JPH01167314A - Polymerization of indene - Google Patents

Polymerization of indene

Info

Publication number
JPH01167314A
JPH01167314A JP32527687A JP32527687A JPH01167314A JP H01167314 A JPH01167314 A JP H01167314A JP 32527687 A JP32527687 A JP 32527687A JP 32527687 A JP32527687 A JP 32527687A JP H01167314 A JPH01167314 A JP H01167314A
Authority
JP
Japan
Prior art keywords
indene
polymerization
polyindene
formula
catalyst
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
Application number
JP32527687A
Other languages
Japanese (ja)
Inventor
Kunitaka Yamada
山田　邦貴
Mitsuhiro Mori
森　充博
Yozo Kondo
近藤　陽三
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tosoh Corp
Original Assignee
Tosoh Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tosoh Corp filed Critical Tosoh Corp
Priority to JP32527687A priority Critical patent/JPH01167314A/en
Publication of JPH01167314A publication Critical patent/JPH01167314A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

PURPOSE:To obtain noncrystalline polyindene with high glass transition temperature, good in transparency, low in birefringence, useful as a heat-resistant polymer or optical material, by polymerization of indene using a specific catalyst. CONSTITUTION:The objective polyindene can be obtained by polymerization of indene in the presence of a catalyst consisting of (A) a vanadium-contg. catalytic component [e.g., a compound of the formula V0(OR)pXq or the formula V(OR)rXs (X is halogen; R is 1-22C hydrocarbon; p and q are each 0-3, p+q=2-3; r and s are each 0-4, r+s=3-4); specifically, VOCl3, VO(OC2H5) Cl3] and (B) a halogenated organoaluminum compound catalytic component [e.g., a compound of the formula AlXnR3-n (X is halogen; R is 1-12C hydrocarbon; n is 1-2); specifically, Al(C2H5)Cl]. The molar ratio: Al/V is pref. 3-100.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、インデンの重合方法に関するものである。さ
らに詳しくは、本発明はインデンの重合において高活性
にインデンを重合する方法に関するものである。得られ
るポリインデンは耐熱性ポリマーとして、また光学材料
として使用可能である。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for polymerizing indene. More specifically, the present invention relates to a method for polymerizing indene with high activity. The resulting polyindene can be used as a heat-resistant polymer and as an optical material.

〔従来の技術〕[Conventional technology]

インデンの重合は従来カチオン重合が知られており、５
７．化ホウ素やハロゲン化アルミニウム化合物等が使用
されるが、活性的には低レベルにあった。Cationic polymerization is conventionally known as the polymerization of indene.
7. Boron oxide and aluminum halide compounds were used, but their activity was at a low level.

そのため、ポリマーから残触媒を除（ため大量のアルコ
ールで処理するなど充分な脱灰処理を行う必要があり、
残触媒の除去が困難であった。Therefore, it is necessary to perform sufficient deashing treatment, such as treatment with a large amount of alcohol, to remove the residual catalyst from the polymer.
Removal of residual catalyst was difficult.

また、ポリマーあたりの触媒の使用量が多いためコスト
的にも非常に不利であった。Furthermore, since the amount of catalyst used per polymer was large, it was very disadvantageous in terms of cost.

〔発明が解決しようとする問題点〕[Problem that the invention seeks to solve]

本発明は、高活性にポリインデンを製造する方法を提供
するものである。The present invention provides a method for producing polyindene with high activity.

〔問題点な解決するための手段〕[Means for solving problems]

本発明は、バナジウム含有触媒成分とハロゲン化有機ア
ルミニウム化合物触媒成分からなる触媒の存在下、イン
デンを重合することを特徴とするポリインデンの製造方
法に関するものである。The present invention relates to a method for producing polyindene, which comprises polymerizing indene in the presence of a catalyst comprising a vanadium-containing catalyst component and a halogenated organic aluminum compound catalyst component.

〔作　用〕[For production]

本発明において使用されるバナジウム含有触媒ｖ（ＯＲ
）ｒｘ８（ｘ：ハロゲ７．Ｒは炭素数１〜２２の炭化水
素基、ｐ、ｑ：Ｏ〜３、ｐ＋ｑ　：　２〜３、ｒ、ｓ　
：　０〜４Ｓｒ十ｓ　：　５〜４　）であられされる化
合物を使用することができる。Vanadium-containing catalyst v (OR
) rx8 (x: Halogen 7. R is a hydrocarbon group having 1 to 22 carbon atoms, p, q: O to 3, p+q: 2 to 3, r, s
: 0 to 4 Sr: 5 to 4) can be used.

