的常溫熔融鹽,且含有此等熔融 鹽之本發明之反應用溶係係可於長期間發揮更充分之安定 性’又’可更提高於各種反應過程中之反應速度。又,熔 融鹽係指於室溫至8(TC之溫度範圍中可安定地保持液體狀 態者。 以上述通式(2)表示之鑌陽離子,更佳者為以下述通式 200710070 表示者Preferably, for example, 'the rust cation represented by the following general formula (7) is used as a necessary component. L——Rs (2) (wherein L represents C, Si, N, P, S or 〇. R is the same or different organic groups, and may also be bonded to each other. 3 is 3, 4 or 5, The cation of the ionic liquid contained in the solvent for the reaction of the present invention is preferably such a cation. Preferably, the ionic liquid is composed of an anion represented by the above formula (1) and a cation represented by the above formula (2). In this case, the ionic liquid composed of the anion represented by the above formula (1) and the cation represented by the above formula (2) is a room temperature molten salt which can be stably maintained in a molten state at normal temperature, and contains such a molten salt. The molten salt of the reaction system of the present invention can exert a more sufficient stability for a long period of time, and can further increase the reaction rate in various reaction processes. Further, the molten salt refers to a liquid which is stable in a temperature range from room temperature to 8 (TC). The phosphonium cation represented by the above formula (2), more preferably represented by the following formula 200710070

Rl~frR RRl~frR R

R R-R R-

RR

RR

R~〇e-R r\^rR~〇e-R r\^r

R R 同 (式中,R為與上述通式(2)相 此等之中尤以由下述(1)〜(IV)之鏘陽離子為更佳。 又,下述(ΐΜΐπ)之表示陽離子之式中,r1〜ru表 同或不同之有機基,亦可為相互鍵結者,較佳為例二目 原子、氟原子、胺基、亞胺基、酿胺基、⑽基、酯基、: 基、緩基、胺甲酿基、氰基、續酿基、硫離子基㈣胞〇)、 或直鏈、分枝鏈或環狀且可含有氮原子、氧原子、硫原子 等之碳數卜18之烴基、碳化氟基等;更佳者為:氫原子、 氟原子、氰基、績酿基、碳數卜8之煙基、碳化a基。 (1)以下述通式表示之10種之雜環鏽陽離子。 11 200710070RR is the same as (wherein R is the same as the above formula (2), and the cation of the following (1) to (IV) is particularly preferable. Further, the following (ΐΜΐπ) represents a cation. In the formula, r1 to ru are the same or different organic groups, and may also be a bond to each other, preferably a dimethane atom, a fluorine atom, an amine group, an imine group, an amine group, a (10) group, an ester group, : a base, a slow base, an amine methyl group, a cyano group, a continuation base, a sulfonyl group (tetra) cytidine, or a linear, branched or cyclic carbon and may contain a nitrogen atom, an oxygen atom, a sulfur atom or the like. More preferably, it is a hydrocarbon group, a carbonized fluorine group or the like; more preferably: a hydrogen atom, a fluorine atom, a cyano group, a mercapto group, a carbon group of a carbon number 8, and a carbonized a group. (1) Ten kinds of heterocyclic rust cations represented by the following formula. 11 200710070

12 200710070 (II)以下述通式表示之5種不飽和鏽陽離子。12 200710070 (II) Five kinds of unsaturated rust cations represented by the following formula.

(III)以下述通式表示之9種飽和環錄彳陽離子。(III) Nine kinds of saturated ring-recording cations represented by the following formula.

13 200710070 (IV) R為Cl〜C8的烷基之鏈狀鏽陽離子。 此等鏽陽離子中,特佳者為··於通式(2)中 子者;最佳者為··以下述通式 L為氡原13 200710070 (IV) R is a chain rust cation of an alkyl group of Cl~C8. Among these rust cations, the most preferable one is the neutron of the general formula (2); the best one is · the following general formula L is the scorpion

