JP2608715B2 - Method for producing 4-methyl-1-pentene - Google Patents
Method for producing 4-methyl-1-penteneInfo
- Publication number
- JP2608715B2 JP2608715B2 JP62088067A JP8806787A JP2608715B2 JP 2608715 B2 JP2608715 B2 JP 2608715B2 JP 62088067 A JP62088067 A JP 62088067A JP 8806787 A JP8806787 A JP 8806787A JP 2608715 B2 JP2608715 B2 JP 2608715B2
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- pentene
- reaction
- producing
- carbon atoms
- 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 - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/24—Catalytic processes with metals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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の二量化による４−メチル−１−
ペンテンに関するものである。４−メチル−１−ペンテ
ンは耐熱性ポリマーの原料，ポリオレフィン用のコモノ
マー等として工業的に極めて有用である。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to 4-methyl-1- by dimerization of propylene.
It is related to penten. 4-Methyl-1-pentene is industrially extremely useful as a raw material of a heat-resistant polymer, a comonomer for polyolefin, and the like.
＜従来の技術＞ プロピレンを二量化して４−メチル−１−ペンテンを
製造する方法はよく知られており，種種の触媒が用いら
れている。またこのプロピレン二量化触媒として無水炭
酸カリウム担体にアルカリ金属を担持した触媒を用いる
ことも知られている（特開昭43−25344号公報）。<Prior Art> A method for producing 4-methyl-1-pentene by dimerizing propylene is well known, and various kinds of catalysts are used. It is also known to use a catalyst in which an alkali metal is supported on an anhydrous potassium carbonate carrier as the propylene dimerization catalyst (JP-A-43-25344).
しかしながらこれらの方法においては，目的の４−メ
チル−１−ペンテンの他にかなりの４−メチル−２−ペ
ンテンが副生する。４−メチル−２−ペンテンは４−メ
チル−１−ペンテンとその沸点が非常に近いために，両
者を分離して４−メチル−１−ペンテンを精製するため
には多段の蒸留塔及び多量のスチームが必要となる。However, in these methods, considerable 4-methyl-2-pentene is by-produced in addition to the desired 4-methyl-1-pentene. Since 4-methyl-2-pentene has a boiling point very close to that of 4-methyl-1-pentene, a multi-stage distillation column and a large amount of 4-methyl-1-pentene are required to separate 4-methyl-1-pentene and purify 4-methyl-1-pentene. Steam is required.
＜発明が解決しようとする問題点＞ 本発明はかかる従来の技術の欠点，即ちプロピレンを
二量化して４−メチル−１−ペンテンを製造する方法に
おいて４−メチル−１−ペンテンの副生を抑制し,4−メ
チル−１−ペンテンを選択的に得る工業的に有利な方法
を提供することを目的とするものである。<Problems to be Solved by the Invention> The present invention has a disadvantage of such a conventional technique, that is, a method for producing 4-methyl-1-pentene by dimerizing propylene, in which a by-product of 4-methyl-1-pentene is produced. It is an object of the present invention to provide an industrially advantageous method for obtaining 4-methyl-1-pentene selectively.
＜問題点を解決するための手段＞ 本発明者らはプロピレンを二量化して４−メチル−１
−ペンテンを製造する方法において,4−メチル−２−ペ
ンテンの副生を抑制し,4−メチル−１−ペンテンを選択
性よく得るための工業的に有利な方法について鋭意研究
を行い，本発明に到達したものであり，以下の要件を備
えることを特徴とする。<Means for Solving the Problems> The present inventors dimerized propylene to give 4-methyl-1
In the process for producing pentene, diligent research has been conducted on an industrially advantageous method for suppressing the by-product of 4-methyl-2-pentene and obtaining 4-methyl-1-pentene with good selectivity. And is characterized by having the following requirements.
