JPH09157190A - Vinylbipheny composition - Google Patents
Vinylbipheny compositionInfo
- Publication number
- JPH09157190A JPH09157190A JP32048395A JP32048395A JPH09157190A JP H09157190 A JPH09157190 A JP H09157190A JP 32048395 A JP32048395 A JP 32048395A JP 32048395 A JP32048395 A JP 32048395A JP H09157190 A JPH09157190 A JP H09157190A
- Authority
- JP
- Japan
- Prior art keywords
- vinylbiphenyl
- composition
- ethylbiphenyl
- content
- weight
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はビニルビフェニル組
成物にかかわり、詳しくは安定性が優れ、使用に有利な
ビニルビフェニル組成物に関する。TECHNICAL FIELD The present invention relates to a vinylbiphenyl composition, and more particularly to a vinylbiphenyl composition which has excellent stability and is advantageous for use.
【０００２】[0002]
【従来の技術】４−ビニルビフェニルは、エチルビフェ
ニルの脱水素反応によって製造することができる（特開
平４−２０２１４５号公報）。この方法は、脱水素反応
油に良溶媒を添加して急冷し、良溶媒を濃縮した後に、
純度９５重量％以上の低級アルコールを添加して晶析に
より精製する方法であり、複雑な精製工程を有してい
る。ここで得られる製品は、常温で固体である。工業的
に生産する場合には、より簡略化された精製方法が望ま
れる。また、４−ビニルビフェニル以外のビニルビフェ
ニルについても、ほぼ同様なことがいえる。2. Description of the Related Art 4-Vinylbiphenyl can be produced by a dehydrogenation reaction of ethylbiphenyl (JP-A-4-202145). This method, after adding a good solvent to the dehydrogenation reaction oil and quenching, and concentrating the good solvent,
This is a method of purifying by crystallization by adding a lower alcohol having a purity of 95% by weight or more, and has complicated purification steps. The product obtained here is solid at room temperature. For industrial production, a more simplified purification method is desired. The same can be said for vinyl biphenyls other than 4-vinyl biphenyl.
【０００３】更に、ビニルビフェニルは重合性があるた
め、ビニルビフェニルを得たとしても、そのままでは保
存安定性が悪く、使用するまでに変質して製品が着色し
たり、重合物が製品に混入したりし、使用しにくいとい
う問題がある。ビニルビフェニル、特に４−ビニルビフ
ェニルは、基本骨格中にビフェニル構造を有するため優
れた樹脂改質剤である。そして、使用性が優れ、取り扱
いの容易な製品が望まれている。Further, since vinyl biphenyl is polymerizable, even if vinyl biphenyl is obtained, it is poor in storage stability as it is, and it deteriorates before use and the product is colored, or the polymer is mixed in the product. However, there is a problem that it is difficult to use. Vinyl biphenyl, especially 4-vinyl biphenyl, is an excellent resin modifier because it has a biphenyl structure in the basic skeleton. A product that is excellent in usability and easy to handle is desired.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、重合性であ
るにもかかわらず、安定性が優れ、且つ使用性の優れた
ビニルビフェニル組成物を提供することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a vinylbiphenyl composition which is excellent in stability and usability even though it is polymerizable.
【０００５】[0005]
【課題を解決するための手段】本発明は、エチルビフェ
ニルの脱水素反応混合物から得られるビニルビフェニル
組成物であって、ビニルビフェニル含有量が５０〜８０
重量％、エチルビフェニル含有量が２０〜４５重量％、
ｔ−ブチルカテコール濃度が５００〜５０００ｐｐｍで
あるビニルビフェニル組成物であり、また本発明は、４
−エチルビフェニルの脱水素反応混合物から得られるビ
ニルビフェニル組成物であって、４−ビニルビフェニル
含有量が８０〜９７重量％、エチルビフェニル含有量が
３〜２０重量％、ｔ−ブチルカテコール濃度が５００〜
５０００ｐｐｍであるビニルビフェニル組成物である。DISCLOSURE OF THE INVENTION The present invention is a vinylbiphenyl composition obtained from a dehydrogenation reaction mixture of ethylbiphenyl having a vinylbiphenyl content of 50-80.
% By weight, ethyl biphenyl content 20-45% by weight,
A vinylbiphenyl composition having a t-butylcatechol concentration of 500 to 5000 ppm, and the present invention also provides
A vinylbiphenyl composition obtained from a dehydrogenation reaction mixture of ethylbiphenyl, wherein the content of 4-vinylbiphenyl is 80 to 97% by weight, the content of ethylbiphenyl is 3 to 20% by weight, and the concentration of t-butylcatechol is 500. ~
It is a vinylbiphenyl composition which is 5000 ppm.