(式中,R1〜R12為與以上述(I)〜(III)通式中之Ri〜Rl2相 同。)表示之6種鑌陽離子、或三乙基甲基銨、二甲基乙美 丙基錢、二乙基甲基甲氧基乙基銨、三甲基丙基銨、三甲 基丁基銨、三甲基己基銨等之鏈狀鑌陽離子等。 於上述反應用溶劑中,陽離子之存在量(全部陽離子之 存在1)之下限值,對存在於反應用溶劑之陰離子1莫耳, 200710070 較佳為〇·5莫耳,更佳為〇·8莫耳。又,上限值較佳為2.〇 莫耳,更佳為1.2莫耳。 又,反應用溶劑中所含有之全陽離子中之以上述通式(2) 表不之鏽陽離子的質量比例,對陽離子總量100質量%, 較佳之下限為80質量%。藉此,可更充分地發揮於長期間 的安定性’且可充分地提高反應速度。更佳之下限為9〇 質量%。 上述反應用溶劑可更進一步含有水或有機溶劑。有機 > 溶劑可舉出例如:1,2_二甲氧基乙烷、四氫呋喃、2-甲基 四氫呋喃、冠驗、三乙二醇甲醚、四乙二醇二甲鱗、二„惡 烧等之鱗類;乙烯碳酸酯、丙烯碳酸酯、二乙基碳酸酯、 曱基乙基碳酸酯等之碳酸酯類;碳酸二甲酯、碳酸乙基甲 基酯、碳酸二乙酯、碳酸二苯酯、碳酸甲基苯基酯等之鏈 狀碳酸酯類;碳酸乙烯酯、碳酸丙稀酯、2,3-二甲基碳酸 乙烯酯、碳酸丁烯酯、碳酸亞乙烯酯、2-亞乙烯碳酸乙烯 酯等之環狀碳酸酯類;甲酸甲酯、乙酸甲酯、丙酸、丙酸 甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸戊酯等之脂 肪族羧酸酯類;苯甲酸甲酯、苯甲酸乙酯等之芳香族羧酸 酯類;Τ -丁内酯、7 -戊内酯、6 -戊内酯等之羧酸酯類; 磷酸三甲酯、磷酸乙基二甲基酯、磷酸二乙基甲基酯、磷 酸三乙酯等之磷酸酯類;乙腈、丙腈、甲氧基丙腈、戊二 腈、己二腈、2-甲基戊二腈等之腈類;Ν-甲基甲醯胺、Ν-乙基曱醯胺、Ν,Ν-二甲基甲醯胺、Ν,Ν-二甲基乙醯胺、Ν-曱基卩比洛烧_ (pyrrolidinon)、Ν-甲基itt σ各烧酮、Ν-乙稀基 15 200710070 毗咯烷酮等之醯胺類;二曱硼、乙基甲基楓、二乙楓、環 丁碾、3_曱基環丁碾、2,4-二甲基環丁楓等之硫化合物類; 乙二醇、丙二醇、乙二酵單甲醚、乙二醇單乙醚等之醇類; 乙二醇二甲醚、乙二醇二乙醚、14-二噁烷、ι,3-二氧五環 烷、四氫呋喃、2_甲基四氫呋喃、2,6_二甲基四氫呋喃、 四氫吡喃等之醚類;二甲亞碾、甲基乙基亞碾、二乙基亞 碾等之亞碾類;苯并腈、甲苯基腈等之芳香族腈類;硝基 曱烧、1,3-二甲基 _2 口米嗤 口定酮(imidazolidinone)、1,3·二甲 基 _3,4,5,6-四氫-2(1H)-嘴咬酮(pyrimidinone)、3-甲基-2-0惡 唑烧酮(oxazolidinone)等,可使用此等之1種或2種以上。 此等之中,以碳酸酯類、脂肪族酯類、崎類為佳,以碳酸 酯類為更佳,尤以7 -丁内酯、7 -戊内酯等之環狀酯類為 最佳。 於上述反應用溶劑含有水或有機溶劑的場合,水 < 有 機溶劑的含有比例之上限值以99質量%為佳。藉此,可充 分降低揮發份,且例如於-55°C之低溫亦不會;東結,為化學 性及熱安定性優異者。較佳為85質量。/◦,更佳為75質量 %,特佳為65質量%。又’下限值以i質量%為佳,較= 為1·5質量%,更佳為20質量%,特佳為5〇質量%。 又,於上述反應用溶劑含有非水系溶劑的場合,以控 制水分含量為佳,藉此,可充分減輕水造成之影響,可提 高反應效率。具體而言,於含有非水系溶劑的場合,上述 反應用溶劑中之水份濃度的上限以1質詈。 只置/〇馮佳,以〇. 1 夤里%為更佳。又,下限值以0.01質量%為佳。 200710070 上述反應用溶劑,以於25°C之黏度為300mpa · s以下 為佳’藉此,可充分提高反應效率。以200mPa · s以下為 更佳,再更佳為lOOmPa · s以下。 上述黏度之測定方法並無特別限定,較佳為例如:於 25°C,使用TV-20型黏度計錐板式(特其枚克公司製)測定 之方法。 上述反應用溶劑,較佳係以具有共軛雙鍵之氮雜環陽 離子為必須成分所構成者,藉此,可提高電化學安定性, 響可適用於更多的反應。 上述具有共軛雙鍵之氮雜環陽離子、與上述⑴之ι〇 種類的雜環鏽陽離子或上述(11)之5種類的不飽和鏽陽離子 等之中,較佳為具有共輛雙鍵、且上述通式(2)中之L為氮 原子者。 上述反應用溶劑之較佳者亦可為含有鹼金屬鹽及/或鹼 土金屬鹽所構成者。此等含有鹼金屬鹽及/或鹼土金屬鹽所 • 構=之本發明反應用溶劑為含有電解質者,亦可適用於電 匕予反應中。鹼金屬鹽以鋰鹽、鈉鹽、鉀鹽為佳,鹼土金 屬鹽以鈣鹽、鎂鹽為佳。尤以鋰鹽為更佳。 ,、上述鹼金屬鹽及/或鹼土金屬鹽可為以上述陰離子為必 肩成刀之化合物,亦可為其他之化合物。 、、以上述陰離子為必須成分之化合物的場合,較佳為上 述通式(1)所表示的陰離子之鹼金屬鹽及/或鹼土金屬鹽 佳,以鐘鹽為更佳。 ^ 旯住此專鋰鹽,除了上述之較佳陰離子的 1 之外,以 LiC(CN)3、LiSi(CN)3、LiB(CN)4、UA1(CN)4、 17 200710070(wherein R1 to R12 are the same as those of Ri to R12 in the above formula (I) to (III)), or triethylmethylammonium or dimethylethlyl. A chain ruthenium cation such as money, diethylmethylmethoxyethylammonium, trimethylpropylammonium, trimethylbutylammonium or trimethylhexylammonium. In the solvent for the above reaction, the amount of the cation (the presence of all cations 1) is the lower limit, and the anion of the anion present in the solvent for the reaction is 1 mol, and 200710070 is preferably 〇·5 mol, more preferably 〇· 8 moles. Further, the upper limit is preferably 2. 莫 Moule, more preferably 1.2 Mo. Further, the mass ratio of the rust cations represented by the above formula (2) in the total cations contained in the solvent for the reaction is 100% by mass based on the total amount of the cations, and the lower limit is preferably 80% by mass. Thereby, the stability in the long period can be more fully exhibited' and the reaction rate can be sufficiently increased. A lower limit is preferably 9 〇 mass%. The solvent for the above reaction may further contain water or an organic solvent. The organic > solvent may, for example, be 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, crown test, triethylene glycol methyl ether, tetraethylene glycol dimethyl scale, and second odor burn Scales; carbonates such as ethylene carbonate, propylene carbonate, diethyl carbonate, mercaptoethyl carbonate; dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, carbonic acid a chain carbonate such as phenyl ester or methyl phenyl carbonate; ethylene carbonate, propylene carbonate, 2,3-dimethylethylene carbonate, butylene carbonate, vinylene carbonate, 2-Asia a cyclic carbonate such as ethylene vinyl carbonate; an aliphatic carboxylic acid ester such as methyl formate, methyl acetate, propionic acid, methyl propionate, ethyl acetate, propyl acetate, butyl acetate or amyl acetate; An aromatic carboxylic acid ester such as methyl benzoate or ethyl benzoate; a carboxylic acid ester such as Τ-butyrolactone, 7-valerolactone or 6-valerolactone; trimethyl phosphate, phosphoric acid Phosphate esters such as ethyl dimethyl ester, diethyl phosphate, and triethyl phosphate; acetonitrile, propionitrile, methoxypropionitrile, glutaronitrile