JPH069531A - Method for producing acrylonitrile dimer - Google Patents
Method for producing acrylonitrile dimerInfo
- Publication number
- JPH069531A JPH069531A JP3295225A JP29522591A JPH069531A JP H069531 A JPH069531 A JP H069531A JP 3295225 A JP3295225 A JP 3295225A JP 29522591 A JP29522591 A JP 29522591A JP H069531 A JPH069531 A JP H069531A
- Authority
- JP
- Japan
- Prior art keywords
- acrylonitrile
- ruthenium
- reaction
- dimer
- compound
- 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.)
- Granted
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
【０００１】[0001]
【産業上の利用分野】本発明は、アクリロニトリルの二
量化反応において、アクリロニトリル直鎖２量体の１，
４−ジシアノブテンおよびアジポニトリルを、ルテニウ
ム触媒を用いて製造するアクリロニトリルの二量体の製
法に関する。１，４−ジシアノブテンおよびアジポニト
リルは、ナイロン−６６原料のヘキサメチレンジアミン
の中間体およびさび止め、ゴムの加硫促進剤の中間体で
ある。FIELD OF THE INVENTION The present invention relates to acrylonitrile linear dimer 1,
The present invention relates to a method for producing a dimer of acrylonitrile, which produces 4-dicyanobutene and adiponitrile using a ruthenium catalyst. 1,4-Dicyanobutene and adiponitrile are intermediates of hexamethylenediamine, which is a raw material of nylon-66, and rust preventives, and vulcanization accelerators of rubber.
【０００２】[0002]
【従来の技術】従来、アクリロニトリルから１，４−ジ
シアノブテン類およびアジポニトリルをルテニウム触媒
を用いて製造する方法は、Ａ．Ｍｉｓｏｎｏ，ｅｔ ａ
ｌ，Ｂｕｌｌ．Ｃｈｅｍ．Ｓｏｃ．Ｊｐｎ．，４０（１
９６７）９３１に記載されており公知である。これはル
テニウム触媒を用いて水素の存在下、アクリロニトリル
を２量化するものであるが、触媒活性が低く、副生成物
であるプロピオニトリルが生成するため、アクリロニト
リル直鎖２量体の選択率が低いという欠点があった。2. Description of the Related Art Conventionally, a method for producing 1,4-dicyanobutenes and adiponitrile from acrylonitrile using a ruthenium catalyst is described in A. Misono, et a
1, Bull. Chem. Soc. Jpn. , 40 (1
967) 931 and is publicly known. This dimerizes acrylonitrile in the presence of hydrogen using a ruthenium catalyst, but the catalytic activity is low, and propionitrile, which is a by-product, is produced, so that the selectivity of the acrylonitrile linear dimer is high. It had the drawback of being low.
【０００３】特公昭４４−２４５８５号では、三塩化ル
テニウム触媒および水素の存在下で、アクリロニトリル
の二量化反応の際に、反応系にアルカリ金属水酸化物を
共存させて二量化反応速度を促進させている。この公知
の技術での直鎖二量体の製法では、副生成物としてアル
コールの消費を伴うメトキシプロピオニトリルが副生
し、工業的に反応速度も遅く十分でなかった。In Japanese Examined Patent Publication No. 44-24585, in the presence of a ruthenium trichloride catalyst and hydrogen, during the dimerization reaction of acrylonitrile, an alkali metal hydroxide coexists in the reaction system to accelerate the dimerization reaction rate. ing. In the method for producing a linear dimer by this known technique, methoxypropionitrile accompanied by consumption of alcohol as a by-product is produced as a by-product, and the reaction rate is industrially slow and not sufficient.
【０００４】特公昭４５−４０４８号では、ハロゲン含
有ルテニウム化合物触媒および水素の存在下でアクリロ
ニトリルの二量化を行う際に、反応系に特定の金属（合
金を含み、また混合物を含む）を存在させて二量化反応
速度を促推させたものである。この公知の技術の直鎖二
量体の製法は、固体と、液体との接触反応であるため、
反応の再現性に乏しく、反応速度も十分ではない問題点
がある。In Japanese Examined Patent Publication (Kokoku) No. 45-4048, when acrylonitrile dimerization is carried out in the presence of a halogen-containing ruthenium compound catalyst and hydrogen, a specific metal (including alloy and mixture) is allowed to be present in the reaction system. It promotes the dimerization reaction rate. Since the method for producing a linear dimer of this known technique is a catalytic reaction between a solid and a liquid,
There are problems that the reproducibility of the reaction is poor and the reaction rate is not sufficient.
