JPH0859557A - Method for producing alkenyl-substituted alkylene carbonate - Google Patents
Method for producing alkenyl-substituted alkylene carbonateInfo
- Publication number
- JPH0859557A JPH0859557A JP6195626A JP19562694A JPH0859557A JP H0859557 A JPH0859557 A JP H0859557A JP 6195626 A JP6195626 A JP 6195626A JP 19562694 A JP19562694 A JP 19562694A JP H0859557 A JPH0859557 A JP H0859557A
- Authority
- JP
- Japan
- Prior art keywords
- substituted alkylene
- alkenyl
- reaction
- alkylene carbonate
- glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 alkylene carbonate Chemical class 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 125000002947 alkylene group Chemical class 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 7
- 229910001513 alkali metal bromide Inorganic materials 0.000 claims abstract description 6
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 5
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UCAOGXRUJFKQAP-UHFFFAOYSA-N n,n-dimethyl-5-nitropyridin-2-amine Chemical compound CN(C)C1=CC=C([N+]([O-])=O)C=N1 UCAOGXRUJFKQAP-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- DBCILFBCLWASPY-UHFFFAOYSA-N 2-(2-chloroethenyl)oxirane Chemical compound ClC=CC1CO1 DBCILFBCLWASPY-UHFFFAOYSA-N 0.000 description 1
- WAVKEPUFQMUGBP-UHFFFAOYSA-N 2-(3-nitrophenyl)acetonitrile Chemical compound [O-][N+](=O)C1=CC=CC(CC#N)=C1 WAVKEPUFQMUGBP-UHFFFAOYSA-N 0.000 description 1
- NOBAKBYLYZQTMS-UHFFFAOYSA-N 2-ethenyl-2-ethyloxirane Chemical compound CCC1(C=C)CO1 NOBAKBYLYZQTMS-UHFFFAOYSA-N 0.000 description 1
- JZQHTTYHPIAPCZ-UHFFFAOYSA-N 2-prop-1-en-2-yloxirane Chemical compound CC(=C)C1CO1 JZQHTTYHPIAPCZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
(57)【要約】
【構成】 触媒として、アルカリ金属の臭化物及び／又
は塩化物を用い、アルケニル置換アルキレンオキシドと
二酸化炭素とを反応せしめてアルケニル置換アルキレン
カーボネートを製造する際に、アルケニル置換アルキレ
ンオキシドに対し０．２〜１重量倍のアルコール類の存
在下に反応せしめることを特徴とするアルケニル置換ア
ルキレンカーボネートの製造方法。
【効果】 温和な反応条件の下にアルケニル置換アルキ
レンカーボネートを高収率で製造することができる。(57) [Summary] [Structure] When an alkenyl-substituted alkylene oxide is reacted with carbon dioxide by using an alkali metal bromide and / or chloride as a catalyst, an alkenyl-substituted alkylene oxide is produced. The method for producing an alkenyl-substituted alkylene carbonate is characterized in that the reaction is carried out in the presence of 0.2 to 1 times by weight of alcohols. [Effect] The alkenyl-substituted alkylene carbonate can be produced in high yield under mild reaction conditions.
Description
【０００１】[0001]
【０００２】本発明はアルケニル置換アルキレンカーボ
ネートと二酸化炭素とからアルケニル置換アルキレンカ
ーボネートを製造する方法に関する。詳しくは触媒とし
てアルカリ金属の臭化物及び／又は塩化物を用い比較的
温和な条件下でアルケニル置換アルキレンオキシドと二
酸化炭素とを反応せしめて、高い反応速度及び収率でア
ルケニル置換アルキレンカーボネートを製造する方法に
関する。The present invention relates to a method for producing alkenyl-substituted alkylene carbonate from alkenyl-substituted alkylene carbonate and carbon dioxide. More specifically, a method for producing an alkenyl-substituted alkylene carbonate at a high reaction rate and yield by reacting an alkenyl-substituted alkylene oxide with carbon dioxide under relatively mild conditions using an alkali metal bromide and / or chloride as a catalyst. Regarding
【０００３】[0003]
【従来の技術】従来、ブタジエンモノオキシドと二酸化
炭素とから４−ビニルエチレンカーボネートを製造する
際に用いる触媒として、有機第３級ホスフィン化合物
（特公昭４８−２２７０２号公報）、クロム、マンガ
ン、ルテニウム、ロジウム、カドミウムの金属のハロゲ
ン化物と有機第３級ホスフィン化合物（特公昭４７−２
６７８６号公報）等が提案されている。しかしこれらの
方法では、反応は１８０℃以上、５０Ｋｇ／ｃｍ2 以上
という高温、高圧下で行われているため、反応器などの
設備費が高くなり経済的に有利な方法とはいえない。2. Description of the Related Art Conventionally, organic tertiary phosphine compounds (Japanese Patent Publication No. 48-22702), chromium, manganese and ruthenium have been used as catalysts for producing 4-vinylethylene carbonate from butadiene monoxide and carbon dioxide. , Rhodium and cadmium metal halides and organic tertiary phosphine compounds (Japanese Patent Publication No. 47-2
No. 6786) has been proposed. However, in these methods, the reaction is carried out at a high temperature of 180 ° C. or higher and at a pressure of 50 Kg / cm 2 or higher and under high pressure, and therefore the equipment cost of the reactor and the like is high, and it cannot be said to be an economically advantageous method.
