JPS59190927A - Dimerization of alpha-methylstyrene - Google Patents
Dimerization of alpha-methylstyreneInfo
- Publication number
- JPS59190927A JPS59190927A JP58065915A JP6591583A JPS59190927A JP S59190927 A JPS59190927 A JP S59190927A JP 58065915 A JP58065915 A JP 58065915A JP 6591583 A JP6591583 A JP 6591583A JP S59190927 A JPS59190927 A JP S59190927A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- cellosolve
- methylstyrene
- clay
- alpha
- 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
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)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
体、特に2,/l−ジフェニル−4−メチルペンテン−
1を高収率で製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION In particular, 2,/l-diphenyl-4-methylpentene-
1 in high yield.
α−メチルスチレンを2量化すると、不飽和線状2量体
である2,4−ジフェニルー4−メチルベンテン−1お
よヒ2,4ージフェニルー4ーメチルペンテン−2、お
よび飽和2量体である 1,1.3−トリメチル−3−
フェニルインダン、サラに3量体以上の高沸点物が得ら
れる。When α-methylstyrene is dimerized, it produces unsaturated linear dimers 2,4-diphenyl-4-methylbentene-1 and 2,4-diphenyl-4-methylpentene-2, and a saturated dimer 1, 1,3-trimethyl-3-
Phenylindane, a trimer or higher boiling point product can be obtained.
これらの生成物のうち、不飽和線状2量体はトラクショ
ンドライブ用潤滑油の原料として、また、% iC 2
. 4 − シ7 −1− =ル−4−メチルベンy
ン− 1は重合調節剤として重要である。そこで、α−
メチルスチレンの2量化により高純度の礼4ージフェニ
ルー4ーメチルペンテン−1ヲ得ル方法カ従来より,い
ろいろ提案されている。Among these products, the unsaturated linear dimers are used as raw materials for traction drive lubricating oils and also as % iC 2
.. 4-C7-1-=-4-methylbeny
N-1 is important as a polymerization regulator. Therefore, α−
Various methods have been proposed for obtaining highly pure 4-diphenyl-4-methylpentene-1 by dimerizing methylstyrene.
たとえば、特開昭4 8 − 4 4 2 4 0号公
報には、触媒として酸性白土、活性白土などの固体酸あ
るいは陽イオン交換樹脂を用い、かつ水あるいは多価ア
ルコールを共存せしめる方法が提案でれている。For example, JP-A-48-44240 proposes a method in which a solid acid such as acid clay or activated clay or a cation exchange resin is used as a catalyst, and water or a polyhydric alcohol is allowed to coexist. It is.
しかし、この方法は酸性白土あるいは活性白土が、水あ
るいは多価アルコールに対して吸着作用が強いため、酸
性白土などと混合した場合、これら触媒のブロッキング
現象が生ずる。このようにブロッキングした触媒は反応
容器壁あるいは、内部コイル加熱の場合には該コイル周
辺に付着し、これにともない触媒効率が低下する。さら
にまた、このようになると熱の伝導が不十分となり、加
熱源であるジャケットあるいは内部コイル表面の温度と
反応液 の温度との差が大きくなり反応の制御が困難と
なるので好ましくない。However, in this method, since acid clay or activated clay has a strong adsorption effect on water or polyhydric alcohol, when mixed with acid clay, etc., a blocking phenomenon of these catalysts occurs. The thus blocked catalyst adheres to the wall of the reaction vessel or, in the case of internal coil heating, to the vicinity of the coil, resulting in a decrease in catalytic efficiency. Furthermore, in this case, heat conduction becomes insufficient, and the difference between the temperature of the surface of the jacket or internal coil, which is a heating source, and the temperature of the reaction liquid increases, making it difficult to control the reaction, which is undesirable.