本発明は、プロピレンを二量化し、４−メチル−１−
ペンテンを製造する方法において、無水炭酸カリウム担
体にナトリウムを担持した触媒の存在下に，反応系に炭
素数３〜30のアミン類及び炭素数３〜20のケトン類から
選ばれる少なくとも１種以上の化合物を存在させ反応せ
しめることを特徴とする４−メチル−１−ペンテンの製
造方法に係るものである。The present invention provides dimerization of propylene, and 4-methyl-1-
In the method for producing pentene, in the presence of a catalyst in which sodium is supported on an anhydrous potassium carbonate carrier, at least one kind selected from amines having 3 to 30 carbon atoms and ketones having 3 to 20 carbon atoms is added to the reaction system. The present invention relates to a method for producing 4-methyl-1-pentene, which comprises reacting a compound in the presence of the compound.
本願発明において用いられる触媒は、無水炭酸カリウ
ム担体にナトリウムを担持した触媒である。The catalyst used in the present invention is a catalyst in which sodium is supported on an anhydrous potassium carbonate carrier.
無水炭酸カリウム担体にナトリウムを担持する方法と
しては液体アンモニアにナトリウムを溶解して担体に含
浸する方法，ナトリウムを担体に蒸着させる方法などが
挙げられるが，好ましい例としてはナトリウムの融解す
る温度で担体とナトリウムを撹拌する方法が挙げられ
る。Examples of a method of supporting sodium on an anhydrous potassium carbonate carrier include a method of dissolving sodium in liquid ammonia and impregnating the carrier, and a method of depositing sodium on the carrier. Preferred examples include a method in which sodium is melted at a temperature at which sodium melts. And sodium is stirred.
ナトリウムの担持量は好ましくは無水炭酸カリウム担
体に対して0.5〜10重量％，さらに好ましくは１〜５重
量％である。The loading amount of sodium is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, based on the anhydrous potassium carbonate carrier.
次に反応系に添加する化合物について説明する。本願
発明方法において反応系に添加する化合物は炭素数３〜
30のアミン類及び炭素数３〜20のケトン類から選ばれる
少なくとも１種以上の化合物である。Next, the compound added to the reaction system will be described. In the method of the present invention, the compound added to the reaction system has 3 to 3 carbon atoms.
It is at least one compound selected from amines having 30 and ketones having 3 to 20 carbon atoms.
炭素数３〜30のアミン類としてはイソブチルアミン,N
−メチルピペリジン，トリオクチルアミン，アニリン等
が挙げられるが，好ましくは炭素数３〜30の脂肪族３級
アミンあるいは炭素数３〜30の肪環式３級アミンが用い
られる。As amines having 3 to 30 carbon atoms, isobutylamine, N
-Methylpiperidine, trioctylamine, aniline and the like, and preferably, an aliphatic tertiary amine having 3 to 30 carbon atoms or an aliphatic tertiary amine having 3 to 30 carbon atoms is used.
炭素数３〜20のケトン類としてはアセトン，メチルエ
チルケトン，ジオクチルケトン，アセトフェノン等が挙
げられる。Examples of ketones having 3 to 20 carbon atoms include acetone, methyl ethyl ketone, dioctyl ketone, acetophenone and the like.
さらに好ましくは炭素数３〜30の脂肪族３級アミン，
炭素数３〜30の肪環式３級アミンから選ばれる少くとも
１種以上の化合物が用いられる。More preferably, an aliphatic tertiary amine having 3 to 30 carbon atoms,
At least one compound selected from aliphatic tertiary amines having 3 to 30 carbon atoms is used.
これらの化合物は通常単独で用いられるが，場合によ
っては２種以上の化合物を混合して用いてもよい。また
同一化合物内にヒドロキシル基，アミノ基，エーテル
基，カルボニル基より選ばれる２種以上の置換基を有す
る化合物を用いてもよい。These compounds are usually used alone, but in some cases, two or more compounds may be used as a mixture. A compound having two or more substituents selected from a hydroxyl group, an amino group, an ether group, and a carbonyl group in the same compound may be used.