【０００４】また、テトラキストリフェニルホスフィン
パラジウムとトリフェニルホスフィンの組み合わせから
なる触媒を用いる方法〔Tatuo Fujinami et al, Chemis
tryLetters, 第２号；199 ページ、（1985年）〕があ
る。しかしこの方法では、触媒として高価で空気に対し
不安定なパラジウム触媒を使用するため、その回収、再
使用に十分な注意が必要であり、少しでも損失があると
コスト高になる欠点がある。Further, a method using a catalyst composed of a combination of tetrakistriphenylphosphine palladium and triphenylphosphine [Tatuo Fujinami et al, Chemis
tryLetters, No. 2; p. 199, (1985)]. However, in this method, since a palladium catalyst which is expensive and unstable to air is used as a catalyst, it is necessary to pay sufficient attention to its recovery and reuse, and there is a disadvantage that even a slight loss causes an increase in cost.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、アルケニル
置換アルキレンオキシドと二酸化炭素を反応させてアル
ケニル置換アルキレンカーボネートを製造するにあた
り、安価なアルカリ金属の臭化物及び／又は塩化物を触
媒として使用し、且つ、反応温度、反応圧力をより温和
とすると共に、高い反応速度及び収率を得る、経済的に
有利にアルケニル置換アルキレンカーボネートの製造方
法を提供することを目的とする。The present invention uses an inexpensive alkali metal bromide and / or chloride as a catalyst in producing an alkenyl-substituted alkylene carbonate by reacting an alkenyl-substituted alkylene oxide with carbon dioxide, In addition, it is an object of the present invention to provide a method for producing an alkenyl-substituted alkylene carbonate that is more economical in terms of obtaining a higher reaction rate and yield while making the reaction temperature and the reaction pressure milder.
【０００６】[0006]
【課題を解決するための手段】即ち、本発明は、アルケ
ニル置換アルキレンカーボネートと二酸化炭素とをアル
カリ金属の臭素化物及び／又は塩化物を触媒としアルケ
ニル置換アルキレンオキシドに対し０．２〜１重量倍の
アルコールの存在下で反応せしめることを特徴とする、
温和な条件下で反応速度が高く、しかも高収率にアルケ
ニル置換アルキレンカーボネートを製造できる、経済的
に有利なアルケニル置換アルキレンカーボネートの製造
方法を提供するものである。That is, the present invention uses alkenyl-substituted alkylene carbonate and carbon dioxide in an amount of 0.2 to 1 times the weight of alkenyl-substituted alkylene oxide by using an alkali metal bromide and / or chloride as a catalyst. Characterized by reacting in the presence of alcohol,
It is intended to provide an economically advantageous method for producing an alkenyl-substituted alkylene carbonate, which has a high reaction rate under mild conditions and can produce an alkenyl-substituted alkylene carbonate in a high yield.
【０００７】アルケニル置換アルキレンオキシドとして
は、下記一般式（１）The alkenyl-substituted alkylene oxide has the following general formula (1)
【０００８】[0008]
【化１】 Embedded image
【０００９】（式中、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 は、水素
原子、ハロゲン原子、又は炭素数１〜４のアルキル基を
示す。）で示される化合物である。具体例としては、ブ
タジエンモノオキシド、イソプレンモノオキシド、１−
クロロ−３，４−エポキシ−１−ブテン、２−エチル−
２ビニルオキシラン等が挙げられる。(Wherein R 1 , R 2 , R 3 and R 4 represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms). Specific examples include butadiene monoxide, isoprene monoxide, 1-
Chloro-3,4-epoxy-1-butene, 2-ethyl-
2 Vinyl oxirane etc. are mentioned.
【００１０】アルケニル置換アルキレンオキシドと二酸
化炭素との反応は下記式（２）に従って進行する。The reaction between the alkenyl-substituted alkylene oxide and carbon dioxide proceeds according to the following formula (2).
