JPH01180852A - Production of isobutyric acid ester - Google Patents
Production of isobutyric acid esterInfo
- Publication number
- JPH01180852A JPH01180852A JP63000637A JP63788A JPH01180852A JP H01180852 A JPH01180852 A JP H01180852A JP 63000637 A JP63000637 A JP 63000637A JP 63788 A JP63788 A JP 63788A JP H01180852 A JPH01180852 A JP H01180852A
- Authority
- JP
- Japan
- Prior art keywords
- acid ester
- propylene
- reaction
- pressure
- formic acid
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 150000002510 isobutyric acid esters Chemical class 0.000 title claims description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 40
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 27
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 16
- 235000019253 formic acid Nutrition 0.000 claims abstract description 15
- -1 formic acid ester Chemical class 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 21
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 21
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 125000005397 methacrylic acid ester group Chemical group 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 18
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 14
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- WDAXFOBOLVPGLV-UHFFFAOYSA-N isobutyric acid ethyl ester Natural products CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 150000001733 carboxylic acid esters Chemical class 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- PRNZBCYBKGCOFI-UHFFFAOYSA-N 2-fluoropropane Chemical compound CC(C)F PRNZBCYBKGCOFI-UHFFFAOYSA-N 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- KFNNIILCVOLYIR-UHFFFAOYSA-N Propyl formate Chemical compound CCCOC=O KFNNIILCVOLYIR-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000010446 mirabilite Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 1
- VUXKVKAHWOVIDN-UHFFFAOYSA-N Cyclohexyl formate Chemical compound O=COC1CCCCC1 VUXKVKAHWOVIDN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- WVRPFQGZHKZCEB-UHFFFAOYSA-N Isopropyl 2-methylpropanoate Chemical compound CC(C)OC(=O)C(C)C WVRPFQGZHKZCEB-UHFFFAOYSA-N 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 229940024423 isopropyl isobutyrate Drugs 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- AVBRYQRTMPHARE-UHFFFAOYSA-N octyl formate Chemical compound CCCCCCCCOC=O AVBRYQRTMPHARE-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RUPAXCPQAAOIPB-UHFFFAOYSA-N tert-butyl formate Chemical compound CC(C)(C)OC=O RUPAXCPQAAOIPB-UHFFFAOYSA-N 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はプロピレンとギ酸エステルからイソ酪酸エステ
ルを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing isobutyric acid ester from propylene and formic acid ester.
イソ酪酸エステルは、ポリマー原料として有用なメタク
リル酸エステルの原料に用いられる。Isobutyric acid ester is used as a raw material for methacrylic acid ester, which is useful as a polymer raw material.
（従来の技術）
カルボン酸エステルは、金属／％１０ゲン化物あるいは
金属カルボニル触媒を用いて、アルコールの存在下でオ
レフィンをカルボニル化することにより生ずることが知
られている。(Prior Art) Carboxylic acid esters are known to be produced by carbonylating olefins in the presence of alcohols using metal/%10 genides or metal carbonyl catalysts.
またプロピレン、一酸化炭素から無機酸中でアシリウム
アニオン生成物を合成し、加水分解あるいはアルコール
でエステル分解させ、イソ酪酸あるいはイソ醋酸エステ
ルを製造する方法が、例えば特開昭５７−１４２９３９
号、特開昭５７−２１２１３４号、特開昭５８−１０５
３５号、特開昭５８−１０５３８号、特開昭５８−６７
６４２号、特開昭６０−８２３６号、特開昭６０−２２
４６５３号などに記載されている。In addition, there is a method of synthesizing an acyl anion product from propylene and carbon monoxide in an inorganic acid, followed by hydrolysis or ester decomposition with alcohol to produce isobutyric acid or isoacetic acid ester, for example, in JP-A-57-142939.
No., JP-A-57-212134, JP-A-58-105
No. 35, JP-A-58-10538, JP-A-58-67
No. 642, JP-A-60-8236, JP-A-60-22
It is described in No. 4653, etc.