これらの化合物を反応系に添加する量はバッチ反応の
場合は無水炭酸カリウム担体に担持したナトリウムのモ
ル数に対して，好ましくは0.01〜1.0モル，さらに好ま
しくは0.05〜0.5モルである。The amount of these compounds added to the reaction system in the case of a batch reaction is preferably 0.01 to 1.0 mol, more preferably 0.05 to 0.5 mol, based on the number of moles of sodium supported on the anhydrous potassium carbonate carrier.
また流通反応の場合は原料プロピレンに対して0.01〜
５％添加され，好ましくは0.05〜３％添加されて用いら
れる。さらに場合によっては原料プロピレンに添加され
るこれらの化合物の添加量を反応初期に高くし，その後
添加量を減少させる方法も本発明方法の好ましい実施方
法である。In the case of a flow reaction, 0.01 to
5% is added, and preferably 0.05 to 3% is used. Further, in some cases, a method of increasing the amount of these compounds added to the starting propylene at the beginning of the reaction and thereafter decreasing the amount is also a preferred method of carrying out the method of the present invention.
次に本発明の実施方法について説明する。反応方法は
特に限定されないが，粉末触媒をオートクレーブに充填
して行うバッチ反応，あるいは流動床方式，固定床方式
の流通反応などが挙げられる。Next, an implementation method of the present invention will be described. The reaction method is not particularly limited, and examples thereof include a batch reaction in which a powder catalyst is charged into an autoclave, and a flow reaction of a fluidized bed system or a fixed bed system.
反応温度は通常50〜300℃が採用され，好ましくは100
〜200℃が採用される。反応圧力は通常大気圧〜300Kg/c
m2が採用され，好ましくは30〜200Kg/cm2が採用され
る。The reaction temperature is usually 50 to 300 ° C, preferably 100 to 300 ° C.
~ 200 ° C is adopted. Reaction pressure is usually atmospheric pressure ~ 300Kg / c
m 2 , preferably 30 to 200 kg / cm 2 .
バッチ反応において触媒の濃度としては通常１〜50重
量％が採用され，好ましくは１〜30重量％が採用され
る。また反応時間は通常１〜15時間であり，好ましくは
２〜５時間である。In the batch reaction, the concentration of the catalyst is usually 1 to 50% by weight, preferably 1 to 30% by weight. The reaction time is generally 1 to 15 hours, preferably 2 to 5 hours.
流通反応において，プロピレン供給速度は通常LHSVで
0.05〜15hr-1であり，好ましくは0.1〜5hr-1が採用され
る。In the flow reaction, the propylene feed rate is usually LHSV
A 0.05~15hr -1, and preferably it is 0.1～5Hr -1 employed.
以下に実施例によって本発明方法をさらに詳細に説明
するが，本発明は以下の実施例によって制約されるもの
ではない。Hereinafter, the method of the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.
＜実施例＞ 比較例１ 粉末無水炭酸カリウム244gを硬質ガラス製フラスコに
入れ，窒素雰囲気下350℃で２時間乾燥し，次いで金属
ナトリウム6.8gを加え，窒素気流中250℃で５時間撹拌
し，触媒を調製した。<Example> Comparative Example 1 244 g of powdered anhydrous potassium carbonate was placed in a hard glass flask, dried at 350 ° C for 2 hours under a nitrogen atmosphere, and then 6.8 g of metallic sodium was added, followed by stirring at 250 ° C for 5 hours in a nitrogen stream. A catalyst was prepared.
磁気撹拌器付200mlオートクレーブに調製した触媒を3
8g仕込み，窒素雰囲気とする。次いで液化プロピレン15
0mlを仕込んだ後，オートクレーブ内温を150℃に加熱
し，窒素ガスで101Kg/cm2に加圧反応を開始した。撹拌
を行いながら3.5時間反応を行った。反応終了後オート
クレーブを冷却し，反応液を分析した。分析はガスクロ
マトグラフィーで行った。反応結果はプロピレン転化率
33％,4−メチル−１−ペンテン選択率87.6％,4−メチル
−２−ペンテン選択率2.9％であった。４−メチル−１
−ペンテン（以下4M1Pと記す）選択率と４−メチル−２
−ペンテン（以下4M2Pと記す）選択率の比は,4M1P/4M2P
＝30であった。Add the prepared catalyst to a 200 ml autoclave with a magnetic stirrer.