a nitrile such as adiponitrile or 2-methylglutaronitrile; Ν-methylformamide, Ν-ethyl decylamine, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethyl Ethyl amide, Ν-曱 卩 洛 洛 _ ( (pyrrolidinon), Ν-methyl itt σ each ketone, Ν-ethylene group 15 200710070 pyrrolidone and other guanamines; Sulfur compounds such as methylmethyl maple, diethylene maple, cyclobutyl milling, 3_fluorene ring milling, 2,4-dimethylcyclobutyl maple; ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, Alcohols such as ethylene glycol monoethyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 14-dioxane, iota, 2-dioxolane, tetrahydrofuran, 2-methyltetrahydrofuran, 2,6 An ether of dimethyltetrahydrofuran or tetrahydropyran; a sub-mill of dimethyl arylene, methyl ethyl yam, diethyl yam, etc.; an aromatic nitrile of benzonitrile, tolyl nitrile, etc. Class; nitropyrrolidine, 1,3-dimethyl-2-mercaptopurine (imidazolidinone), 1,3·dimethyl-3,4,5,6-tetrahydro-2(1H)- One or two or more of these may be used, such as pyrimidinone and 3-methyl-2-oxazolidine. Among them, carbonates, aliphatic esters, and sulphones are preferred, and carbonates are more preferred, and cyclic esters such as 7-butyrolactone and 7-valerolactone are preferred. When the solvent for the above reaction contains water or an organic solvent, the upper limit of the content ratio of the water to the organic solvent is preferably 99% by mass. Thereby, the volatile matter can be sufficiently reduced, and for example, at a low temperature of -55 ° C. It is not; East knot, which is excellent in chemical and thermal stability. It is preferably 85 mass%./◦, more preferably 75 mass%, especially preferably 65 mass%. The lower limit is i mass%. Preferably, the ratio is 1.5% by mass, more preferably 20% by mass, and particularly preferably 5% by mass. Further, when the solvent for the reaction contains a nonaqueous solvent, it is preferred to control the moisture content, whereby the influence of water can be sufficiently reduced, and the reaction efficiency can be improved. Specifically, when a nonaqueous solvent is contained, the upper limit of the concentration of the water in the solvent for the reaction is 1 詈. Only set / 〇 Feng Jia, to 〇. 1 夤 % % is better. Further, the lower limit is preferably 0.01% by mass. 200710070 The solvent for the above reaction is preferably a viscosity of 300 mPa·s or less at 25 ° C, whereby the reaction efficiency can be sufficiently improved. It is preferably 200 mPa·s or less, and more preferably 100 mPa·s or less. The method for measuring the viscosity is not particularly limited, and is preferably, for example, a method of measuring at a temperature of 25 ° C using a TV-20 type viscometer cone-and-plate type (manufactured by Hitachi, Ltd.). The solvent for the above reaction is preferably composed of a nitrogen heterocyclic cation having a conjugated double bond as an essential component, whereby electrochemical stability can be improved, and the reaction can be applied to more reactions. The nitrogen heterocyclic cation having a conjugated double bond, the heterocyclic rust cation of the oxime type of the above (1) or the unsaturated rust cation of the above five types (11) preferably have a common double bond. Further, in the above formula (2), L is a nitrogen atom. The solvent for the above reaction may preferably be one which contains an alkali metal salt and/or an alkaline earth metal salt. The solvent for the reaction of the present invention containing an alkali metal salt and/or an alkaline earth metal salt is electrolyte-containing, and may be suitable for use in an electric reaction. The alkali metal salt is preferably a lithium salt, a sodium salt or a potassium salt, and the alkaline earth metal salt is preferably a calcium salt or a magnesium salt. Especially lithium salt is better. Further, the alkali metal salt and/or the alkaline earth metal salt may be a compound which is formed by the above anion, or may be another compound. In the case of a compound having an anion as an essential component, it is preferably an alkali metal salt and/or an alkaline earth metal salt of an anion represented by the above formula (1), more preferably a clock salt. ^ Hold this lithium salt, in addition to the above preferred anion 1 , with LiC(CN)3, LiSi(CN)3, LiB(CN)4, UA1(CN)4, 17 200710070