さらに、特開昭57−62228号公報では、酸性白土
あるいは活性白土を触媒とし、反応系内に脂肪族単一エ
ーテル、脂肪族混成エーテルあるいは環式エーテルを共
存させてα−メチルスチレンを2量化する方法が提案さ
れている。この方法では前述した触媒のブロッキング現
象などは生じがたいものの、たとえば反応生成物中の3
量体以上の高沸点物の量が5%以上と多く、不飽和2量
体の収率は必らずしも良くない。また、触媒の使用量も
α−メチルスチレンに対し4〜6%と多く、また共存さ
せるエーテルもα−メチルスチレンの10〜50チと多
いなど不経済でもある。Furthermore, in JP-A-57-62228, α-methylstyrene is dimerized by using acid clay or activated clay as a catalyst and coexisting an aliphatic single ether, aliphatic hybrid ether, or cyclic ether in the reaction system. A method has been proposed. Although this method is unlikely to cause the aforementioned blocking phenomenon of the catalyst, for example,
The amount of high-boiling substances higher than the dimer is as large as 5% or more, and the yield of unsaturated dimer is not necessarily good. Further, the amount of catalyst used is large at 4 to 6% based on α-methylstyrene, and the amount of ether coexisting is also large at 10 to 50% based on α-methylstyrene, which is uneconomical.
本発明者らは、上述の事情に鑑み鋭意研究した結果、触
媒としての白土類の存在下、セロソルブを共存するなら
ば、触媒のブロッキングが防止できるとともに、高収率
で不飽和2量体が得られ、かつ共存物質の優も少なくて
よいことを見い出し本発明を完成させたものである。The present inventors conducted intensive research in view of the above circumstances, and found that if cellosolve is coexisting in the presence of white earth as a catalyst, blocking of the catalyst can be prevented, and unsaturated dimers can be produced in high yield. The inventors have completed the present invention by discovering that the present invention can be obtained with less predominance of coexisting substances.
すなわち、本発明は酸性白土または活性白土の存在下、
反応系内にセロソルブを共存させること全特徴とするα
−メチルスチレンの不飽和線状2量体の製造方法に関す
る。That is, in the present invention, in the presence of acid clay or activated clay,
α is characterized by the coexistence of cellosolve in the reaction system.
- A method for producing an unsaturated linear dimer of methylstyrene.
触媒としての白土類の使用量は、特に限定されろもので
はないが、α−メチルスチレンに対して0.1〜20重
量係、より好ましくは0.5〜5重量係である。触媒の
使用量を多くすると、共存させるべきセロソルブの使用
量も多くする必要があり、経済的に不利である。The amount of white earth used as a catalyst is not particularly limited, but is 0.1 to 20 parts by weight, more preferably 0.5 to 5 parts by weight, based on α-methylstyrene. If the amount of catalyst used is increased, the amount of cellosolve that must be present must also be increased, which is economically disadvantageous.
本発明のセロソルブはエチレングリコールのモノエーテ
ルであって、エーテル結合トアルコール性の水酸基を同
一分子内に有するものである。The cellosolve of the present invention is a monoether of ethylene glycol, and has an ether-bonded alcoholic hydroxyl group in the same molecule.
本発明の如きセロソルブを白土類と共存させてα−メチ
ルスチレンを2量化する例は知られていない。また、共
存物質としてのアルコールと比較−すると、前述した如
き触媒のブロッキング現象はほとんど生じない。また、
前述したモノエーテルと比較すると、高沸点の生成物が
少なく、不飽和2量体、%に2.4−ジフェニル−4−
メチルペンテン−1の収率が良く、触媒や共存物質の使
用量も少なくて良いという利点を有するものである。There is no known example of dimerizing α-methylstyrene by coexisting cellosolve with white earth metals as in the present invention. Furthermore, compared to alcohol as a coexisting substance, the blocking phenomenon of the catalyst as described above hardly occurs. Also,
Compared to the monoethers mentioned above, there are fewer high-boiling products, less unsaturated dimer, % 2.4-diphenyl-4-
This method has the advantage that the yield of methylpentene-1 is high and the amount of catalyst and coexisting substances used can be small.