Charge 8 g and use a nitrogen atmosphere. Then liquefied propylene 15
After charging 0 ml, the internal temperature of the autoclave was heated to 150 ° C., and the pressurization reaction was started to 101 kg / cm 2 with nitrogen gas. The reaction was performed for 3.5 hours while stirring. After completion of the reaction, the autoclave was cooled and the reaction solution was analyzed. The analysis was performed by gas chromatography. Reaction result is propylene conversion
The selectivity was 33%, the selectivity for 4-methyl-1-pentene was 87.6%, and the selectivity for 4-methyl-2-pentene was 2.9%. 4-methyl-1
-Penten (hereinafter referred to as 4M1P) selectivity and 4-methyl-2
-Penten (hereinafter referred to as 4M2P) selectivity ratio is 4M1P / 4M2P
= 30.
実施例１〜４ 比較例１と同様にして触媒を調製した。磁気撹拌器付
200mlオートクレーブに調製した触媒を仕込み，窒素雰
囲気とする。次に乾燥ヘプタン20mlに溶解した添加剤を
仕込み，室温で10分間撹拌した後，液化プロピレン150m
lを仕込んだ。以下比較例１と同様にして反応を行っ
た。以下添加剤の種類を変えて反応を行った。表１に仕
込み触媒量，添加剤の種類と量および反応結果を比較例
１とともに示した。Examples 1 to 4 Catalysts were prepared in the same manner as in Comparative Example 1. With magnetic stirrer
Charge the prepared catalyst in a 200 ml autoclave, and make it a nitrogen atmosphere. Next, the additive dissolved in 20 ml of dry heptane was charged, and the mixture was stirred at room temperature for 10 minutes.
l was charged. Thereafter, the reaction was carried out in the same manner as in Comparative Example 1. The reaction was carried out by changing the type of the additive. Table 1 shows the amounts of the charged catalysts, the types and amounts of additives, and the reaction results together with Comparative Example 1.
以上の実験結果から解るように，高い4M1Pの選択率を
得た。特に4M1Pと4M2Pの選択率の比4M1P/4M2Pが大巾に
向上し，反応物の蒸留等による分離が容易になることを
示している。As can be seen from the above experimental results, a high 4M1P selectivity was obtained. In particular, the ratio of selectivity between 4M1P and 4M2P, 4M1P / 4M2P, was greatly improved, indicating that the separation of the reactants by distillation or the like became easy.
＜発明の効果＞ 以上の如く本発明によりプロピレンを二量化し,4−メ
チル−１−ペンテンを製造する方法において,4−メチル
−２−ペンテンをほとんど副生することなく,4−メチル
−１−ペンテンを高選択率で製造できるようになった。 <Effects of the Invention> As described above, in the method for producing 4-methyl-1-pentene by dimerizing propylene according to the present invention, 4-methyl-1-pentene is produced almost without by-producing 4-methyl-1-pentene. Pentene can be produced with high selectivity;
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭49−93303（ＪＰ，Ａ) 特開 昭60−215638（ＪＰ，Ａ) 特開 昭61−106526（ＪＰ，Ａ) 特公 昭39−19622（ＪＰ，Ｂ１) 特公 昭46−43365（ＪＰ，Ｂ１) 特公 昭43−25344（ＪＰ，Ｂ１) 特公 昭47−25041（ＪＰ，Ｂ１) 特公 昭39−12905（ＪＰ，Ｂ１) 特公 昭40−20373（ＪＰ，Ｂ１) ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-49-93303 (JP, A) JP-A-60-215638 (JP, A) JP-A-61-106526 (JP, A) 19622 (JP, B1) JP-B 46-43365 (JP, B1) JP-B 43-25344 (JP, B1) JP-B 47-25041 (JP, B1) JP-B 39-12905 (JP, B1) Tokiko 40-20373 (JP, B1)
Claims (1)
ペンテンを製造する方法において、無水炭酸カリウム担
体にナトリウムを担持した触媒の存在下に、反応系に炭
素数３〜30ののアミン類及び炭素数３〜20のケトン類か
ら選ばれる少なくとも１種以上の化合物を存在させ反応
せしめることを特徴とする４−メチル−１−ペンテンの
製造方法。(1) dimerization of propylene to give 4-methyl-1-