LiP(CN)2、LiP(CN)6、LiAs(CN)6、LiOCN、LiSCN 等為佳。 於其他化合物的場合,以在反應用溶劑中之解離常數 大的電解質鹽為佳,較佳為例如:LiCF3S03、NaCF3S03、 KCFsSO3等之三說甲烷磺酸之鹼金屬鹽或鹼土金屬鹽;LiP(CN)2, LiP(CN)6, LiAs(CN)6, LiOCN, LiSCN, etc. are preferred. In the case of other compounds, an electrolyte salt having a large dissociation constant in the solvent for the reaction is preferred, and for example, an alkali metal salt or an alkaline earth metal salt of methanesulfonic acid is preferably referred to as LiCF3S03, NaCF3S03, KCFsSO3 or the like;

LiN(CF3S03)3、LiN(CF3CF3S02)2 等之全氟鏈烷(alkane)磺Perfluoroalkane (alkane) sulfonate such as LiN(CF3S03)3 and LiN(CF3CF3S02)2

酸亞胺之驗金屬鹽或鹼土金屬鹽;LipF6、NaPF6、KPF6等 之六氟磷酸之鹼金屬鹽或鹼土金屬鹽;Licl〇4、NaC1〇4等 之過氣酸鹼金屬鹽或鹼土金屬鹽;LiBF4、NaBF4等之四氟 朋酉夂孤,LiAsF6、Lil、Nal、NaAsF6、KI等之鹼金屬鹽。 此等之中,就溶解性或離子傳導度考量,以、UBF4、 LiAsF6、全氟鏈烷磺酸亞胺之鹼金屬鹽或鹼土金屬鹽為佳。 ’迷反應用溶劑,亦可含有其他電解質鹽,較佳 ,:過氣酸四乙基錄等之過氣酸之四級録鹽;AH山卿4 等之四氟硼酸之四級錢蹿、γΓ 孤 (c2h5)4npf6 4之四級錢鹽; (CH3)4P · BF4、(C2H5)4p · z 丄 、2 bf4 4之四級鱗鹽等,就溶解性 或離子傳導度考量以四級銨鹽為佳。 上述反應用溶劑中之雷醢併输> 士丄Θ 南丨 解貝孤之存在1,對反應用溶 片J 100質置%,較佳之雷 权 冤解質鹽下限為0.1質量%,較佳之 電解質鹽上限為50質量%。若来谋里杈佳之 . 士 右未滿0.1質$%,離子之絕 對里不足,有無法充分提高 Α ,χ ^ ^ 疋性之虞,若超過50質量〇/〇, 貝厂、、、去使離子之移動更加順 〇/ 〇 貝馋更佳之上限值為30質量 電化〜可藉由含有質+而成為更適於 电化學反應之溶劑。此等更 尺遇於 更進—步含有質子所成之反應用 18 200710070 溶劑亦為本發明之較佳形態之一。又,本發明中藉由含有 可解離並產生質子之化合物,而使得溶劑中會有質子存 在。 上述反應用溶劑中質子之存在量,較佳之下限為對反 應用溶劑0·01莫耳/L,又,較佳之上限為1 〇莫耳/L。若 未滿0.01莫耳/L,質子之絕對量不足,有無法提高質子傳 導度之虞;若超過10莫耳/L,質子之移動無法更順暢。更 佳之上限為5莫耳/L。 上述反應用〉谷劑,只要可發揮本發明之作用效果,亦 可含有1種或2種以上之上述以外的構成要素,例如,亦 可含有各種無機氧化物微粒子。 上述無機氧化物微粒子,較佳為有安定之非電子傳導 ^生、電化學性者。此等微粒子,較佳為:α、冷、7 _氧化 鋁、二氧化矽、二氧化鈦(titania)、氧化鍅、氧化鎂、鈦酸 鋇、氧化鈦(titanium oxide)、水滑石等之離子傳導性戋非A metal salt or an alkaline earth metal salt of an acid imine; an alkali metal salt or an alkaline earth metal salt of a hexafluorophosphoric acid such as LipF6, NaPF6 or KPF6; a peroxyacid alkali metal salt or an alkaline earth metal salt such as LiCl〇4 or NaC1〇4; ; LiBF4, NaBF4, etc., tetracycline, LiAsF6, Lil, Nal, NaAsF6, KI, etc. alkali metal salts. Among these, in view of solubility or ionic conductivity, it is preferred to use an alkali metal salt or an alkaline earth metal salt of UBF4, LiAsF6 or perfluoroalkanesulfinate. The solvent for the reaction may also contain other electrolyte salts, preferably: a tetrabasic salt of a peroxyacid such as a peroxyacid tetraethyl group; a fourth-grade tetrahydrotetrafluoroborate of AH Shanqing 4 or the like; Γ Γ ( (c2h5) 4npf6 4 quaternary salt; (CH3) 4P · BF4, (C2H5) 4p · z 丄, 2 bf4 4 quaternary salt, etc., in terms of solubility or ionic conductivity, quaternary ammonium Salt is better. In the above reaction, the solvent is used in the presence of a Thunder and a sputum, and the presence of a scorpion, a scorpion, and a lower limit of 0.1% by mass. The upper limit of the electrolyte salt is 50% by mass. If you come to the market, you can't get it. The right is less than 0.1%, and the ion is not enough. You can't fully improve it. χ ^ ^ 疋 虞 虞 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若 若The ion movement is made smoother. The upper limit of the yttrium is 30 masses. The electrophoresis can be made into a solvent more suitable for electrochemical reaction by containing the substance. These are more suitable for the reaction of protons. 2007 2007070 Solvent is also one of the preferred forms of the invention. Further, in the present invention, protons are present in the solvent by containing a compound which can dissociate and generate protons. The amount of proton present in the solvent for the above reaction is preferably 0. 01 mol/L for the anti-application solvent, and preferably 1 〇 mol/L. If it is less than 0.01 m/L, the absolute amount of protons is insufficient, and there is no possibility of improving the proton conductivity; if it exceeds 10 m/L, the movement of protons cannot be smoother. A preferred upper limit is 5 moles/L. In the above-mentioned reaction, the granules may contain one or more of the above-mentioned constituent elements, and may contain various inorganic oxide fine particles, as long as the effects of the present invention are exerted. The inorganic oxide fine particles are preferably those which have stable non-electron conduction and electrochemical properties. Such fine particles are preferably ion conductivity of α, cold, 7-alumina, cerium oxide, titania, cerium oxide, magnesium oxide, barium titanate, titanium oxide, hydrotalcite, and the like.戋非