【００１１】[0011]
【化２】 Embedded image
【００１２】本発明の方法において、触媒として用いら
れるアルカリ金属の臭化物及び／又は塩化物としては、
ナトリウム、カリウム、ルビジウム、セシウム、及びリ
チウムの臭化物、並びに、塩化物であり、これらは、比
較的安価に入手できしかも安定であるので回収、再使用
も容易である。価格の面からは特にナトリウム、カリウ
ムの臭化物及び／又は塩化物が好ましい。In the method of the present invention, as the alkali metal bromide and / or chloride used as a catalyst,
Bromides of sodium, potassium, rubidium, cesium, and lithium, and chlorides, which are relatively inexpensively available and stable, and thus can be easily recovered and reused. From the viewpoint of cost, bromide and / or chloride of sodium and potassium are particularly preferable.
【００１３】触媒の使用量は、原料アルケニル置換アル
キレンオキシド１ｍｏｌに対して０．００１ｍｏｌ％〜
１０ｍｏｌ％、好ましくは０．０１ｍｏｌ％〜５ｍｏｌ
％であり、一般的にはその使用量が多いほど反応促進効
果は向上するが、効果の向上にも自ら限界があり、反応
液への溶解量の制限から、実用的には反応液に対する飽
和溶解量の範囲である。The amount of the catalyst used is 0.001 mol% to 1 mol of the starting alkenyl-substituted alkylene oxide.
10 mol%, preferably 0.01 mol% to 5 mol
%, Generally, the larger the amount used, the higher the reaction accelerating effect, but there is a limit to the improvement of the effect, and due to the limitation of the amount dissolved in the reaction solution, it is practically saturated with the reaction solution. It is the range of the amount of dissolution.
【００１４】溶媒として用いるアルコールとしては特に
制限はなく、経済的に有利なものであればよい。具体例
としては、メタノール、エタノール、ｎ−プロパノー
ル、ｉ−プロパノール、等の炭素数１〜３の脂肪族１価
アルコール、エチレングリコール、プロピレングリコー
ル、１．３−プロパンジオール、１．２−ブタンジオー
ル、１．４−ブタンジオール、１．６−ヘキサンジオー
ル等の脂肪族２価アルコール、シクロヘキサンジオー
ル、シクロヘキサンジメタノール等の脂環族２価アルコ
ール、ベンゼンジメタノール（ｏ、ｍ、ｐ、）等の芳香
族２価アルコール、グリセリン等の脂肪族多価アルコー
ル、ジエチレングリコール、ジプロピレングリコール、
トリエチレングリコール、トリプロピレングリコール等
のポリアルキレングリコールが挙げられる。The alcohol used as the solvent is not particularly limited and may be any one which is economically advantageous. Specific examples include aliphatic monohydric alcohols having 1 to 3 carbon atoms such as methanol, ethanol, n-propanol and i-propanol, ethylene glycol, propylene glycol, 1.3-propanediol, 1.2-butanediol. , Aliphatic dihydric alcohols such as 1.4-butanediol and 1.6-hexanediol, alicyclic dihydric alcohols such as cyclohexanediol and cyclohexanedimethanol, and benzenedimethanol (o, m, p,) Aromatic dihydric alcohol, aliphatic polyhydric alcohol such as glycerin, diethylene glycol, dipropylene glycol,
Examples thereof include polyalkylene glycols such as triethylene glycol and tripropylene glycol.
【００１５】反応性の面から、アルキレングリコール及
びポリアルキレングリコール、特に、ジエチレングリコ
ール、プロピレングリコール、トリエチレングリコール
が好ましい。From the viewpoint of reactivity, alkylene glycols and polyalkylene glycols, particularly diethylene glycol, propylene glycol and triethylene glycol are preferred.
【００１６】アルコール類の使用量は、原料のアルケニ
ル置換アルキレンオキシドの０．２〜１重量倍である。
その量が多くなるほど反応促進効果が向上するが、多す
ぎると反応帯域のアルケニル置換アルキレンオキシドの
濃度が低くなり反応速度が著しく遅くなり、反応器当た
りのアルケニル置換アルキレンカーボネートの生産量は
低いものとなる。The amount of alcohol used is 0.2 to 1 times by weight that of the alkenyl-substituted alkylene oxide used as the raw material.