【０００５】また、特公昭５４−１２４５０号では、無
機ルテニウム誘導体、カルボン酸ルテニウムまたはルテ
ニウム錯体を触媒として用い二量化する製法で行い、
鉛、亜鉛、カドミウム、錫、鉄およびマンガンからなる
群から選ばれた元素のカルボン酸金属塩を存在させて二
量化反応を促進させている。この公知技術でのアクリロ
ニトリル直鎖二量体の製法では、選択率も低く反応速度
も遅いという問題点がある。In Japanese Patent Publication No. 54-12450, a dimerization method using an inorganic ruthenium derivative, ruthenium carboxylate or ruthenium complex as a catalyst is used.
The dimerization reaction is promoted by the presence of a carboxylic acid metal salt of an element selected from the group consisting of lead, zinc, cadmium, tin, iron and manganese. This known method for producing an acrylonitrile linear dimer has a problem that the selectivity is low and the reaction rate is slow.
【０００６】従って、上記従来のアクリロニトリル直鎖
二量体の製法では、プロピオニトリルおよび直鎖二量体
以外のアクリロニトリル低重合体その他が副生し、アク
リロニトリル直鎖二量体の生成率および選択率が低く、
反応速度も遅くまだ不充分で有るという問題点がある。Therefore, in the above-described conventional method for producing acrylonitrile linear dimer, acrylonitrile low polymer and the like other than propionitrile and linear dimer are by-produced, and the production rate and selection of acrylonitrile linear dimer. Low rate,
There is a problem that the reaction rate is slow and still insufficient.
【０００７】[0007]
【発明が解決しようとする課題】本発明者等は、上記問
題点について鋭意研究した結果、アクリロニトリルのル
テニウム触媒を用いる二量化反応において、ルテニウム
触媒に少量の物質を添加する簡単な操作により、アクリ
ロニトリル直鎖二量体の高い選択率が達せられ、反応速
度を向上させる本発明に至った。DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies on the above problems, and as a result, in the dimerization reaction of acrylonitrile with a ruthenium catalyst, a simple operation of adding a small amount of a substance to the ruthenium catalyst gives acrylonitrile. The high selectivity of the linear dimer has been achieved, and the present invention has been achieved which improves the reaction rate.
【０００８】[0008]
【課題を解決するための手段】本発明は、アクリロニト
リルの二量化により直鎖２量体の１，４−ジシアノブテ
ンおよびアジポニトリルを製造するアクリロニトリルの
二量化反応方法において、ルテニウム化合物とＨＳｎＲ
１Ｒ２Ｒ３の存在下に、アクリロニトリルを二量化する
ことを特徴とするアクリロニトリル二量体の製法に関す
る。（Ｒ１，Ｒ２は、水素原子または炭素数が１〜２０
個のアルキル基もしくはアルケニル基、フェニル基、ベ
ンジル基を示し、Ｒ３は、炭素数が１〜２０個のアルキ
ル基もしくはアルケニル基、フェニル基、ベンジル基を
示す。）DISCLOSURE OF THE INVENTION The present invention relates to a dimerization reaction of acrylonitrile for producing a linear dimer of 1,4-dicyanobutene and adiponitrile by dimerization of acrylonitrile, and a ruthenium compound and HSnR.
It relates to a process for producing an acrylonitrile dimer, which comprises dimerizing acrylonitrile in the presence of 1 R 2 R 3 . (R 1 and R 2 are each a hydrogen atom or a carbon number of 1 to 20.
Represents an alkyl group or an alkenyl group, a phenyl group or a benzyl group, and R 3 represents an alkyl group or an alkenyl group having a carbon number of 1 to 20, a phenyl group or a benzyl group. )
【０００９】本発明者らは、工業的により有利なアクリ
ロニトリルの二量体の製法を見出すために、前述した問
題点を解決すべく鋭意研究を行い、ルテニウム化合物を
触媒とし、水素存在下アクリロニトリルの二量化反応を
行う際に錫ハイドライドを添加すると、二量体を優先的
に与える触媒活性種が、非常に効率よく生成することを
見出し、その結果二量体を選択率よく得ることができ、
更に反応速度も向上させることができるようになり本発
明に到達したのである。In order to find a more industrially advantageous method for producing a dimer of acrylonitrile, the inventors of the present invention have conducted diligent research to solve the above-mentioned problems, using a ruthenium compound as a catalyst, and reacting acrylonitrile in the presence of hydrogen. When tin hydride is added during the dimerization reaction, the catalytically active species that preferentially give the dimer is found to be generated very efficiently, and as a result, the dimer can be obtained with high selectivity,
Furthermore, the reaction rate can be improved and the present invention has been reached.