導電性陶瓷微粒子。 / 上述無機氧化物微粒子之比表面積以儘可能大為佳, 具體而言,為卩BET法為5m2/g以上為佳,以5〇m2/g以 上為更佳。此等無機氧化物微粒子之結晶粒徑只要為可與 反應用溶劑中之其他構成要素混合即可,其大小(平均結曰曰、 粒徑)以〇.〇l"m以上為佳,又以20"m以下為佳 者為o.l/zm以上且2/zm以下。 上述無機氧化物微粒子之形狀,可使用球形、卵形、 立方體狀、長方體狀、圓筒狀、棒狀等之各種形狀者。 200710070 上述無機氧化物微粒子之添加量,對反應用溶劑loo 重量份,其上限以100重量份為佳。若超過1〇〇重量份, 離子之移動有無法更順暢之虞;更佳者為;下限為重 量份,上限為20重量份。 又,此外亦可添加:乙酸酐、苯二甲酸酐、馬來釀酐、 琥珀酸酐、均苯四甲酸酐等之酸酐或其酸化合物,三 甲基咪唑等之鹼性化合物。對反應用溶劑1 質量%,添 加量以50質量%以下為佳。以〇〇1質量%以上、2〇二: 以下為更佳。 里/〇 於上述反應用溶劑中,除上述鹽或溶劑之外亦可含有 各種添加劑。添加添加劑有各種目的,可舉出:提言 罕、提南熱安定性、抑制因水合或溶解所致之電極劣化、 抑制氣體產生、提高耐電壓、改善親和性等。此等添加劑 可使用下述之1種或2種以上,該等為例如:對硝基笨酚、J 間硝基乙醯苯酚、對硝基苯甲酸等之硝基化合物;磷酸二 y 1磷酸單丁酯、磷酸二辛酯、辛基膦酸單辛酯、磷酸 等之磷化合物;硼酸或硼酸與多元醇(乙二醇、甘油、甘+ = 糖醇、聚乙烯醇等)或與多醣類之配位化5合物等之硼化人 物’亞硝基化合物;尿素化合物;砷化合物;鈥化合物· 矽酸化合物;鋁酸化合物;硝酸及亞硝酸化合物;2_羥基 N-甲基笨甲酸、二(三)羥基苯甲酸等之苯甲酸類;葡萄糖 西文、重鉻酸、山梨酸、二羧酸、EDTA、氟羧酸、苦味酸、 己一 S文、癸_酸、雜多酸(鶴酸、|目酸)、龍膽酸 硼二龍膽酸、水揚酸、N-胺基水揚酸、硼二原兒茶酸 200710070 硼二焦兒茶酚 (borodiprotocatechuic acid) (borodipyrocatechol)、胺基曱酸(carbamic acid)、爛酸、蝴 二間經苯酸、間羥苯酸、戊二酸、二硫代胺基甲酸等之酸 類;該等之酯、該等之醯胺及其鹽;矽烷偶合劑;二Conductive ceramic microparticles. The specific surface area of the inorganic oxide fine particles is preferably as large as possible. Specifically, the 卩BET method is preferably 5 m 2 /g or more, more preferably 5 〇 m 2 /g or more. The crystal grain size of the inorganic oxide fine particles may be mixed with other components in the solvent for reaction, and the size (average crucible, particle diameter) is preferably 〇. 20"m below is better than ol/zm and below 2/zm. As the shape of the inorganic oxide fine particles, various shapes such as a spherical shape, an oval shape, a cubic shape, a rectangular parallelepiped shape, a cylindrical shape, and a rod shape can be used. 200710070 The amount of the inorganic oxide fine particles added is preferably 100 parts by weight based on the weight of the solvent loo for the reaction. If it exceeds 1 part by weight, the movement of the ions may not be smoother; more preferably, the lower limit is the weight, and the upper limit is 20 parts by weight. Further, an acid anhydride such as acetic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride or pyromellitic anhydride or an acid compound thereof, or a basic compound such as trimethylimidazole may be added. The solvent for the reaction is 1% by mass, and the amount added is preferably 50% by mass or less. 〇〇 1% by mass or more, 2 〇 2: The following is more preferable. In the solvent for the above reaction, various additives may be contained in addition to the above salts or solvents. The addition of the additive has various purposes, such as: introduction of rare, heat sensitivity of the heat, suppression of electrode deterioration due to hydration or dissolution, suppression of gas generation, improvement of withstand voltage, improvement of affinity, and the like. These additives may be used alone or in combination of two or more of the following: nitro compounds such as p-nitrophenol, J-nitroethyl phenol, p-nitrobenzoic acid, etc.; Phosphate compounds such as monobutyl ester, dioctyl phosphate, octylphosphonic acid monooctyl ester, phosphoric acid, etc.; boric acid or boric acid and polyhydric alcohol (ethylene glycol, glycerin, glycerol + = sugar alcohol, polyvinyl alcohol, etc.) or more Boron-like compound of saccharide, such as nitroso compound; urea compound; arsenic compound; bismuth compound, phthalic acid compound; aluminate compound; nitric acid and nitrous acid compound; 2-hydroxyl N-methyl Benzoic acid, di(tri)hydroxybenzoic acid, etc.; benzoic acid; digluconate, dichromic acid, sorbic acid, dicarboxylic acid, EDTA, fluorocarboxylic acid, picric acid, hexa-S, s-acid, miscellaneous Polyacids (haric acid, | acid), gentisic acid uronic acid, salicylic acid, N-aminosalicylic acid, boron di-catechin acid 200710070 boron di pyrocatechol (borodiprotocatechuic acid) ( Borodipyrocatechol), carbamic acid, rotten acid, phthalic acid, meta-hydroxybenzoic acid, pentane Acids such as acid, dithiocarbamic acid, etc.; such esters, such guanamines and salts thereof; decane coupling agents;