In the method for producing pentene, at least one or more selected from amines having 3 to 30 carbon atoms and ketones having 3 to 20 carbon atoms in a reaction system in the presence of a catalyst in which sodium is supported on an anhydrous potassium carbonate carrier. A process for producing 4-methyl-1-pentene, characterized by the presence of the compound of the formula (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62088067A JP2608715B2 (en) | 1987-04-09 | 1987-04-09 | Method for producing 4-methyl-1-pentene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62088067A JP2608715B2 (en) | 1987-04-09 | 1987-04-09 | Method for producing 4-methyl-1-pentene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63253037A JPS63253037A (en) | 1988-10-20 |
| JP2608715B2 true JP2608715B2 (en) | 1997-05-14 |
Family
ID=13932507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62088067A Expired - Lifetime JP2608715B2 (en) | 1987-04-09 | 1987-04-09 | Method for producing 4-methyl-1-pentene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2608715B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5317561B2 (en) * | 1973-01-11 | 1978-06-09 | ||
| JPS60215638A (en) * | 1984-04-11 | 1985-10-29 | Nippon Oil Co Ltd | Preparation of 4-methyl-1-pentene |
| JPS61106526A (en) * | 1984-10-31 | 1986-05-24 | Nippon Oil Co Ltd | Production of 4-methyl-1-pentene |
-
1987
- 1987-04-09 JP JP62088067A patent/JP2608715B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63253037A (en) | 1988-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4375566A (en) | Process for producing ortho-alkylated phenols from anisoles | |
| JPH01151941A (en) | Catalyst composition for producing 5-membered saturated nitrogen-containing heterocyclic compound | |
| JP2608715B2 (en) | Method for producing 4-methyl-1-pentene | |
| JP2608722B2 (en) | Method for producing 4-methyl-1-pentene | |
| JPS6362525B2 (en) | ||
| US4329500A (en) | Catalysts for the hydration of nitriles to amides | |
| US4230636A (en) | Process for producing dimethyl formamide | |
| JPS5923306B2 (en) | Method for producing indole or indole derivatives | |
| JPH0987224A (en) | Production of vinyl ether compounds | |
| JPH0717935A (en) | Production of 3-aminopropionitrile | |
| KR860002165B1 (en) | The process for preparing of amino benzylamine | |
| CN117886718B (en) | Preparation method of high-selectivity asymmetric urea compound and asymmetric urea compound | |
| CN112625015B (en) | Preparation method of 2- (1, 3-dihydro-2-isobenzofuran) -1-acetophenone compound | |
| JPS6326094B2 (en) | ||
| JPS6251267B2 (en) | ||
| JPH05255210A (en) | Preparation of tetramethyl diamino-polyoxyethylene | |
| JPS63246370A (en) | Production of amine compound | |
| JPH062716B2 (en) | Method for producing aromatic secondary amino compound | |
| JP2727359B2 (en) | 4,4'-Difluorodibenzylamine and process for producing the same | |
| JPS58167536A (en) | Preparation of acetaldehyde | |
| GB2118172A (en) | Preparation of a 2-alkyl-4- amino-5-aminomethylpyrimidine | |
| KR900001197B1 (en) | Process for preparing 2-alkyl-4-amino-5-aminomethyl pyrimidine | |
| JPS6011438A (en) | Production of ethylene glycol dialkyl ether | |
| JPS62129227A (en) | Production of ethane and ethylene by partial oxidization of methane | |
| JPH04264056A (en) | Preparation of n-methyl alkylamine |