【００１０】次に、本発明の詳しい説明を以下に行う。
本発明における反応方法としては、アクリロニトリル、
ルテニウム化合物ならびにＨＳｎＲ１Ｒ２Ｒ３を反応器
に仕込み、反応器を窒素置換した後、さらに常圧で水素
を導入し、水素で窒素ガスを置換し、攪拌下に反応温度
まで昇温する。その後水素を導入し、反応圧力迄昇圧し
て所定の時間まで、反応を行うことが好ましい。Next, a detailed description of the present invention will be given below.
As the reaction method in the present invention, acrylonitrile,
A ruthenium compound and HSnR 1 R 2 R 3 are charged into a reactor, the reactor is purged with nitrogen, hydrogen is further introduced at normal pressure, the nitrogen gas is purged with hydrogen, and the temperature is raised to the reaction temperature with stirring. After that, it is preferable to introduce hydrogen, pressurize to the reaction pressure, and carry out the reaction for a predetermined time.
【００１１】アクリロニトリルの２量化反応の条件とし
ては、反応速度は、低すぎると反応速度が遅く、高すぎ
ると触媒の失活が速いため、好適には７０〜２００℃で
あり、好ましくは１００〜１５０℃の反応温度が望まし
い。水素量は、アクリロニトリルに対し０．１モル比以
上を存在させ反応させる。水素圧力は、低すぎると反応
速度が遅く、高すぎると設備費が高くなるため、好適に
は１〜１００ｋｇ／ｃｍ２であり、好ましくは１０〜５
０ｋｇ／ｃｍ２の水素圧力が望ましい。As conditions for the dimerization reaction of acrylonitrile, if the reaction rate is too low, the reaction rate is slow, and if it is too high, the deactivation of the catalyst is fast. Therefore, the reaction rate is preferably 70 to 200 ° C., preferably 100 to 200 ° C. A reaction temperature of 150 ° C is desirable. The amount of hydrogen is allowed to react in the presence of a molar ratio of 0.1 or more relative to acrylonitrile. If the hydrogen pressure is too low, the reaction rate is slow, and if it is too high, the equipment cost becomes high. Therefore, the hydrogen pressure is preferably 1 to 100 kg / cm 2 , and preferably 10 to 5
A hydrogen pressure of 0 kg / cm 2 is desirable.
【００１２】本発明の反応時間は、湿度、水素圧力、触
媒により異なるが、好適には１〜１０時間が望ましい。
溶媒は用いる必要はないが、アルコール、炭化水素、水
およびニトリル等の溶媒も使用することができる。The reaction time of the present invention varies depending on humidity, hydrogen pressure and catalyst, but is preferably 1 to 10 hours.
It is not necessary to use a solvent, but solvents such as alcohol, hydrocarbon, water and nitrile can also be used.
【００１３】本発明において使用されるルテニウム化合
物としては、塩化ルテニウム、臭化ルテニウム、沃化ル
テニウム、ＲｕＣｌ２（アクリロニトリル）４、ＲｕＣ
ｌ２（トリフェニルフォスフィン）３、ＲｕＣｌ２（ト
リフェニルフォスフィン）４などのハロゲン化ルテニウ
ム化合物を使用する。The ruthenium compounds used in the present invention include ruthenium chloride, ruthenium bromide, ruthenium iodide, RuCl 2 (acrylonitrile) 4 , RuC.
Ruthenium halide compounds such as l 2 (triphenylphosphine) 3 and RuCl 2 (triphenylphosphine) 4 are used.
【００１４】この発明において、添加するＨＳｎＲ１Ｒ
２Ｒ３としては、例えばトリメチル錫ハイドライド、ト
リエチル錫ハイドライド、トリ−ｎ−プロピル錫ハイド
ライド、トリ−ｎ−ブチル錫ハイドライド、トリフェニ
ル錫ハイドライド、ジ−ｎ−プロピル錫ジハイドライ
ド、ジ−ｎ−ブチル錫ジハイドライドなどの有機錫ハイ
ドライド化合物があげられる。In the present invention, HSnR 1 R added
Examples of 2 R 3 include trimethyltin hydride, triethyltin hydride, tri-n-propyltin hydride, tri-n-butyltin hydride, triphenyltin hydride, di-n-propyltin dihydride, di-n-butyl. An organic tin hydride compound such as tin dihydride can be used.