石夕、胺基矽酸鹽等之矽化合物;三乙胺、六亞曱基四胺等 之胺化合物;L-胺基酸類;苯(benzol);多元苯紛;氧喹 啉;氫醌;N-曱基焦兒茶酚;喹啉;硫代苯甲醚、硫代甲 齡、硫代苯甲酸等之硫化合物;山梨糖醇;組氨酸等。 上述添加劑之含有量並無特別限定,例如對反應用溶 劑100質量%,較佳為〇·1質量%以上且為2〇質量%以下, 更佳為以0.5質量%以上1〇質量%以下。 本發明之反應用溶劑,於各種反應過程中有經時安定 性’且可充分提南反應效率,故可用於各種反應中。可較 佳地適於下述諸反應,較佳為例如:自由基聚合、陰離子 聚合、陽離子聚合、配位聚合、光聚合、放射線聚合、開 環聚合、加成聚合、聚縮合、加成縮合、電解聚合、氧化 聚合、高分子反應、脫_聚合等之聚合反應;共軛二烯之 短鏈聚合(telomerization);烯烴之二量化、烯烴之寡聚合、 稀煙之聚合、烯烴之烧基化、烯烴之氫化、烯烴複分解、 烯煙之加氫甲醯化、烯烴之閉環複分解、烯烴之開環複分 解聚合、烯烴之對稱或不對稱環氧化(含雜原子取代之烯 fe )、婦煙之ί哀丙烧化等之稀煙之反應;縮合反應、氫化反 應、異構化反應、鈴木交聯偶合反應、胺基化反應、鏈烷 之部分氧化、消旋混合物之動態分割、亞胺之氫化、酮之 21 200710070 氫化移動5L氫化、芳香族有機化合物之經基化等反應。 如上述般,本發明亦為使用上述反應用溶劑之方法。 於上述反應之中,較佳為用於聚合反應,上述反應用 溶劑為聚合用溶劑之形態亦為本發明之較佳形態之一。將 上述反應用溶劑使用於聚合反應中時,可充分抑制上述反 應用溶劑與原料單體和生成之聚合物等之反應,同時聚合 反應速度可大幅地提高,且可大幅提高聚合效率。Anthraquinone compounds such as Shixi, amino phthalate, etc.; amine compounds such as triethylamine and hexamethylenetetramine; L-amino acids; benzol; polyphenylene; oxyquinoline; N-fluorenyl pyrocatechol; quinoline; thioanisole, thio-methyl, thiobenzoic acid and the like sulfur compounds; sorbitol; histidine and the like. The content of the above-mentioned additive is not particularly limited, and is, for example, 100% by mass of the solvent for the reaction, preferably 〇·1% by mass or more and 2% by mass or less, more preferably 0.5% by mass or more and 1% by mass or less. The solvent for the reaction of the present invention has stability over time in various reaction processes and can sufficiently increase the efficiency of the reaction, so that it can be used in various reactions. It is preferably suitable for the following reactions, and is preferably, for example, radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, photopolymerization, radiation polymerization, ring-opening polymerization, addition polymerization, polycondensation, addition condensation Polymerization of electrolytic polymerization, oxidative polymerization, polymer reaction, depolymerization, etc.; telomerization of conjugated diene; quantification of olefins, oligomerization of olefins, polymerization of smoky tobacco, alkylation of olefins , hydrogenation of olefins, metathesis of olefins, hydroformylation of olefins, ring closure metathesis of olefins, ring-opening metathesis of olefins, symmetry or asymmetric epoxidation of olefins (hetero-substituted olefins), maternity The reaction of dilute smoke, such as condensation, hydrogenation, isomerization, Suzuki cross-linking, amination, partial oxidation of alkanes, dynamic partitioning of racemic mixtures, imine Hydrogenation and ketone 21 200710070 Hydrogenation moves 5L hydrogenation, reaction of alkaloids such as aromatic organic compounds. As described above, the present invention is also a method of using the solvent for the above reaction. Among the above reactions, preferred is a polymerization reaction, and the solvent for the above reaction is a solvent for polymerization. When the solvent for the above reaction is used in the polymerization reaction, the reaction between the above-mentioned counter solvent and the raw material monomer and the produced polymer can be sufficiently suppressed, and the polymerization reaction rate can be greatly improved, and the polymerization efficiency can be greatly improved.

