JP2830959B2 - Preparation of acrylonitrile dimer - Google Patents
Preparation of acrylonitrile dimerInfo
- Publication number
- JP2830959B2 JP2830959B2 JP3295225A JP29522591A JP2830959B2 JP 2830959 B2 JP2830959 B2 JP 2830959B2 JP 3295225 A JP3295225 A JP 3295225A JP 29522591 A JP29522591 A JP 29522591A JP 2830959 B2 JP2830959 B2 JP 2830959B2
- Authority
- JP
- Japan
- Prior art keywords
- acrylonitrile
- reaction
- ruthenium
- hydrogen
- dimer
- 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.)
- Expired - Fee Related
Links
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)
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。BACKGROUND OF THE INVENTION The present invention relates to an acrylonitrile dimerization reaction,
The present invention relates to a process for producing a dimer of acrylonitrile in which 4-dicyanobutene and adiponitrile are produced using a ruthenium catalyst. 1,4-dicyanobutene and adiponitrile are intermediates of hexamethylenediamine, a raw material of nylon-66, and intermediates of vulcanization accelerators for rust and 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 has been described in A.I. Misono, et a
1, Bull. Chem. Soc. Jpn. , 40 (1
967) 931 and is well known. This is to dimerize acrylonitrile in the presence of hydrogen using a ruthenium catalyst, but the catalytic activity is low and propionitrile as a by-product is generated, so that the selectivity of acrylonitrile linear dimer is reduced. There was a disadvantage 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 Patent Publication No. 44-24585, in the presence of a ruthenium trichloride catalyst and hydrogen, an acrylonitrile dimerization reaction is carried out by coexisting an alkali metal hydroxide in the reaction system to accelerate the dimerization reaction rate. ing. In the method for producing a linear dimer according to this known technique, methoxypropionitrile accompanied by consumption of alcohol is produced as a by-product, and the reaction rate is industrially low 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 Patent Publication No. 45-4048, when dimerizing acrylonitrile in the presence of a halogen-containing ruthenium compound catalyst and hydrogen, a specific metal (including an alloy and a mixture) is present in a reaction system. This promotes the dimerization reaction rate. Since the production method of the linear dimer of this known technique is a contact reaction between a solid and a liquid,
There is a problem that the reproducibility of the reaction is poor and the reaction speed 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, dimerization is carried out using an inorganic ruthenium derivative, ruthenium carboxylate or a ruthenium complex as a catalyst.
The dimerization reaction is promoted by the presence of a metal carboxylate of an element selected from the group consisting of lead, zinc, cadmium, tin, iron and manganese. The method for producing an acrylonitrile linear dimer according to this known technique has a problem that the selectivity is low and the reaction rate is low.
【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。Accordingly, in the above-mentioned conventional method for producing an acrylonitrile linear dimer, an acrylonitrile low polymer other than propionitrile and the linear dimer and the like are by-produced, and the production rate and selection of the acrylonitrile linear dimer are increased. Rate is low,
There is a problem that the reaction speed is low 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。The present inventors have conducted intensive studies on the above problems, and as a result, in a dimerization reaction of acrylonitrile using a ruthenium catalyst, acrylonitrile was obtained by a simple operation of adding a small amount of a substance to the ruthenium catalyst. High selectivity of the linear dimer was achieved, leading to the present invention in which the reaction rate was improved.
【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。）SUMMARY OF THE INVENTION The present invention relates to a method for dimerizing acrylonitrile to produce linear dimer 1,4-dicyanobutene and adiponitrile by dimerizing acrylonitrile.
The present invention 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 each represent a hydrogen atom or a group having 1 to 20 carbon atoms.
R 3 represents an alkyl or alkenyl group, a phenyl group or a benzyl group having 1 to 20 carbon atoms. )
【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 acrylonitrile dimer, the present inventors have conducted intensive studies to solve the above-mentioned problems, and carried out the reaction of acrylonitrile in the presence of hydrogen using a ruthenium compound as a catalyst. When tin hydride is added during the dimerization reaction, a catalytically active species that preferentially gives a 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, the present invention will be described in detail below.
As the reaction method in the present invention, acrylonitrile,
After a ruthenium compound and HSnR 1 R 2 R 3 are charged into a reactor and the reactor is purged with nitrogen, hydrogen is further introduced at normal pressure, nitrogen gas is replaced with hydrogen, and the temperature is raised to the reaction temperature with stirring. Thereafter, it is preferable to introduce hydrogen, raise the pressure 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 the conditions for the acrylonitrile dimerization reaction, if the reaction rate is too low, the reaction rate is slow, and if it is too high, the catalyst is quickly deactivated. A reaction temperature of 150 ° C. is desirable. The reaction is carried out in the presence of 0.1 mole ratio or more of hydrogen to acrylonitrile. If the hydrogen pressure is too low, the reaction rate is slow, and if it is too high, the equipment cost increases. Therefore, the hydrogen pressure is suitably 1 to 100 kg / cm 2 , preferably 10 to 5 kg / cm 2.