【００１５】本発明で使用する触媒のルテニウム化合物
の使用する量は、アクリロニトリルに対して０．００１
〜０．２モル％を使用する。また、ＨＳｎＲ１Ｒ２Ｒ３
の添加量は、少ないと添加効果が少なく、多すぎると２
量体選択率が低下するため、使用したルテニウム化合物
に対して好適には０．５〜３０倍モル、好ましくは１〜
１０倍モルを使用する。The amount of the ruthenium compound used in the catalyst of the present invention is 0.001 with respect to acrylonitrile.
~ 0.2 mol% is used. In addition, HSnR 1 R 2 R 3
If the addition amount is too small, the effect will be small, and if too much, 2
Since the monomer selectivity decreases, it is preferably 0.5 to 30 times mol, preferably 1 to 30 times, the molar amount of the ruthenium compound used.
Use 10 times the mole.
【００１６】[0016]
【実施例】次に、実施例を挙げてさらに具体的に説明す
るが、本発明はこれに限定されるものではない。 実施例１ 反応装置としては、攪拌装置付きの１００ｍｌステンレ
ス製オートクレーブを使用し、アクリロニトリル２０．
０ｇ（３７７ミリモル）を入れ、三塩化ルテニウム三水
和物０．１００ｇ（０．３８２ミリモル）とトリ−ｎ−
ブチル錫ハイドライド０．５５５ｇ（１．９１ミリモ
ル）を加え、窒素置換を数回行い、次いで水素を道入
し、水素置換を数回行う。攪拌しながら反応液の温度が
１１５℃になるまで加熱し、１１５℃に達した時点で、
全圧が２０ｋｇ／ｃｍ２になるように水素で加圧する。
水素を補充しながら圧力を保ち、２時間反応した。EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. Example 1 As a reactor, a 100 ml stainless steel autoclave equipped with a stirrer was used, and acrylonitrile 20.
0 g (377 mmol) was added, and 0.100 g (0.382 mmol) of ruthenium trichloride trihydrate and tri-n-
Butyltin hydride (0.555 g, 1.91 mmol) is added, nitrogen replacement is carried out several times, then hydrogen is introduced, and hydrogen replacement is carried out several times. The temperature of the reaction solution was heated to 115 ° C with stirring, and when the temperature reached 115 ° C,
Pressurize with hydrogen to a total pressure of 20 kg / cm 2 .
The pressure was maintained while replenishing hydrogen, and the reaction was performed for 2 hours.
【００１７】オートクレーブを冷却し、反応液について
ガスクロマトグラフィーで分析した。その結果、反応液
中には未反応アクリロニトリル３．６０ｇ（６７．９ミ
リモル）、シス−１，４−ジシアノ−１−ブテン５．１
５ｇ（４８．６ミリモル）、トランス−１，４−ジシア
ノ−１−ブテン５．１０ｇ（４８．２ミリモル）、アジ
ポニトリル０．７２７ｇ（６．７３ミリモル）、プロピ
オニトリル５．１０ｇ（９２．７ミリモル）が含まれて
いた。The autoclave was cooled and the reaction mixture was analyzed by gas chromatography. As a result, the reaction solution contained 3.60 g (67.9 mmol) of unreacted acrylonitrile, 5.1 of cis-1,4-dicyano-1-butene.
5 g (48.6 mmol), trans-1,4-dicyano-1-butene 5.10 g (48.2 mmol), adiponitrile 0.727 g (6.73 mmol), propionitrile 5.10 g (92.7). Was included).
【００１８】この結果より、アクリロニトリルの転化率
は８２％であり、直鎖二量体（シス−１，４−ジシアノ
−１−ブテン、トランス−１，４−ジシアノ−１−ブテ
ン、およびアジポニトリル）の選択率は、６７％であ
り、プロピオニトリルの選択率は３０％であった。選択
率の計算式は、数式１，２で表す。From this result, the conversion rate of acrylonitrile was 82%, and the linear dimer (cis-1,4-dicyano-1-butene, trans-1,4-dicyano-1-butene, and adiponitrile) was obtained. Was 67% and propionitrile was 30%. Formulas for calculating the selectivity are represented by Formulas 1 and 2.
【００１９】[0019]
【数１】 [Equation 1]
【００２０】[0020]
【数２】 [Equation 2]
【００２１】実施例２〜８ 錫化合物の種類または添加量（Ｓｎ／Ｒｕ原子比で示
す）を変える以外は、実施例１と同様の操作を行った。
その結果は表１に示す。Examples 2 to 8 The same operation as in Example 1 was carried out except that the kind or addition amount of tin compound (indicated by Sn / Ru atomic ratio) was changed.