より具体的にはＶＯＯＩ、　、　Ｔｏ（００，Ｈ％）０
４　、　ＶＯ（ｏｉｓｏｏ晶）Ｃ４、ＶＯ（Ｏｎ−０４
Ｈ１１）０４　、　ｖＯ（００晶入、　ＶＯＢｒ、　、
　ＶＣｌ２　。More specifically, VOOI, , To(00,H%)0
4, VO (oisoo crystal) C4, VO (On-04
H11) 04, vO (00 crystal included, VOBr, ,
VCl2.

ｖＯＣ４，ｖＯ（Ｏｎ−０４Ｈ，ｌ入などを例示するこ
とができる。Examples include vOC4, vO(On-04H, 1-on, etc.).

ハロゲン化有機アルミニウム化合物触媒成分としては、
−数式ＡｔＸｎへ−ｒｌ（ｘ：ハロゲン、Ｒ：炭素数１
〜１２の炭化水素基、ｎ：１〜２）であられされる化合
物が使用できる。As the halogenated organoaluminum compound catalyst component,
-To the formula AtXn -rl (x: halogen, R: carbon number 1
-12 hydrocarbon groups, n: 1-2) can be used.

具体的にはＡｚ（、）Ｉ５）、ｃｚ、　Ａｔ（ｃ、４）
、Ｂｒ、　ｈｔ（ｃ、ｚ’）、ａｔ。Specifically, Az(,)I5), cz, At(c, 4)
,Br,ht(c,z'),at.

Ａ４（ｃ！Ｔｌ５）ｓＣ４、Ａ４　（ｃ’４４）ｓＣ４
、Ａ４（ｃ２Ｈａ）ｓＢｒｓ　。A4 (c!Tl5)sC4, A4 (c'44)sC4
, A4(c2Ha)sBrs.

Ａｔ（ｃ、４）Ｃ４、ｈｔ（ｃ、馬）Ｃ４、Ａｔ（Ｃ４
％）Ｂｒｔ　などを例示できる。At (c, 4) C4, ht (c, horse) C4, At (C4
%)Brt.

これら２成分な用いてインデンを重合するにあたり、２
成分の使用量比はＡ２７７モル比で１以上、好ましくは
５〜１００で使用できる。In polymerizing indene using these two components, 2
The usage ratio of the components can be 1 or more, preferably 5 to 100 in A277 molar ratio.

触媒の使用量は溶媒に対し、バナジウムについてα００
１〜１５０　ｍｍｏｔ／Ｊ！　ｓ好ましくはα０１〜５
０　ｍｍｏｔ／ｌで使用される。The amount of catalyst used is α00 for vanadium relative to the solvent.
1~150 mmot/J! s preferably α01-5
used at 0 mmot/l.

七ツマ−としてはインデン以外にインデン環に１〜６の
炭化水素基が１〜７個結合したものおよびこれらの混合
物も使用できる。これらモノマーとしては具体的には１
−メチルインデン、２−メチルインデン、３−メチルイ
ンデン、４，５，６．７−チトラメチルインデンなどが
例示される。As the hepatomer, in addition to indene, compounds having 1 to 7 hydrocarbon groups of 1 to 6 bonded to an indene ring and mixtures thereof can also be used. Specifically, these monomers are 1
Examples include -methylindene, 2-methylindene, 3-methylindene, and 4,5,6.7-titramethylindene.

インデンの重合はインデンをモノマー兼溶媒として使用
することも可能であり、また不活性溶媒を使用すること
も可能である。In the polymerization of indene, it is possible to use indene as both a monomer and a solvent, and it is also possible to use an inert solvent.

この不活性溶媒としては炭素数４〜２０の炭化水素カ用
いられ、具体的にはペンタン、ヘキサン。As this inert solvent, a hydrocarbon having 4 to 20 carbon atoms is used, specifically pentane or hexane.

ヘプタン、オクタン、シクロヘキサン、ベンゼン。Heptane, octane, cyclohexane, benzene.

トルエン、キシレンなどが使用できる。Toluene, xylene, etc. can be used.

本発明における重合条件は特に限定されないが、重合温
度としては一５０〜２００℃、好ましくは一２０〜１３
０℃で行われる。The polymerization conditions in the present invention are not particularly limited, but the polymerization temperature is -50 to 200°C, preferably -20 to 13°C.
Performed at 0°C.