更にプロピレン、ギ酸メチルとから無機酸触媒存在下に
イソ酪酸／またはそのエステルを製造する方法が特開昭
５５−７９３３９号に記載されている。Furthermore, a method for producing isobutyric acid/or its ester from propylene and methyl formate in the presence of an inorganic acid catalyst is described in JP-A-55-79339.
（発明が解決しようとする問題点）
金属ハロゲン化物あるいは金属カルボニル触媒を用いて
、アルコールの存在下でオレフィンをカルボニル化して
カルボン酸エステルを製造する方法は、カルボン酸エス
テル生成物は直鎮および分岐異性体の混合物であり、こ
れらの各成分の生成比率は触媒や反応条件を選ぶことに
よりある程度の調節できるが、選択的に分岐カルボン酸
エステルを造ることができない。アルコールの存在下で
プロピレンをカルボニル化した場合も、生成物はノルマ
ル醋酸エステルとイソ酪酸エステルの混合物であり、イ
ソ酪酸エステルのみを選択的に合成することが困難であ
る。(Problems to be Solved by the Invention) A method for producing a carboxylic acid ester by carbonylating an olefin in the presence of an alcohol using a metal halide or metal carbonyl catalyst is a method for producing a carboxylic acid ester, in which the carboxylic acid ester product is either direct or branched. It is a mixture of isomers, and although the production ratio of each of these components can be controlled to some extent by selecting the catalyst and reaction conditions, it is not possible to selectively produce a branched carboxylic acid ester. Even when propylene is carbonylated in the presence of alcohol, the product is a mixture of normal acetic acid ester and isobutyric acid ester, and it is difficult to selectively synthesize only isobutyric acid ester.
またプロピレンと一酸化炭素からフッ化水素酸中でアシ
リウムアニオン生成物を合成し、加水分解あるいはアル
コールによるエステル分解でイソ酪酸あるいはイソ酪酸
エステルを製造する方法は、アシリウムアニオン生成物
を高収率で得るためには１５０〜２００Ｋｇ／ｃｍ２Ｇ
の高圧が必要であり、加水分解あるいはエステル化分解
では水あるいはアルコールをアシリウムアニオン生成物
に対し当モル以下の使用でイソ醋酸あるいはイソ酪酸エ
ステルを得ている。この方法においては未反応アシリニ
ウムアニオンを残存させる必要があり、分離・精製が繁
雑であり、更にアシリニウムアニオンの製造に高圧が必
要なことと合わせて、工業的に問題がある。In addition, the method of synthesizing an acylium anion product from propylene and carbon monoxide in hydrofluoric acid and producing isobutyric acid or isobutyric acid ester by hydrolysis or ester decomposition with alcohol produces an acylium anion product in high yield. To obtain a rate of 150-200Kg/cm2G
In hydrolysis or esterification, isoacetic acid or isobutyric acid ester is obtained by using water or alcohol in an amount equal to or less than the molar amount of the acylium anion product. In this method, it is necessary to leave unreacted acylinium anions, the separation and purification are complicated, and together with the fact that high pressure is required for the production of acylinium anions, there are industrial problems.
プロピレンとギ酸メチルからイソ酪酸／およびイソ酪酸
メチルを製造する方法は、直接イソ酪酸／およびイソ酪
酸メチルを製造出来るが、収率は精々６５％と満足すべ
きものではない。また生成物はイソ酪酸とイソ酪酸メチ
ル混合物として得られ、その分離・精製の面でも問題が
あり、この方法も工業的には有利な方法とは言い難い。Although the method for producing isobutyric acid/and methyl isobutyrate from propylene and methyl formate can directly produce isobutyric acid/and methyl isobutyrate, the yield is at most 65%, which is not satisfactory. Furthermore, the product is obtained as a mixture of isobutyric acid and methyl isobutyrate, and there are problems in its separation and purification, and this method cannot be said to be industrially advantageous.