共存さすべきセロソルブの種類は特に限定されるもので
はないが、メチル、エチル、n−プロピル、1so−プ
ロピル、n−ブチル、 1so−ブチル、tert−
ブチルセロソルブなどの如く炭素数が6以下のセロソル
ブが好ましい。炭素数が6を越えるセロソルブも使用す
ることができるが、セロソルブとしての性質よりも炭化
水素としての性質が強くなるので、セロソルブの使用量
を多くせざるを得ず好ま1〜くない。さらに、炭素数が
多くなってより高沸点となると、その回収に要する熱量
も多大となり、また、2量体の沸点に近接してくるので
1反応後における2量体との分離も学なる蒸留では困難
となるので不利である。The types of cellosolves that should coexist are not particularly limited, but include methyl, ethyl, n-propyl, 1so-propyl, n-butyl, 1so-butyl, tert-
Cellosolve having 6 or less carbon atoms, such as butyl cellosolve, is preferred. Cellosolve having more than 6 carbon atoms can also be used, but since the properties as a hydrocarbon are stronger than as a cellosolve, the amount of cellosolve used must be increased, which is not preferred. Furthermore, as the number of carbon atoms increases and the boiling point becomes higher, the amount of heat required for recovery becomes large, and since the boiling point approaches the dimer, it is difficult to separate the dimer after one reaction by distillation. This is disadvantageous because it becomes difficult.
セロソルブの使用量けその種類により適宜の量を用いう
るが、炭素数6以下のセロソルブでは触媒の2〜40倍
、より好ましくは5〜20倍である。The amount of cellosolve to be used can be appropriately determined depending on the type of material, but in the case of cellosolve having 6 or less carbon atoms, the amount is 2 to 40 times, more preferably 5 to 20 times the amount of the catalyst.
セロソルブがこの量よりも少ないと、2,4−ジフェニ
ル−4−メチルペンテン−1の選択率が低下し、またよ
り多量のセロソルブを共存させるならば、触媒の活性が
低下1−1α−メチルスチレンの転化率が低下するので
いずれも好ましくない。If cellosolve is less than this amount, the selectivity of 2,4-diphenyl-4-methylpentene-1 will decrease, and if a larger amount of cellosolve is present, the activity of the catalyst will decrease. Both are unfavorable because they reduce the conversion rate.
反応温度は通常は40〜150℃、より好ましくは50
〜120℃である。40℃未満の反応温度ではα−メチ
ルスチレンの2量化速度が遅く、反応時間がかがシすぎ
るので好ましくない。また150℃を越えると2,4−
ジフェニル−4−メチルペンテン−1の選択率が低下し
、3量体以上の高沸点物の生成が多くなる。The reaction temperature is usually 40 to 150°C, more preferably 50°C.
~120°C. A reaction temperature lower than 40° C. is not preferred because the dimerization rate of α-methylstyrene is slow and the reaction time is too long. Also, if the temperature exceeds 150℃, 2,4-
The selectivity of diphenyl-4-methylpentene-1 decreases, and the production of high boiling point products such as trimer or higher increases.
本発明を無溶媒でおこなうこともできるが、n−パラフ
ィンの如き反応に不活性な溶媒を用いておこなうことも
できる。反応温度の調節が困難なときは1溶媒を用いる
のがよい。Although the present invention can be carried out without a solvent, it can also be carried out using a solvent inert to the reaction, such as n-paraffin. When it is difficult to control the reaction temperature, it is preferable to use one solvent.
反応形式はバッチ式あるいは流通式のいずれの形式でも
おこないうるが、活性白土あるいは酸性白土は通常、微
細な粉末として入手されるので普通はバッチ式が適当で
ある。The reaction may be carried out either batchwise or in a flow manner; however, since activated clay or acid clay is usually obtained as a fine powder, a batchwise manner is usually appropriate.
反応終了後、たとえば蒸留などにより、未反応α−メチ
ルスチレン、セロソルブなどを分離することにより目的
物たる不飽和線状2量体が得られる。After the reaction is completed, unreacted α-methylstyrene, cellosolve, etc. are separated by distillation, for example, to obtain the desired unsaturated linear dimer.