If the amount is too large, the reaction promoting effect is improved, but if it is too large, the concentration of the alkenyl-substituted alkylene oxide in the reaction zone becomes low and the reaction rate becomes remarkably slow, and the production amount of alkenyl-substituted alkylene carbonate per reactor is low. Become.
【００１７】アルコールの適量使用により、アルケニル
置換アルキレンオキシド、二酸化炭素、及び触媒のアル
カリ金属ハライドを好適に溶解し、反応帯液中における
これらの接触反応が有利に行われる。その結果、後述の
実施例で明らかなごとく、低い反応温度及び反応圧力に
て速い反応速度が得られる。By using an appropriate amount of alcohol, the alkenyl-substituted alkylene oxide, carbon dioxide, and the alkali metal halide of the catalyst are preferably dissolved, and their catalytic reaction in the reaction zone liquid is advantageously carried out. As a result, a fast reaction rate can be obtained at a low reaction temperature and a reaction pressure, as will be apparent from the examples described later.
【００１８】反応は、通常、アルケニル置換アルキレン
オキシドと触媒とアルコール類とを反応器に仕込み、こ
れに二酸化炭素を供給し、撹拌等により混合しつつ加熱
を行い反応を開始せしめる。反応の進行とともに二酸化
炭素が消費されるので、二酸化炭素を連続的に供給して
反応を完結せしめる。In the reaction, the alkenyl-substituted alkylene oxide, the catalyst and the alcohol are usually charged in a reactor, carbon dioxide is supplied to the reactor, and the mixture is heated by stirring or the like to start the reaction. Since carbon dioxide is consumed as the reaction progresses, carbon dioxide is continuously supplied to complete the reaction.
【００１９】反応温度は、通常５０℃〜２００℃、好ま
しくは５０℃〜１５０℃の範囲である。反応圧力は、反
応温度、二酸化炭素量、および反応液組成等により変化
し、また反応の進行（経過）に応じても反応圧力を変化
させることができるが、通常、全圧で１〜２０Kg/cm2G
（０．１〜２．０ＭＰａ）、好ましくは、全圧で１〜１
０Kg/cm2G （０．１〜１．０ＭＰａ）の範囲である。The reaction temperature is usually 50 ° C to 200 ° C, preferably 50 ° C to 150 ° C. The reaction pressure varies depending on the reaction temperature, the amount of carbon dioxide, the composition of the reaction solution, and the like, and the reaction pressure can also be changed depending on the progress (elapsed time) of the reaction, but normally, the total pressure is 1 to 20 Kg / cm 2 G
(0.1 to 2.0 MPa), preferably 1 to 1 at total pressure
It is in the range of 0 kg / cm 2 G (0.1 to 1.0 MPa).
【００２０】反応時間は、触媒の種類により異なるが通
常０．５時間〜４時間である。The reaction time varies depending on the type of catalyst, but is usually 0.5 to 4 hours.
【００２１】[0021]
【実施例】以下に実施例を挙げ、本発明をさらに具体的
に説明する。なお、アルケニル置換アルキレンカーボネ
ートの定量はガスクロマトグラフィーで行った。EXAMPLES The present invention will be described in more detail with reference to the following examples. The alkenyl-substituted alkylene carbonate was quantified by gas chromatography.
【００２２】実施例１： 容量５０ｍｌの撹拌機を備え
たステンレス製オートクレーブに、ブタジエンモノオキ
シド１７．５ｇ、触媒として臭化カリウム０．３ｇ、お
よびトリエチレングリコール１１．４ｇ仕込み、反応器
内を二酸化炭素で置換したのち、二酸化炭素を圧入し２
Kg/cm2G とした後、１１０℃まで昇温した。Example 1: A stainless steel autoclave equipped with a stirrer having a capacity of 50 ml was charged with 17.5 g of butadiene monooxide, 0.3 g of potassium bromide as a catalyst, and 11.4 g of triethylene glycol, and the inside of the reactor was oxidized. After substituting with carbon, pressurize with carbon dioxide to 2
After setting to Kg / cm 2 G, the temperature was raised to 110 ° C.
【００２３】昇温に伴い圧力は若干上昇したが、反応の
進行に伴い圧力が下降するので、圧力を常に９．５Ｋｇ
／ｃｍ2 に保つように二酸化炭素をボンベより連続供給
した。かかる状態を維持して３時間反応を継続させた。
反応終了後、内容物を分析したところ４−ビニルエチレ
ンカーボネートの収率は８６．０％であった。Although the pressure increased slightly as the temperature increased, the pressure decreased as the reaction proceeded, so the pressure was constantly maintained at 9.5 Kg.