【０００６】[0006]
【発明の実施の形態】エチルビフェニルとしては適宜の
純度のものが使用できるが、４−ビニルビフェニルを目
的とする場合は、４−エチルビフェニルの純度が８０重
量％以上のものが適当であり、異性体混合物を目的とす
る場合は、エチルビフェニルの濃度が８０重量％以上の
もので、異性体の混合割合は、３−エチルビフェニルが
６５重量％以上、４−エチビフェニルが２５重量％以
下、好ましくは３−エチルビフェニルが７５重量％以
上、４−エチルビフェニルが１５重量％以下である組成
物を用いることがよい。BEST MODE FOR CARRYING OUT THE INVENTION Although ethyl biphenyl having an appropriate purity can be used, 4-ethyl biphenyl having a purity of 80% by weight or more is suitable for the purpose of 4-vinyl biphenyl. When the isomer mixture is intended, the concentration of ethylbiphenyl is 80% by weight or more, and the mixing ratio of the isomers is 65% by weight or more of 3-ethylbiphenyl, 25% by weight or less of 4-ethibiphenyl, It is preferable to use a composition containing 75% by weight or more of 3-ethylbiphenyl and 15% by weight or less of 4-ethylbiphenyl.
【０００７】エチルビフェニルの脱水素反応は、反応温
度５００〜６８０℃、スチーム／エチルビフェニル重量
比１〜２０、ＬＨＳＶ０．０５〜０．５、反応圧力０．
２〜１．０Ｋｇ／ｃｍ2 ・Ｇのような条件で、鉄−カリ
ウム−クロム−酸素系、マグネシウム−鉄−銅−カリウ
ム−酸素系、鉄−クロム−バナジウム−コバルト−カリ
ウム−酸素系触媒などの触媒の存在下で行うことができ
る。また、この反応の転化率は６５〜８５％程度とする
ことがよい。The dehydrogenation reaction of ethylbiphenyl is carried out at a reaction temperature of 500 to 680 ° C., a steam / ethylbiphenyl weight ratio of 1 to 20, LHSV of 0.05 to 0.5, and a reaction pressure of 0.
Under the conditions of 2 to 1.0 kg / cm 2 · G, iron-potassium-chromium-oxygen system, magnesium-iron-copper-potassium-oxygen system, iron-chromium-vanadium-cobalt-potassium-oxygen system catalyst, etc. Can be carried out in the presence of the catalyst. The conversion rate of this reaction is preferably about 65 to 85%.
【０００８】４−ビニルビフェニルは常温で固体である
ので、晶析法により純度８０重量％以上の製品を得るこ
とができる。４−ビニルビフェニルの含有量の少ないビ
ニルビフェニルは、常温で液体であるため、晶析法によ
る精製は困難であるので、脱水素生成油を活性炭等で、
脱色又は吸着処理しただけで製品とすることが有利であ
る。しかしながら、このような製品は重合性であって、
保存安定性が劣るので、ｔ−ブチルカテコールを配合す
る。Since 4-vinylbiphenyl is a solid at room temperature, a product having a purity of 80% by weight or more can be obtained by the crystallization method. Since vinylbiphenyl, which has a low content of 4-vinylbiphenyl, is liquid at room temperature, it is difficult to purify it by the crystallization method.
It is advantageous that the product is simply decolorized or adsorbed. However, such products are polymerizable and
Since the storage stability is poor, t-butylcatechol is added.
【０００９】本発明のビニルビフェニル組成物におい
て、４−ビニルビフェニルを主とする組成物にあって
は、４−ビニルビフェニル含有量を８０〜９７重量％、
好ましくは８５〜９５重量％、エチルビフェニル含有量
を３〜２０重量％、好ましくは５〜１５重量％、ｔ−ブ
チルカテコール濃度を５００〜５０００ｐｐｍ、好まし
くは１０００〜３０００ｐｐｍとする。また、４−ビニ
ルビフェニルの含有量の少ないビニルビフェニルを主と
する組成物にあっては、ビニルビフェニル含有量が５０
〜８０重量％、好ましくは５５〜７０重量％、エチルビ
フェニル含有量を２０〜５０重量％、好ましくは３０〜
４５重量％、ｔ−ブチルカテコール濃度が５００〜５０
００ｐｐｍ、好ましくは１０００〜３０００ｐｐｍであ
る。In the vinyl biphenyl composition of the present invention, a composition mainly comprising 4-vinyl biphenyl has a 4-vinyl biphenyl content of 80 to 97% by weight,
The content is preferably 85 to 95% by weight, the ethylbiphenyl content is 3 to 20% by weight, preferably 5 to 15% by weight, and the t-butylcatechol concentration is 500 to 5000 ppm, preferably 1000 to 3000 ppm. Further, in a composition mainly containing vinyl biphenyl having a low content of 4-vinyl biphenyl, the vinyl biphenyl content is 50
-80 wt%, preferably 55-70 wt%, ethylbiphenyl content 20-50 wt%, preferably 30-
45% by weight, t-butylcatechol concentration of 500 to 50
It is 00 ppm, preferably 1000 to 3000 ppm.
