JPS6217571B2 - - Google Patents
Info
- Publication number
- JPS6217571B2 JPS6217571B2 JP54011831A JP1183179A JPS6217571B2 JP S6217571 B2 JPS6217571 B2 JP S6217571B2 JP 54011831 A JP54011831 A JP 54011831A JP 1183179 A JP1183179 A JP 1183179A JP S6217571 B2 JPS6217571 B2 JP S6217571B2
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- reaction
- oligomers
- reaction temperature
- producing
- 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
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 2
- 150000001768 cations Chemical class 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000003440 styrenes Chemical class 0.000 description 5
- 239000013638 trimer Substances 0.000 description 5
- 239000003729 cation exchange resin Substances 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- -1 alicyclic hydrocarbons Chemical class 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 238000012719 thermal polymerization Methods 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)
Description
【発明の詳細な説明】
本発明は３〜４量体を主成分とするスチレンオ
リゴマーを選択的に製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for selectively producing styrene oligomers mainly composed of trimers and tetramers.
従来のスチレンオリゴマーの製造方法としては
２量体を主たる目的とするもの（特開昭49−
126655）、または熱重合により分子量1000前後の
オリゴマーを生成するもの（特開昭48−12887）
などがあり、この他に３量体以上のオリゴマーの
製造方法には特公昭50−4696などがある。 Conventional methods for producing styrene oligomers mainly aim at producing dimers (Japanese Unexamined Patent Application Publication No. 1989-1999).
126655), or those that produce oligomers with a molecular weight of around 1000 by thermal polymerization (Japanese Patent Application Laid-Open No. 12887-1987)
In addition, there are other methods for producing oligomers of trimer or higher, such as Japanese Patent Publication No. 50-4696.
しかし、スチレンの３〜４量体のオリゴマーを
選択的に製造する方法は見当らない。 However, no method has been found to selectively produce styrene trimer-tetramer oligomers.
本発明者らは、陽イオン交換樹脂を用いてスチ
レンオリゴマーを製造するための反応条件を種々
検討した結果、たとえば反応温度に関し、スチレ
ン２量体を得るためには反応温度を高める程良い
のに反し、スチレン３〜４量体のオリゴマーを収
率良く得るためには特定の温度範囲があることを
見い出し本発明を完成させたものである。 The present inventors investigated various reaction conditions for producing styrene oligomers using cation exchange resins, and found that, for example, with regard to reaction temperature, it is better to raise the reaction temperature in order to obtain styrene dimers. On the other hand, we have completed the present invention by discovering that there is a specific temperature range in order to obtain styrene trimer-tetramer oligomers in good yield.
すなわち、本発明は、溶媒中、陽イオン交換樹
脂の存在下、スチレン濃度10容量％以下、反応温
度10〜120℃好ましくは30〜90℃なる反応条件で
スチレンを重合することにより、３〜４量体を主
成分とするスチレンオリゴマーを選択的に製造す
る方法である。 That is, in the present invention, 3 to 4 This is a method for selectively producing styrene oligomers whose main components are styrene oligomers.
反応温度が10℃より低いとスチレンの転化率が
低下し、また120℃を越える場合はスチレン２量
体が多量に生成するのでいずれも好ましくない。 If the reaction temperature is lower than 10°C, the conversion rate of styrene will decrease, and if it exceeds 120°C, a large amount of styrene dimer will be produced, which is not preferable.
スチレン濃度を20容量％以下で反応させるなら
ばポリマーの生成は少く、またスチレン３量体お
よび４量体ともスチレン２量体より多く生成す
る。 If the reaction is carried out at a styrene concentration of 20% by volume or less, little polymer will be produced, and more styrene trimers and tetramers will be produced than styrene dimers.
この観点から、スチレン濃度は20容量％を越え
ることは好ましくない。 From this point of view, it is not preferable for the styrene concentration to exceed 20% by volume.
溶媒は、ベンゼン、トルエンなどの芳香族炭化
水素、ヘキサン、オクタンなどの脂肪族炭化水
素、シクロヘキサンなどの脂環式炭化水素、およ
び二塩化エチレン、四塩化炭素などのハロゲン化
炭化水素などが使用される。 The solvents used include aromatic hydrocarbons such as benzene and toluene, aliphatic hydrocarbons such as hexane and octane, alicyclic hydrocarbons such as cyclohexane, and halogenated hydrocarbons such as ethylene dichloride and carbon tetrachloride. Ru.
また、本発明では上記の溶媒中、陽イオン交換
樹脂の存在下でスチレンを重合させる。陽イオン
交換樹脂は、たとえばスチレン−ジビニルベンゼ
ン共重合体にスルホン基を導入したものなどがそ
の例である。その使用量は反応をバツチ式でおこ
なう場合には0.01〜1.0wt％あれば良い。 Moreover, in the present invention, styrene is polymerized in the above-mentioned solvent in the presence of a cation exchange resin. An example of the cation exchange resin is a styrene-divinylbenzene copolymer into which a sulfone group is introduced. The amount used may be 0.01 to 1.0 wt% when the reaction is carried out in batches.
本発明においては反応時間は通常１〜３時間で
良い。 In the present invention, the reaction time may generally be 1 to 3 hours.
また、反応形式はバツチ式のほか、たとえば、
固定床による流通式でもおこなうことができる。 In addition to the batch type reaction format, for example,
It can also be carried out using a fixed bed flow system.
なお、本発明により反応させた場合、反応生成
物中には、溶媒、３〜４量体のスチレンオリゴマ
ーの他、スチレン２量体、およびスチレン５〜６
量体も同時に副生するが、必要に応じて蒸留等に
より各々を容易に分離することができる。 In addition, when the reaction is carried out according to the present invention, the reaction product contains a solvent, a styrene dimer, and a styrene 5-6 styrene oligomer, as well as a styrene oligomer of 3-4 styrene.