Carbon dioxide was continuously supplied from a cylinder so as to keep the pressure at / cm 2 . While maintaining this state, the reaction was continued for 3 hours.
After the completion of the reaction, the content was analyzed and the yield of 4-vinylethylene carbonate was 86.0%.
【００２４】実施例２： 実施例１において、ブタジエ
ンモノオキシドに代えてイソプレンモノオキシド１７．
５ｇを用いた他は、実施例１と同様にして反応を行った
結果、４−メチル−４−ビニルエチレンカーボネートの
収率は８４．０％であった。Example 2: In Example 1, instead of butadiene monooxide, isoprene monooxide 17.
As a result of carrying out the reaction in the same manner as in Example 1 except that 5 g was used, the yield of 4-methyl-4-vinylethylene carbonate was 84.0%.
【００２５】比較例： 実施例１において、トリエチレ
ングリコールを仕込まなかった他は実施例と同様にして
反応を行った結果、二酸化炭素の消費はなく、３時間経
過後の４−ビニルエチレンカーボネートの収率は０％で
あった。Comparative Example: As a result of carrying out the reaction in the same manner as in Example 1 except that triethylene glycol was not charged, carbon dioxide was not consumed, and 4-vinylethylene carbonate after 3 hours had passed. The yield was 0%.
Claims (4)
酸化炭素とをアルカリ金属の臭化物及び／又は塩化物を
触媒とし、アルケニル置換アルキレンオキシドに対し
０．２〜１重量倍のアルコールの存在下で反応せしめる
ことを特徴とするアルケニル置換アルキレンカーボネー
トの製造方法。1. A method for reacting an alkenyl-substituted alkylene oxide with carbon dioxide in the presence of an alcohol in an amount of 0.2 to 1 weight times that of the alkenyl-substituted alkylene oxide, using an alkali metal bromide and / or chloride as a catalyst. A method for producing an alkenyl-substituted alkylene carbonate, which is characterized.
１に記載の方法。2. The method according to claim 1, wherein the alcohol is a dihydric alcohol.
プロピレングリコール、ジエチレングリコール、ジプロ
ピレングリコール、トリエチレングリコール、及びトリ
プロピレングリコールから選ばれるものである請求項２
に記載の方法。3. The dihydric alcohol is ethylene glycol,
3. A compound selected from propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tripropylene glycol.
The method described in.
（０．１ＭＰａ〜２．０ＭＰａ）の範囲で行われる請求
項１に記載の方法。4. The reaction is carried out at a pressure of 1 to 20 kg / cm 2 G
The method according to claim 1, wherein the method is performed in the range of (0.1 MPa to 2.0 MPa).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6195626A JPH0859557A (en) | 1994-08-19 | 1994-08-19 | Method for producing alkenyl-substituted alkylene carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6195626A JPH0859557A (en) | 1994-08-19 | 1994-08-19 | Method for producing alkenyl-substituted alkylene carbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0859557A true JPH0859557A (en) | 1996-03-05 |
Family
ID=16344301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6195626A Pending JPH0859557A (en) | 1994-08-19 | 1994-08-19 | Method for producing alkenyl-substituted alkylene carbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0859557A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6315918B1 (en) | 1997-09-11 | 2001-11-13 | Mitsui Chemicals Inc. | Non-aqueous electrolytic solution for capacitor and capacitor containing non-aqueous electrolytic solution |
| JP2005200323A (en) * | 2004-01-14 | 2005-07-28 | Mitsubishi Chemicals Corp | Method for producing 3,4-diacetoxy-1-butene and derivatives using the same |
| JP2011219394A (en) * | 2010-04-07 | 2011-11-04 | Kuraray Co Ltd | METHOD FOR PRODUCING α,β-UNSATURATED ESTER |
-
1994
- 1994-08-19 JP JP6195626A patent/JPH0859557A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6315918B1 (en) | 1997-09-11 | 2001-11-13 | Mitsui Chemicals Inc. | Non-aqueous electrolytic solution for capacitor and capacitor containing non-aqueous electrolytic solution |
| JP2005200323A (en) * | 2004-01-14 | 2005-07-28 | Mitsubishi Chemicals Corp | Method for producing 3,4-diacetoxy-1-butene and derivatives using the same |
| JP2011219394A (en) * | 2010-04-07 | 2011-11-04 | Kuraray Co Ltd | METHOD FOR PRODUCING α,β-UNSATURATED ESTER |
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