【００１０】ビフェニルビフェニル含有量が高すぎると
保存安定性に問題があり、エチルビフェニル含有量が高
すぎると使用性の問題があり、ｔ−ブチルカテコール濃
度が低すぎると保存安定性が劣り、必要以上に高くする
とこれを除去する際の負荷が増大するなどの問題が生ず
る。なお、固体である４−ビニルビフェニル組成物にｔ
−ブチルカテコ−ルを均一に配合するためには、溶剤に
４−ビニルビフェニルとｔ−ブチルカテコ−ルとを溶解
させたのち、晶析させる方法が有利である。When the content of biphenylbiphenyl is too high, there is a problem in storage stability, when the content of ethylbiphenyl is too high, there is a problem of usability, and when the concentration of t-butylcatechol is too low, storage stability becomes poor. If it is set higher than the above, there arises a problem that the load for removing it increases. In addition, the solid 4-vinylbiphenyl composition has t
In order to uniformly mix -butylcatechol, 4-vinylbiphenyl and t-butylcatechol are dissolved in a solvent and then crystallized.
【００１１】本組成物を樹脂改質剤として利用すること
により、弾力性等の樹脂特性を向上することや、樹脂の
表面硬度を改善することができる。By using the present composition as a resin modifier, it is possible to improve the resin properties such as elasticity and to improve the surface hardness of the resin.
【００１２】[0012]
【実施例】以下、本発明を実施例により説明するが、本
発明はこれに限定されるものではない。なお、％は重量
％を示す。 実施例１〜３ ３−エチルビフェニル９９％、その他１％のエチルビフ
ェニルを脱水素反応して得られた脱水素反応油を活性炭
により脱色して、３−ビニルビフェニル５７％、エチル
ビフェニル３０％、その他１４％の３−ビニルビフェニ
ルを得た。これに対して表１に示す配合割合でｔ−ブチ
ルカテコール（ＴＢＣ）を配合し均一に溶解した後、２
０℃に保たれた室内で放置してポリマーの生成量を測定
したところ、ポリマー生成量は以下のとおりであった。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. In addition,% shows weight%. Examples 1-3 Dehydrogenation reaction oil obtained by dehydrogenating 3-ethylbiphenyl 99% and other 1% ethylbiphenyl was decolorized with activated carbon to give 3-vinylbiphenyl 57%, ethylbiphenyl 30%, In addition, 14% of 3-vinylbiphenyl was obtained. On the other hand, t-butylcatechol (TBC) was blended at a blending ratio shown in Table 1 and uniformly dissolved, and then 2
When the amount of polymer produced was measured by leaving it in a room kept at 0 ° C., the amount of polymer produced was as follows.
【００１３】[0013]
【表１】 [Table 1]
【００１４】このビニルビフェニル組成物に溶剤を加え
てからＴＢＣを直前に除去して、スチレンモノマーに対
して１，０００ｐｐｍを添加して塊状重合した後に脱気
装置付押し出し機で成形した。この成形品の揮発分はビ
ニルビフェニル組成物を使用しないときと比べて有意差
は認められなかった。A solvent was added to the vinyl biphenyl composition, TBC was immediately removed, 1,000 ppm was added to the styrene monomer, and bulk polymerization was carried out, followed by molding with an extruder with a deaerator. The volatile content of this molded product was not significantly different from that when the vinyl biphenyl composition was not used.
【００１５】比較例１ 重合防止剤として、ｔ−ブチルカテコールを配合しない
他は、実施例１〜３と同じ操作を行ったところ、２０日
程度で製品中のポリマー濃度が増加し、樹脂改質剤とし
ての用途には使用不能となった。Comparative Example 1 When the same operation as in Examples 1 to 3 was carried out except that t-butylcatechol was not added as a polymerization inhibitor, the polymer concentration in the product increased in about 20 days, and the resin modification It became unusable for use as an agent.