（問題点を解決するための手段）
発明者らは、以上の如き間趣点を有するイソ酪酸エステ
ルの工業的に有利な製造方法について鋭意検討した結果
、プロピレンとギ酸エステルとを一酸化炭素の雰囲気中
、無水フッ化水素酸触媒の存在下で反応させることによ
り、高収率、且つ高選択率でイソ酪酸エステルが得られ
ることを見出し本発明に至った。(Means for Solving the Problems) As a result of intensive study on an industrially advantageous method for producing isobutyric acid ester having the above-mentioned points, the inventors found that propylene and formic acid ester were combined into carbon monoxide. The present invention was based on the discovery that isobutyric acid ester can be obtained in high yield and high selectivity by reacting in an atmosphere in the presence of an anhydrous hydrofluoric acid catalyst.
即ち本発明は、一酸化炭素雰囲気中、無水フッ化水素酸
触媒存在下でプロピレンとギ酸エステルを反応させるこ
とを特徴とするイソ酪酸エステルの製造方法である。That is, the present invention is a method for producing isobutyric acid ester, which is characterized by reacting propylene and formic acid ester in a carbon monoxide atmosphere in the presence of an anhydrous hydrofluoric acid catalyst.
本発明における反応式は次の如く表される。The reaction formula in the present invention is expressed as follows.
Ｃ３Ｈ５＋ ｌＩｃ０ＯＲ→ＣＨ３ＣＨ（ＣＨ３） Ｃ
０ＯＲ上式のＲは１〜２０個の炭素原子を有するアルキ
ルである。C3H5+ lIc0OR→CH3CH(CH3) C
0OR R in the above formula is alkyl having 1 to 20 carbon atoms.
本発明におけるプロピレンおよびギ酸エステルは、でき
るだけ高純度のものが好ましく、実質的に無水のものが
使用される。The propylene and formic acid ester used in the present invention are preferably as pure as possible, and are substantially anhydrous.
また触媒として使用するフッ化水素酸も無水物を使用す
る。本発明の反応系において水が存在すると、生成した
イソ酪酸エステルが加水分解してイソ酪酸となるので、
イソ酪酸エステルの選択率が低下し、その分離・精製が
困難となる。Anhydrous forms of hydrofluoric acid are also used as catalysts. When water is present in the reaction system of the present invention, the produced isobutyric acid ester is hydrolyzed to become isobutyric acid.
The selectivity of isobutyric acid ester decreases, making it difficult to separate and purify it.
本発明の方法においては、まずプロピレンに無水フッ化
水素酸が付加しイソプロピルフルオライドとなり、次い
で一酸化炭素が無水フッ化水素酸触媒下付加しイソプロ
ピオニルフルオライドとなった後、ギ酸エステルと反応
しイソ酪酸エステルが生成する。この時に始めに付加し
た一酸化炭素が放畠されるので、本発明においては一酸
化炭素は必要であるが実際に消費されない。また予めプ
ロピレンと無水フッ化水素酸を反応させて得られたイソ
プロピルフルオライドを本発明の原料に用いることもで
きる。In the method of the present invention, first, anhydrous hydrofluoric acid is added to propylene to form isopropyl fluoride, and then carbon monoxide is added under the catalyst of hydrofluoric anhydride to form isopropionyl fluoride, which is then reacted with a formic acid ester. Isobutyric acid ester is produced. At this time, the carbon monoxide initially added is released, so although carbon monoxide is necessary in the present invention, it is not actually consumed. Further, isopropyl fluoride obtained by reacting propylene and anhydrous hydrofluoric acid in advance can also be used as the raw material of the present invention.
本発明において使用するギ酸エステルは、アルキル基の
炭素数が２０以下のギ酸アルキルエステルであり、ギ酸
メチル、ギ酸エチル、ギ酸ｎ−プロピル、ギ酸１−プロ
ピル、ギ酸ｎ−ブチル、ギ酸ｌ−ブチル、ギ酸ｔ−ブチ
ル、ギ酸ｎ−オクチル、ギ酸シクロヘキシル等が挙げら
れる。The formic acid esters used in the present invention are formic acid alkyl esters in which the alkyl group has 20 or less carbon atoms, such as methyl formate, ethyl formate, n-propyl formate, 1-propyl formate, n-butyl formate, l-butyl formate, Examples include t-butyl formate, n-octyl formate, and cyclohexyl formate.