本發明亦為製造使用上述反應用溶劑所得之化合物的 製造方法。又,所得之化合物亦含聚合物,藉由此種製造 方法所得到之化合物亦為本發明之一。 於上述製造方法中,反應用溶劑之使用量可依待進行 之反應而適當地選擇,並無特別限定。例如,於使用反應 用溶劑進行聚合反應以得到聚合物的場合,對原料之單體 總量100重量份,較佳為反應用溶劑之下限定為5〇重量 份,上限定為10000重量份,更佳為下限為1〇〇重量份、 上限為5000重量份。 又’上述製造方法中之反應溫度或反應時間、原料量 等之反應條件可依待進行之反應而適當地設定。 本發明之反應用溶劑,由於為上述般的構成,於各種 反應過程中,不會揮發、亦不會與原料和生成物反應,有 經時安定性且可充分提高反應效率,故可較佳地適合於各 種反應中。 【實施方式】 以下,揭示實施例以更詳細地說明本發明,惟,本發 22 「%」 於下述實施例等中The present invention is also a process for producing a compound obtained by using the above solvent for reaction. Further, the obtained compound also contains a polymer, and the compound obtained by such a production method is also one of the inventions. In the above production method, the amount of the solvent for the reaction can be appropriately selected depending on the reaction to be carried out, and is not particularly limited. For example, when a polymerization reaction is carried out using a solvent for a reaction to obtain a polymer, 100 parts by weight of the total amount of monomers of the raw material is preferably limited to 5 parts by weight, and upper limit is 10,000 parts by weight. More preferably, the lower limit is 1 part by weight and the upper limit is 5000 parts by weight. Further, the reaction conditions such as the reaction temperature, the reaction time, and the amount of the raw materials in the above production method can be appropriately set depending on the reaction to be carried out. Since the solvent for the reaction of the present invention has the above-described constitution, it does not volatilize during various reaction processes, does not react with raw materials and products, and has stability over time and can sufficiently improve reaction efficiency. Suitable for various reactions. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples, however, the present invention 22 "%" is in the following examples and the like.

200710070 明並非僅限定於此等實施例。又,只要未 令狩別說明 係指「質量%」。 ^ ^ ^ _ ▼ 夂夕分散度係藉 由依據笨乙烯換算之GPC(凝膠滲透色層分析)來測— 機種:東曹公司製HLC-8020200710070 is not limited to only these embodiments. In addition, as long as the description of the hunting is not made, it means "% by mass". ^ ^ ^ _ ▼ The degree of dispersion is measured by GPC (gel permeation chromatography) based on stupid ethylene conversion. Model: HTC-8020 manufactured by Tosoh Corporation