【００１６】実施例４〜６、比較例２ ４−エチルビフェニル９９％、その他１％のエチルビフ
ェニルを脱水素反応して得られた脱水素反応油を−２０
℃で晶析し、これを２０℃、３８００ｒｐｍ、４５分間
の条件で遠心分離して４−ビニルビフェニル９０％、４
−エチルビフェニル６％、その他４％の４−ビニルビフ
ェニル組成物を得た。なお、晶析を行う前に母液に対し
て３，３００ｐｐｍ、１，８００ｐｐｍ、９００ｐｐｍ
及び０ｐｐｍのｔ−ブチルカテコール（ＴＢＣ）を溶解
させて、４−ビニルビフェニル組成物中のＴＢＣ量を
２，０００ｐｐｍから０ｐｐｍの間で変化させた。この
組成物を、２０℃に保たれた室内で放置してポリマーの
生成量を測定したところ、ポリマー生成量は表２のとお
りであった。Examples 4 to 6 and Comparative Example 2 The dehydrogenation reaction oil obtained by dehydrogenating 4-ethylbiphenyl 99% and other 1% ethylbiphenyl was -20.
Crystallization was performed at 20 ° C., and the mixture was centrifuged at 20 ° C., 3800 rpm for 45 minutes to give 4-vinylbiphenyl 90%, 4%.
A 4-vinylbiphenyl composition containing 6% of ethylbiphenyl and 4% of others was obtained. It should be noted that before crystallization, 3,300 ppm, 1,800 ppm, 900 ppm relative to the mother liquor
And 0 ppm of t-butylcatechol (TBC) were dissolved to change the amount of TBC in the 4-vinylbiphenyl composition between 2,000 ppm and 0 ppm. When this composition was left in a room kept at 20 ° C. and the amount of polymer produced was measured, the amount of polymer produced was as shown in Table 2.
【００１７】[0017]
【表２】 [Table 2]
【００１８】このビニルビフェニル組成物に溶剤を加え
てからＴＢＣを直前に除去して、スチレンモノマーに対
して１，０００ｐｐｍを添加して塊状重合した後に脱気
装置付押し出し機で成形した。この成形品の揮発分はビ
ニルビフェニル組成物を使用しないときと比べて有意差
は認められなかった。A solvent was added to this vinylbiphenyl composition, TBC was immediately removed, 1,000 ppm was added to the styrene monomer, and bulk polymerization was carried out, followed by molding with an extruder equipped with a deaerator. The volatile content of this molded product was not significantly different from that when the vinyl biphenyl composition was not used.
【００１９】[0019]
【発明の効果】本発明のビニルビフェニル組成物は、安
定性が優れるので長期間の保存、輸送に耐えることがで
きる。また、これを樹脂用原料、樹脂改質剤等として使
用すると、樹脂改質効果が大きいだけでなく、使いやす
さの点でも優れる。The vinyl biphenyl composition of the present invention has excellent stability and can withstand long-term storage and transportation. Further, when this is used as a resin raw material, a resin modifier, etc., not only is the resin modifying effect large, but it is also easy to use.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｆ 212/32 ＭＪＹ Ｃ０８Ｆ 212/32 ＭＪＹ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication C08F 212/32 MJY C08F 212/32 MJY
Claims (2)
ら得られるビニルビフェニル組成物であって、ビニルビ
フェニル含有量が５０〜８０重量％、エチルビフェニル
含有量が２０〜４５重量％、ｔ−ブチルカテコール濃度
が５００〜５０００ｐｐｍであるビニルビフェニル組成
物。1. A vinylbiphenyl composition obtained from a dehydrogenation reaction mixture of ethylbiphenyl, which has a vinylbiphenyl content of 50 to 80% by weight, an ethylbiphenyl content of 20 to 45% by weight, and a t-butylcatechol concentration. Is 500 to 5000 ppm.
物から得られるビニルビフェニル組成物であって、４−
ビニルビフェニル含有量が８０〜９７重量％、エチルビ
フェニル含有量が３〜２０重量％、ｔ−ブチルカテコー
ル濃度が５００〜５０００ｐｐｍであるビニルビフェニ
ル組成物。2. A vinylbiphenyl composition obtained from a dehydrogenation reaction mixture of 4-ethylbiphenyl, which comprises:
A vinylbiphenyl composition having a vinylbiphenyl content of 80 to 97% by weight, an ethylbiphenyl content of 3 to 20% by weight, and a t-butylcatechol concentration of 500 to 5000 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32048395A JPH09157190A (en) | 1995-12-08 | 1995-12-08 | Vinylbipheny composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32048395A JPH09157190A (en) | 1995-12-08 | 1995-12-08 | Vinylbipheny composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09157190A true JPH09157190A (en) | 1997-06-17 |
Family
ID=18121955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32048395A Pending JPH09157190A (en) | 1995-12-08 | 1995-12-08 | Vinylbipheny composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09157190A (en) |
-
1995
- 1995-12-08 JP JP32048395A patent/JPH09157190A/en active Pending
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