無水フッ化水素酸の使用量はギ酸エステル１モルあたり
１〜３０モル、好ましくは３〜２０モルである。またプ
ロピレンとギ酸エステルのモル比はプロピレン１モル当
りギ酸エステル０．５〜１０モル、好ましくは１〜５モ
ルであり、プロピレンの重合を抑制するためにギ酸エス
テルはプロピレンに対し微過剰であることが好ましい。The amount of anhydrous hydrofluoric acid used is 1 to 30 mol, preferably 3 to 20 mol, per mol of formic acid ester. The molar ratio of propylene and formate is 0.5 to 10 moles, preferably 1 to 5 moles, of formate per 1 mole of propylene, and the formate should be in slight excess relative to propylene in order to suppress the polymerization of propylene. is preferred.
本発明における一酸化炭素は、どんな一酸化炭素源から
でもよいが、実質的に無水の反応条件を保つようにする
ため、水を実質的に含まないガスを用いる。一酸化炭素
は反応を妨害しない他の物質で希釈することができ、例
えば乾燥合成ガスまたは部分燃焼ガスを使用することが
できるが、乾燥した一酸化炭素自体を用いることが好ま
しい。Carbon monoxide in the present invention may be from any carbon monoxide source, but in order to maintain substantially anhydrous reaction conditions, a gas substantially free of water is used. The carbon monoxide can be diluted with other substances that do not interfere with the reaction, for example dry synthesis gas or partially combusted gas can be used, but it is preferred to use dry carbon monoxide itself.
本発明において反応は一酸化炭素雰囲気中で実施する。In the present invention, the reaction is carried out in a carbon monoxide atmosphere.
一酸化炭素圧力は１〜１００Ｋｇ／ｃｍ２Ｇの範囲で行
なうことができるが、特に３０〜７０Ｋｇ／ｃｍ２Ｇで
行うことが好ましい。一酸化炭素圧力がｌ Ｋｇ／ｃｍ
２Ｇ未満では反応速度が遅く、またプロピレンの重合が
起こるのでイソ醋酸エステルの収率が低下する。１００
Ｋｇ／ｃｍ２Ｇを越えると反応速度の向上が無くなるの
で有利でない。The carbon monoxide pressure can be carried out in the range of 1 to 100 kg/cm2G, but it is particularly preferable to carry out the carbon monoxide pressure in the range of 30 to 70 kg/cm2G. Carbon monoxide pressure is l Kg/cm
If it is less than 2G, the reaction rate is slow and propylene polymerization occurs, resulting in a decrease in the yield of isoacetic acid ester. 100
If it exceeds Kg/cm2G, there will be no improvement in the reaction rate, which is not advantageous.
本発明の反応温度は０〜１５０℃であり、特に３０〜１
００℃が好ましい。温度が０℃未満では反応速度は著し
く遅く、１５０℃を超えると高沸重合物が副生ずる。The reaction temperature of the present invention is 0 to 150°C, especially 30 to 1
00°C is preferred. If the temperature is less than 0°C, the reaction rate is extremely slow, and if it exceeds 150°C, high-boiling polymers are produced as by-products.
本発明における反応方式としては流通方式、半回分方式
及び回分方式のいずれの方式でも行なうことができる。As the reaction method in the present invention, any of a distribution method, a semi-batch method, and a batch method can be used.
回分方式の場合無水フッ化水素酸にギ酸エステルを添加
してからプロピレンを導いて行なう。無水フッ化水素酸
にプロピレンをギ酸エステルに先立って導くことはプロ
ピレンが重合する結果となり好ましくない。好ましい反
応方式は、無水フッ化水素酸にギ酸エステルを添加し、
一酸化炭素で加圧後、所定反応温度に維持し、プロピレ
ンを少量ずつ導入する方法である。In the case of a batch method, propylene is introduced after adding formic acid ester to anhydrous hydrofluoric acid. It is not preferable to introduce propylene into the anhydrous hydrofluoric acid prior to the formic acid ester because it results in polymerization of the propylene. A preferred reaction method is to add formic acid ester to anhydrous hydrofluoric acid,
In this method, after pressurizing with carbon monoxide, the reaction temperature is maintained at a predetermined temperature, and propylene is introduced little by little.