管柱:TSKgel GMHxl-L (2 支) 開展溶劑:THF 流速:lmL/分 標準:使用標準聚苯乙烯 <作為離子性液體之聚合用溶劑之使用> (實施例1) 於試驗管中加入作為溶劑之EMlmDCA 2mL、作為單 體之甲基丙烯酸甲酯(MMA)lg、作為起始劑且對單體1莫 耳為5毫莫耳的偶氮雙異丁腈,在氮氣環境氣氛下,於7〇 C進行聚合20小時。聚合物之回收則藉由再沈澱於甲醇 來進行。 得到之聚合物之產率為63.1°/。、數量平均分子量為16.6 萬’多分散度為4.3。 (實施例2〜3及比較例1) 除了將溶劑改為EMImTCM(實施例2)、EMImTFSI(實 ^例3)或曱苯(比較例丨)之外,係以與實施例1相同的條 件進行MMA之聚合,所得到之聚合物的物性以與實施例 1相同的做法求出。結果示於表i。 23 200710070 [表i] 溶劑 產率 數量平均分子量 多分散度 實施例1 EMImDCA 63.1 16.6 萬 4.3 實施例2 EMImTCM 26.9 8.9萬 2.4 實施例3 EMImTFSI 40.6 11.5 萬 2.6 比較例1 甲苯 33.1 4.3萬 1.8 表1中之記載係如下述: EMImDCA: 1-乙基-3-曱基咪唑鏽二氰基醯胺 EMImTCM: 1-乙基-3-甲基咪唑鏽三氰基甲基化物 EMImTFSI : 1 -乙基-3-甲基咪唑鏽雙(三氟甲烷磺醯基 亞胺) <作為離子性溶液之反應用溶劑之使用(離子性液體中 之有機合成實施例)〉 (實施例4) 於離子性液體中進行下述之有機合成反應。 於 EMImDCA 5mL 中加入三乙胺 0.86mL與乙醇 0.3 6mL。對其滴入丙浠酸氯化物0.5mL。由反應後之溶液 得到丙烯酸乙酯。對合成之化合物以iH-NMR進行構造確 認’得到化學位移(shift)為 l-3ppm(t)、4_2ppm(q)、 5.8ppm(d)、6.1ppm(q)、6.4ppm(d) 〇 (實施例5〜6) 除了使用EMImTCM(實施例5)或EMImTFSI(實施例6) 代替EMImDCA之外,係以與實施例4同樣的做法進行反 應,得到丙烯酸乙酯。對合成之化合物以1H-NMR進行構 造確認,得到之化學位移,於實施例5及實施例6皆為 1.3ppm(t)、4.2ppm(q)、5.8ppm(d)、6.1ppm(q)、6.4ppm(d) 〇 24 200710070 由於本發明之反應用溶劑係如上述之構成,故於各種 反應過程中不會揮發、亦不會與原料或生成物反應、經時 性安定且可充分提高反應效率,可較佳地適用於各種反應 中 〇 本申請案,係依據2005年7月27日提出申請之日本 專利申請案第2005-217419號「反應用溶劑及使用其之製 造方法」主張優先權。將該申請案之内容全部援用於本申 請案中。 【圖式簡單說明】 無 【主要元件符號說明】 無 25Column: TSKgel GMHxl-L (2) Solvent: THF Flow rate: 1 mL/min Standard: Use standard polystyrene <Use as polymerization solvent for ionic liquid> (Example 1) In test tube 2 mL of EMlmDCA as a solvent, dimethyl methacrylate (MMA) as a monomer, azobisisobutyronitrile as a starter and 5 mmol of monomer 1 molar, under a nitrogen atmosphere The polymerization was carried out at 7 ° C for 20 hours. The recovery of the polymer is carried out by reprecipitation in methanol. The yield of the obtained polymer was 63.1 ° /. The number average molecular weight was 166,000' and the polydispersity was 4.3. (Examples 2 to 3 and Comparative Example 1) The same conditions as in Example 1 were carried out except that the solvent was changed to EMImTCM (Example 2), EMImTFSI (Real Example 3) or toluene (Comparative Example). The polymerization of MMA was carried out, and the physical properties of the obtained polymer were determined in the same manner as in Example 1. The results are shown in Table i. 23 200710070 [Table i] Solvent yield number average molecular weight polydispersity Example 1 EMImDCA 63.1 16.6 million 4.3 Example 2 EMImTCM 26.9 89,000 2.4 Example 3 EMImTFSI 40.6 11.5 million 2.6 Comparative Example 1 Toluene 33.1 4.3 million 1.8 Table 1 The description is as follows: EMImDCA: 1-ethyl-3-mercaptoimidazole rust dicyanamide EMImTCM: 1-ethyl-3-methylimidazole rust tricyanomethylated product EMImTFSI : 1-ethyl- 3-methylimidazole rust bis(trifluoromethanesulfonimide) <Use as solvent for reaction of ionic solution (organic synthesis example in ionic liquid)> (Example 4) In ionic liquid The following organic synthesis reaction was carried out. 0.86 mL of triethylamine and 0.36 mL of ethanol were added to 5 mL of EMImDCA. 0.5 mL of propionate chloride was added thereto. Ethyl acrylate was obtained from the solution after the reaction. The structure of the synthesized compound was confirmed by iH-NMR to obtain a chemical shift of l-3 ppm (t), 4_2 ppm (q), 5.8 ppm (d), 6.1 ppm (q), and 6.4 ppm (d) 〇 ( Examples 5 to 6) Ethyl acrylate was obtained in the same manner as in Example 4 except that EMImTCM (Example 5) or EMImTFSI (Example 6) was used instead of EMImDCA. The structure of the synthesized compound was confirmed by 1H-NMR, and the chemical shift was obtained. In Example 5 and Example 6, 1.3 ppm (t), 4.2 ppm (q), 5.8 ppm (d), and 6.1 ppm (q) were obtained. 6.4 ppm (d) 〇24 200710070 Since the solvent for the reaction of the present invention is as described above, it does not volatilize during various reaction processes, does not react with raw materials or products, and is stable over time and can be sufficiently improved. The reaction efficiency is preferably applied to various reactions. The present application is based on Japanese Patent Application No. 2005-217419, the entire disclosure of which is incorporated herein by reference. right. The contents of this application are all used in this application. [Simple description of the diagram] None [Key component symbol description] None 25

Claims (1)

200710070 十、申請專利範固·· l 一種反應用溶劑,其特徵在於,係含有具有以下述 通式⑴表示之陰離子之離子性液體。200710070 C. Patent application: A solvent for the reaction, which is characterized in that it contains an ionic liquid having an anion represented by the following formula (1). (1) (式中 ’X 表示擇自 B、C、N、〇、AhSi、P、S、As 及Se所構成的群中之至少1種元素丨八及^表示相同或 不同之有機連結基;Q表示有機基;a為1以上之整數、b、 0、(1及6為〇以上之整數。) 2·如申請專利範圍第丨項之反應用溶劑,該反應用溶 劑為聚合用溶劑。 3· —種製造方法,其特徵在於,係使用申請專利範圍 第1或2項之反應用溶劑來製造化合物。 十一、囷式: 益 η、、 26 200710070 七、指定代表圖: (一) 本案指定代表圖為:第(無)圖。 (二) 本代表圖之元件符號簡單說明: 無 八、本案若有化學式時,請揭示最能顯示發明特徵的化學式:(1) (wherein 'X represents at least one element selected from the group consisting of B, C, N, 〇, AhSi, P, S, As, and Se. 丨8 and ^ denote the same or different organic linking group ;Q represents an organic group; a is an integer of 1 or more, b, 0, (1 and 6 are integers of 〇 or more.) 2. The solvent for the reaction of the ninth aspect of the patent application, the solvent for the reaction is a solvent for polymerization 3. A manufacturing method characterized in that a compound is produced by using a solvent for the reaction of the first or second aspect of the patent application. XI. 囷: Yi η, 26 200710070 VII. Designated representative map: (1) The representative representative picture of this case is: the (none) picture. (2) The simple description of the symbol of the representative figure: No. 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 44
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