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 the humidity, hydrogen pressure and catalyst, but is preferably 1 to 10 hours.
Solvents need not be used, but solvents such as alcohols, hydrocarbons, water and nitriles 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, the added HSnR 1 R
The 2 R 3, for example trimethyltin hydride, triethyl tin hydride, tri -n- propyl tin hydride, tri -n- butyl tin hydride, triphenyltin hydride, di -n- propyl tin dihydride, di -n- butyl Organic tin hydride compounds such as tin dihydride are exemplified.
【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 used in the present invention is 0.001 to acrylonitrile.
Use ~ 0.2 mol%. Also, HSnR 1 R 2 R 3
If the amount of addition is small, the effect of addition is small, and if it is too large, 2
Since the monomer selectivity is lowered, it is suitably 0.5 to 30 times mol, preferably 1 to 30 times mol, of the ruthenium compound used.
Use 10-fold molar.
【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。Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Example 1 A 100 ml stainless steel autoclave equipped with a stirrer was used as a reactor, and acrylonitrile 20.
0 g (377 mmol), 0.100 g (0.382 mmol) of ruthenium trichloride trihydrate and tri-n-
0.555 g (1.91 mmol) of butyltin hydride is added, nitrogen is replaced several times, then hydrogen is introduced, and hydrogen is replaced several times. The mixture was heated with stirring until the temperature of the reaction solution reached 115 ° C. When the temperature reached 115 ° C,
Pressurize with hydrogen so that the total pressure becomes 20 kg / cm 2 .
The reaction was maintained for 2 hours while maintaining the pressure while replenishing hydrogen.
【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 solution was analyzed by gas chromatography. As a result, unreacted acrylonitrile (3.60 g, 67.9 mmol) and cis-1,4-dicyano-1-butene 5.1 in the reaction solution.
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) Mmol).
【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 these results, the conversion of acrylonitrile was 82%, and the linear dimers (cis-1,4-dicyano-1-butene, trans-1,4-dicyano-1-butene, and adiponitrile) were obtained. Was 67%, and the selectivity for propionitrile was 30%. The formula for calculating the selectivity is 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 type or amount of tin compound (indicated by the 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 performed except that no tin compound was added. Table 1 shows the results.
【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 and 20 hours.
The same operation as in Example 1 was performed, except that the type of the tin compound was changed in minutes. Table 2 shows the results.
【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 performed except that no tin compound was added. Table 2 shows the results.
【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 changed to 100 ° C. Table 3 shows the results.
【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 performed except that no tin compound was added. Table 3 shows the results.
───────────────────────────────────────────────────── フロントページの続き 審査官 藤森 知郎 (56)参考文献 特公 昭54−12450（ＪＰ，Ｂ１) 特公 昭48−43095（ＪＰ，Ｂ１) 特公 昭46−9451（ＪＰ，Ｂ１) 特公 昭45−4048（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.6，ＤＢ名) C07C 255/04 B01J 27/13 C07C 253/30 C07C 255/09────────────────────────────────────────────────── ─── Continuing on the front page Examiner Toshiro Fujimori (56) References JP-B-54-12450 (JP, B1) JP-B-48-43095 (JP, B1) JP-B-46-9451 (JP, B1) No. 45-4048 (JP, B1) (58) Field surveyed (Int. Cl. 6 , DB name) C07C 255/04 B01J 27/13 C07C 253/30 C07C 255/09
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 producing a linear dimer of 1,4-dicyanobutene and adiponitrile by dimerization of acrylonitrile, which comprises reacting acrylonitrile with a ruthenium compound and HSnR 1 R 2 R 3. A method for producing acrylonitrile dimer, which is characterized by dimerization. (R 1 and R 2 each represent a hydrogen atom or an alkyl or alkenyl group having 1 to 20 carbon atoms, a phenyl group or a benzyl group, and R 3 represents an alkyl or alkenyl group having 1 to 20 carbon atoms. , A phenyl group and a 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 JPH069531A (en) | 1994-01-18 |
| JP2830959B2 true 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) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2198081A1 (en) * | 1995-06-29 | 1997-01-16 | Yasuhiko Suzuki | Method for producing dimerization product of acrulonitrile |
-
1991
- 1991-08-23 JP JP3295225A patent/JP2830959B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH069531A (en) | 1994-01-18 |
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