（効果）
本発明によればプロピレンとギ酸エステルとからイソ酪
酸エステルが高収率、且つ高選択率で製造される。また
本発明の方法は比較的低圧で容易に反応が行われ、イソ
醋酸等の副反応生成物が殆ど無い。このため本発明では
低圧の製造装置で済むと同時に、製品の分離・精製装置
も非常に簡略化される。以上による本発明の産業上の意
義が大きい。(Effects) According to the present invention, isobutyric acid ester is produced from propylene and formic acid ester with high yield and high selectivity. Further, in the method of the present invention, the reaction is easily carried out at a relatively low pressure, and there are almost no side reaction products such as isoacetic acid. Therefore, in the present invention, a low-pressure production apparatus is sufficient, and at the same time, the product separation and purification apparatus is also greatly simplified. According to the above, the present invention has great industrial significance.
（実施例）
次に実施例により本発明を更に具体的に説明する。勿論
本発明はこれらの実施例により制限されるものではない
。(Example) Next, the present invention will be explained in more detail with reference to Examples. Of course, the present invention is not limited to these examples.
実施例１
電磁撹拌装置を備えた２００ｍ １ハステロイ−Ｃ製オ
ートクレーブに、無水フッ化水素酸６０．４ｇ （３，
０２モル）、ギ酸メチル１７．７ｇ （０，２９５モル
）を仕込み、一酸化炭素で７０ｋｇ／ｃｍ’Ｇに加圧し
た。温度を５０℃に昇温し後、プロピレン１１．９ｇ
（０，２８３モル）を７５分で反応器に供給した。圧力
の低下が見られが、再び圧力の上昇が始まった時点で反
応温度を７０℃に上げ、最初の圧力まで復帰したところ
で反応を終了した。反応時間は３．５ｆｌｒを要した。Example 1 60.4 g of anhydrous hydrofluoric acid (3,
02 mol) and 17.7 g (0,295 mol) of methyl formate were charged and pressurized to 70 kg/cm'G with carbon monoxide. After raising the temperature to 50℃, 11.9g of propylene
(0,283 mol) was fed to the reactor in 75 minutes. A decrease in pressure was observed, but when the pressure started to increase again, the reaction temperature was raised to 70°C, and the reaction was terminated when the pressure returned to the initial pressure. The reaction time required 3.5 flr.
反応終了後オートクレーブを冷却し、無水フッ化水素酸
の５倍量の氷水に内容物を取り出した。芒硝で無水フッ
化水素酸を固定化した後トルエンで有機物を抽出し、ガ
スクロマトグラフィーで分析した結果、イソ醋酸メチル
収率は８８．２％であり、イソ酪酸およびイソ醋酸プロ
ピル等の副生物の生成は無かった。After the reaction was completed, the autoclave was cooled and the contents were taken out into ice water in an amount five times that of anhydrous hydrofluoric acid. After immobilizing anhydrous hydrofluoric acid with Glauber's salt, the organic matter was extracted with toluene and analyzed by gas chromatography. As a result, the yield of methyl isoacetate was 88.2%, and by-products such as isobutyric acid and propyl isoacetate were detected. There was no generation of
比較例
一酸化炭素による加圧を実施しない他は、無水フッ化水
素酸、ギ酸メチル、プロピレンの仕込み条件及び反応温
度、反応時間を実施例１と同様として反応を行った。そ
の結果イソ酪酸メチルの収率は３２．８％であり、その
他側生物としてイソ酪酸およびイソ酪酸イソプロピルが
、それぞれ４．０％、０．２％の収率で生成していた。Comparative Example A reaction was carried out under the same conditions as in Example 1 for charging hydrofluoric acid anhydride, methyl formate, and propylene, as well as reaction temperature and reaction time, except that pressurization with carbon monoxide was not carried out. As a result, the yield of methyl isobutyrate was 32.8%, and isobutyric acid and isopropyl isobutyrate were produced as other side products at yields of 4.0% and 0.2%, respectively.