The results are shown in Table 1.
【００２２】[0022]
【表１】 [Table 1]
【００２３】比較例１ 錫化合物を添加しない以外は、実施例１と同様の操作を
行った。その結果を表１に示す。Comparative Example 1 The same operation as in Example 1 was carried out except that no tin compound was added. The results are shown in Table 1.
【００２４】実施例９〜１１ 反応圧を３０Ｋｇ／ｃｍ２にし、反応時間を１時間２０
分で、錫化合物の種類を変える以外は、実施例１と同様
の操作を行った。その結果を表２に示す。Examples 9 to 11 The reaction pressure was 30 Kg / cm 2 and the reaction time was 1 hour 20.
The same operation as in Example 1 was performed except that the type of tin compound was changed depending on the minutes. The results are shown in Table 2.
【００２５】[0025]
【表２】 [Table 2]
【００２６】比較例２ 錫化合物を添加しない以外は、実施例９と同様の操作を
行った。その結果を表２に示す。Comparative Example 2 The same operation as in Example 9 was carried out except that no tin compound was added. The results are shown in Table 2.
【００２７】実施例１２ 反応温度を１００℃にする以外は、実施例１と同様の操
作を行った。その結果を表３に示す。Example 12 The same operation as in Example 1 was carried out except that the reaction temperature was 100 ° C. The results are shown in Table 3.
【００２８】[0028]
【表３】 [Table 3]
【００２９】比較例３ 錫化合物を添加しない以外は、実施例１２と同様の操作
を行った。その結果を表３に示す。Comparative Example 3 The same operation as in Example 12 was carried out except that no tin compound was added. The results are shown in Table 3.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 白井 昌志 山口県宇部市大字小串1978番地の５ 宇部 興産株式会社宇部研究所内 (72)発明者 島川 敏弘 山口県宇部市大字小串1978番地の５ 宇部 興産株式会社宇部研究所内 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Masashi Shirai, 5 1978, Ogushi, Ube City, Yamaguchi Prefecture 5 1978, Ube Institute of Industrial Research, Ltd. Ube Institute Co., Ltd.
Claims (1)
体の１，４−ジシアノブテンおよびアジポニトリルを製
造するアクリロニトリルの二量化反応方法において、ル
テニウム化合物とＨＳｎＲ１Ｒ２Ｒ３の存在下に、アク
リロニトリルを二量化することを特徴とするアクリロニ
トリル二量体の製法。（Ｒ１，Ｒ２は、水素原子または
炭素数が１〜２０個のアルキル基もしくはアルケニル
基、フェニル基、ベンジル基を示し、Ｒ３は、炭素数が
１〜２０個のアルキル基もしくはアルケニル基、フェニ
ル基、ベンジル基を示す。）1. A method for dimerizing acrylonitrile, which comprises producing a linear dimer of 1,4-dicyanobutene and adiponitrile by dimerization of acrylonitrile, wherein acrylonitrile is added in the presence of a ruthenium compound and HSnR 1 R 2 R 3. A process for producing an acrylonitrile dimer, which is characterized by dimerization. (R 1 and R 2 represent a hydrogen atom or an alkyl group or alkenyl group having 1 to 20 carbon atoms, a phenyl group or a benzyl group, and R 3 represents an alkyl group or alkenyl group having 1 to 20 carbon atoms. , Phenyl group, benzyl group.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3295225A JP2830959B2 (en) | 1991-08-23 | 1991-08-23 | Preparation of acrylonitrile dimer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3295225A JP2830959B2 (en) | 1991-08-23 | 1991-08-23 | Preparation of acrylonitrile dimer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH069531A true JPH069531A (en) | 1994-01-18 |
| JP2830959B2 JP2830959B2 (en) | 1998-12-02 |
Family
ID=17817835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3295225A Expired - Fee Related JP2830959B2 (en) | 1991-08-23 | 1991-08-23 | Preparation of acrylonitrile dimer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2830959B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997001531A1 (en) * | 1995-06-29 | 1997-01-16 | Mitsui Petrochemical Industries, Ltd. | Process for the production of acrylonitrile dimers |
-
1991
- 1991-08-23 JP JP3295225A patent/JP2830959B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997001531A1 (en) * | 1995-06-29 | 1997-01-16 | Mitsui Petrochemical Industries, Ltd. | Process for the production of acrylonitrile dimers |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2830959B2 (en) | 1998-12-02 |
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