Although polymers are also produced as by-products, they can be easily separated by distillation or the like if necessary.
次に実施例により本発明を詳述する。 Next, the present invention will be explained in detail with reference to Examples.
実施例 １
0.02ｇ／10c.c.溶媒になる様に秤量した
Amberlyst15（Rohm ＆ Haas社製、強酸性陽
イオン交換樹脂）を、乾燥したN2ガスシールを
した三角フラスコにあらかじめ加え、さらにスチ
レン濃度0.1mol／（1.2容量％に相当）となる
ようにベンゼンを加えて反応を開始したが、反応
温度は10〜120℃の間で変化させた。約60分間マ
グネテイツクスターラーで激しく撹拌した後、反
応溶液を抜き取り、HLC（高速液体クロマトグ
ラフイー）により反応生成物を分析し、３量体〜
４量体および２量体のスチレンオリゴマー分率を
求めた。結果は図１に示した。Example 1 Weighed to give 0.02g/10c.c. solvent
Amberlyst 15 (manufactured by Rohm & Haas, strong acidic cation exchange resin) was added in advance to a dry Erlenmeyer flask sealed with N2 gas, and benzene was added to make the styrene concentration 0.1 mol/(equivalent to 1.2% by volume). In addition, the reaction was started, but the reaction temperature was varied between 10 and 120°C. After stirring vigorously with a magnetic stirrer for about 60 minutes, the reaction solution was extracted and the reaction products were analyzed by HLC (high performance liquid chromatography).
The styrene oligomer fractions of tetramer and dimer were determined. The results are shown in Figure 1.
実施例 ２
前記実施例１において、反応温度を50℃一定と
し、スチレン濃度を0.1〜1.0mol／（1.2〜12.0
容量％に相当）の間で、変化させたほかは同様に
反応させ、３〜４量体スチレンオリゴマーの分率
を求めた。結果は図２に示した。Example 2 In Example 1, the reaction temperature was kept constant at 50°C, and the styrene concentration was 0.1 to 1.0 mol/(1.2 to 12.0
The reaction was carried out in the same manner except that the reaction volume was changed between (corresponding to volume %), and the fraction of 3-4 styrene oligomers was determined. The results are shown in Figure 2.
比較例
前記実施例１において、スチレンの代わりにα
−メチルスチレンを用いたほかは同様にして反応
温度70℃で反応させた。Comparative Example In Example 1, α was used instead of styrene.
-The reaction was carried out in the same manner at a reaction temperature of 70°C except that methylstyrene was used.
分析によると、α−メチルスチレンの反応率は
95％であり、反応生成物における２量体（殆ど環
状２量体）分率96％、また３量体以上の合計分率
は４％であつた。 According to the analysis, the reaction rate of α-methylstyrene is
The dimer (mostly cyclic dimer) fraction in the reaction product was 96%, and the total fraction of trimers and higher was 4%.
第１図と２図はそれぞれ反応温度（℃）および
スチレン濃度（mol／）を横軸にとり、これら
に対する全スチレンオリゴマー中に占めるスチレ
ン２量体および３〜４量体分率（wt％）を縦軸
にとつて図示したものである。第１図および第２
図において実線は３〜４量体のグラフ、点線は２
量体のグラフを示す。
In Figures 1 and 2, the reaction temperature (°C) and styrene concentration (mol/) are plotted on the horizontal axis, and the styrene dimer and trimer-tetramer fractions (wt%) in the total styrene oligomer are plotted in Figures 1 and 2, respectively. It is illustrated along the vertical axis. Figures 1 and 2
In the figure, the solid line is a graph of trimers and tetramers, and the dotted line is a graph of 2-mers.
Shows a graph of quantities.
Claims (1)
ン濃度10容量％以下、反応温度10〜120℃なる反
応条件でスチレンを重合することにより、３〜４
量体を主成分とするスチレンオリゴマーを選択的
に得ることを特徴とするスチレンオリゴマーの製
造方法。 ２ 反応温度30〜90℃である特許請求の範囲第１
項記載のスチレンオリゴマーの製造方法。[Claims] 1. Polymerization of styrene in a solvent in the presence of a cation conversion resin under reaction conditions of a styrene concentration of 10% by volume or less and a reaction temperature of 10 to 120°C.
1. A method for producing a styrene oligomer, the method comprising selectively obtaining a styrene oligomer containing a styrene oligomer as a main component. 2 Claim 1 in which the reaction temperature is 30 to 90°C
A method for producing a styrene oligomer as described in Section 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1183179A JPS55104219A (en) | 1979-02-06 | 1979-02-06 | Production of styrene oligomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1183179A JPS55104219A (en) | 1979-02-06 | 1979-02-06 | Production of styrene oligomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55104219A JPS55104219A (en) | 1980-08-09 |
| JPS6217571B2 true JPS6217571B2 (en) | 1987-04-18 |
Family
ID=11788692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1183179A Granted JPS55104219A (en) | 1979-02-06 | 1979-02-06 | Production of styrene oligomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55104219A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0423640U (en) * | 1990-06-20 | 1992-02-26 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61243030A (en) * | 1984-12-03 | 1986-10-29 | Mitsui Toatsu Chem Inc | Production of oligomer of alpha-methylstyrene |
| JPS61233004A (en) * | 1985-04-09 | 1986-10-17 | Kawasaki Steel Corp | Production of resin |
-
1979
- 1979-02-06 JP JP1183179A patent/JPS55104219A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0423640U (en) * | 1990-06-20 | 1992-02-26 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55104219A (en) | 1980-08-09 |
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