実施例２
実施例１におけるギ酸メチルをギ酸エチルに変えた他は
、全く同じ条件で反応を行なった。反応時間は４Ｈｒを
要した。その結果イソ酪酸エチル収率は８４．９％であ
り、その他の副生物は無かった。Example 2 The reaction was carried out under exactly the same conditions as in Example 1, except that methyl formate was replaced with ethyl formate. The reaction time required 4 hours. As a result, the yield of ethyl isobutyrate was 84.9%, and there were no other by-products.
実施例３
１００ｎ＋Ａ’ハステロイ−Ｃ製オートクレーブに、無
水フッ化水素酸１０ｇ （０，５モル）、ギ酸メチル３
ｇ （０゜０５モル）を仕込み、これにイソプロピルフ
ルオライド２．５ｇ （０，０４０３モル）を供給した
。次に一酸化炭素で４０ｋｇ／ｃｍ２Ｇに加圧し、反応
温度５５℃で反応を行なった。最初圧力の低下が見られ
たが、この圧力に復帰するまで反応を継続した。反応時
間は３Ｈｒを要した。オートクレーブを室温まで冷却後
、内容物を無水フッ化水素酸の５倍量の氷水に取り出し
た。芒硝で無水フッ化水素酸を固定化しトルエンで有機
物を抽出した。トルエン相をガスクロマトグラフィーで
分析した結果、イソ酪酸メチルの収率は９４．７％であ
り、その他の副生物は無かった。Example 3 In a 100n+A' Hastelloy-C autoclave, 10 g (0.5 mol) of anhydrous hydrofluoric acid and 3 methyl formate were added.
g (0.05 mol) was charged, and 2.5 g (0.0403 mol) of isopropyl fluoride was fed thereto. Next, the pressure was increased to 40 kg/cm2G with carbon monoxide, and a reaction was carried out at a reaction temperature of 55°C. Initially, a decrease in pressure was observed, but the reaction was continued until this pressure was restored. The reaction time required 3 hours. After the autoclave was cooled to room temperature, the contents were taken out into ice water in an amount five times that of anhydrous hydrofluoric acid. Anhydrous hydrofluoric acid was immobilized with Glauber's salt and organic matter was extracted with toluene. Analysis of the toluene phase by gas chromatography revealed that the yield of methyl isobutyrate was 94.7% and no other by-products were present.
特許出願人 三菱瓦斯化学株式会社 代理人 弁理士 小 堀 貞 文Patent applicant: Mitsubishi Gas Chemical Co., Ltd. Agent: Patent Attorney Sadafumi Kohori
Claims (2)
下でプロピレンとギ酸エステルを反応させることを特徴
とするイソ酪酸エステルの製造方法(1) A method for producing isobutyric acid ester, which comprises reacting propylene and formic acid ester in a carbon monoxide atmosphere in the presence of an anhydrous hydrofluoric acid catalyst.
で反応させる特許請求範囲第１項の方法(2) Carbon monoxide pressure 1-100kg/cm^2G
The method according to claim 1, in which the reaction is performed with
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63000637A JPH01180852A (en) | 1988-01-07 | 1988-01-07 | Production of isobutyric acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63000637A JPH01180852A (en) | 1988-01-07 | 1988-01-07 | Production of isobutyric acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01180852A true JPH01180852A (en) | 1989-07-18 |
Family
ID=11479234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63000637A Pending JPH01180852A (en) | 1988-01-07 | 1988-01-07 | Production of isobutyric acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01180852A (en) |
-
1988
- 1988-01-07 JP JP63000637A patent/JPH01180852A/en active Pending
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