次に実施例をもって本発明を説明する。Next, the present invention will be explained with reference to examples.
実施例1
攪拌器付きの反応容器にn−ブチルセロソルブ20g、
活性白土(水沢化学社製ガI/オナイト236)2gを
入れ15分攪拌する。続いてα−メチルスチレン200
gを入れ攪拌しながら徐々に加熱し、110°C(これ
を反応温度という)にて60分(これを反応時間という
)攪拌を続けた。冷却後液組成:計分析したところ表1
に示すとおりであった。Example 1 20 g of n-butyl cellosolve was placed in a reaction vessel equipped with a stirrer.
Add 2 g of activated clay (Ga I/Onite 236, manufactured by Mizusawa Chemical Co., Ltd.) and stir for 15 minutes. Next, α-methylstyrene 200
g was added thereto and gradually heated while stirring, and stirring was continued at 110°C (this is referred to as reaction temperature) for 60 minutes (this is referred to as reaction time). Liquid composition after cooling: Table 1 based on total analysis
It was as shown in
実施例2〜6
表1に示す条件で実施例1と同じ方法でα−メチルスチ
レンの重合を行った。反応液の組成1:ハ表1のとおり
であった。Examples 2 to 6 α-methylstyrene was polymerized in the same manner as in Example 1 under the conditions shown in Table 1. Composition 1 of the reaction solution was as shown in Table 1.
比較例1,2
比較例1では、活性白土2.Op、α−メチルスチレン
200gおよびn−ブタノール20gの混合物を90℃
で;3時間、反応させた。Comparative Examples 1 and 2 In Comparative Example 1, activated clay 2. Op, a mixture of 200 g of α-methylstyrene and 20 g of n-butanol was heated at 90°C.
The reaction was allowed to proceed for 3 hours.
捷た、比較例2では、活性白土6g1α−メチルスチレ
ン200g、ジイソプロピルエーテル25yの混合物ケ
90°Cで3時間反応させた。In Comparative Example 2, a mixture of 6 g of activated clay, 200 g of α-methylstyrene, and 25 g of diisopropyl ether was reacted at 90° C. for 3 hours.
結果1は次表に示すが、いずれの場合も3量体以上の高
沸点物が多い。Results 1 are shown in the following table, and in all cases there were many high-boiling substances of trimer or higher.
Claims (1)
ソルブを共存させるととを特徴とするα−メチルスチレ
ンの不飽和線状2量体の製造方法。(1) A method for producing an unsaturated linear dimer of α-methylstyrene, which comprises allowing cellosolve to coexist in the reaction system in the presence of active white clay or acid clay.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58065915A JPS59190927A (en) | 1983-04-14 | 1983-04-14 | Dimerization of alpha-methylstyrene |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58065915A JPS59190927A (en) | 1983-04-14 | 1983-04-14 | Dimerization of alpha-methylstyrene |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59190927A true JPS59190927A (en) | 1984-10-29 |
JPH0332530B2 JPH0332530B2 (en) | 1991-05-13 |
Family
ID=13300741
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP58065915A Granted JPS59190927A (en) | 1983-04-14 | 1983-04-14 | Dimerization of alpha-methylstyrene |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59190927A (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4844240A (en) * | 1971-08-06 | 1973-06-26 | ||
JPS5762228A (en) * | 1980-10-03 | 1982-04-15 | Nippon Oil & Fats Co Ltd | Preparation of 2,4-diphenyl-4-methyl-pentene |
-
1983
- 1983-04-14 JP JP58065915A patent/JPS59190927A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4844240A (en) * | 1971-08-06 | 1973-06-26 | ||
JPS5762228A (en) * | 1980-10-03 | 1982-04-15 | Nippon Oil & Fats Co Ltd | Preparation of 2,4-diphenyl-4-methyl-pentene |
Also Published As
Publication number | Publication date |
---|---|
JPH0332530B2 (en) | 1991-05-13 |
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