〔発明の効果〕〔Effect of the invention〕

以上に示した特定の触媒を使用し、インデンを重合する
ことにより高活性にポリインデンを得ることができる。Polyindene can be obtained with high activity by polymerizing indene using the specific catalyst shown above.

また触媒当りの活性が高いため、容易に残触媒を除去す
ることが可能である。Furthermore, since the activity per catalyst is high, residual catalyst can be easily removed.

このようにして得られたポリインデンのガラス転移温度
は１５０℃以上と高く、耐熱性ポリマーとしての使用が
可能であり、また透明性がよく、非品性で複屈折も低い
ため光学材料としての使用も可能である。The glass transition temperature of the polyindene obtained in this way is as high as 150°C or higher, making it possible to use it as a heat-resistant polymer.It also has good transparency, low quality, and low birefringence, so it can be used as an optical material. is also possible.

〔実施例〕〔Example〕

以下、本発明を実施例によって説明するが、これらの実
施例によって何ら制限されるものではな実施例１ （インデンの重合） 充分窒素置換した３　００　ｃｃフラスコにトルエン２
５０ｄ、エチルアルミニウムセスキクロライドｃＬ９５
９および５塩化バナジル１５０■を入れ、内温を１０℃
にし、インデン４０９を入れ、１０℃で１２０分反応さ
せた。Hereinafter, the present invention will be explained by examples, but the present invention is not limited in any way by these examples. Example 1 (Polymerization of indene) 2 toluene was added to a 300 cc flask which had been sufficiently purged with nitrogen.
50d, ethylaluminum sesquichloride cL95
Add 150cm of vanadyl chloride 9 and 5 and bring the internal temperature to 10℃.
Then, indene 409 was added and reacted at 10°C for 120 minutes.

反応液はその後１ｔのメタノールに入れ、析出物をろ別
し、さらに１ｔのメタノールで３回洗浄した。収量は２
４．０９であった。Thereafter, the reaction solution was poured into 1 ton of methanol, and the precipitate was filtered off and further washed three times with 1 ton of methanol. Yield is 2
It was 4.09.

また、ポリマーのガラス転移温度は示差熱走査熱量計（
セイコー電子′ＩＡＤｓｃ２００）で測定したところ１
８１℃であった。In addition, the glass transition temperature of a polymer can be measured using a differential scanning calorimeter (
Measured with Seiko Electronics' IADsc200) 1
The temperature was 81°C.

比較例１ （インデンの重合） 実施例１で３塩化バナジルを使用しなかった以外は実施
例１と同様の操作により重合を行った。Comparative Example 1 (Polymerization of indene) Polymerization was carried out in the same manner as in Example 1 except that vanadyl trichloride was not used in Example 1.

収量は１．３９であった。The yield was 1.39.

実施例２．５ ’ｆｉ例１でエチルアルミニウムセスキクロライドのか
わりにエチルアルミニウムジクロライドをα９５９、ジ
エチルアルミニウムクロライドを０．９１９使用した以
外は実施例１と同様の操作により重合を行った。Example 2.5'fi Polymerization was carried out in the same manner as in Example 1 except that ethylaluminum dichloride was used at α959 and diethylaluminum chloride was used at 0.919 in place of ethylaluminum sesquichloride.

収量はそれぞれ５１５９．５１５９であった。The yield was 5159.5159, respectively.

比較例２．３ 実施例２．３で３塩化バナジルを用いなかった以外は実
施例λ３と同様の操作により重合を行った。Comparative Example 2.3 Polymerization was carried out in the same manner as in Example λ3 except that vanadyl trichloride was not used in Example 2.3.

収量はそれぞれ５．５９，４．６９であった。The yields were 5.59 and 4.69, respectively.

実施例４．５ （インデンの重合） 実施例１で５塩化バナジルのかわりに２塩化エトキシバ
ナジル、４塩化バナジルを用いる以外は実施例１と同様
の操作により重合を行った。Example 4.5 (Polymerization of indene) Polymerization was carried out in the same manner as in Example 1 except that ethoxyvanadyl dichloride and vanadyl tetrachloride were used instead of vanadyl pentachloride.

収量はそれぞれ３４．５り、２１．５ｇであった。The yield was 34.5 g and 21.5 g, respectively.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は本発明に用いる触媒調製図（フローチャート）
である。Figure 1 is a catalyst preparation diagram (flow chart) used in the present invention.
It is.

Claims (1)

【特許請求の範囲】[Claims] （１）バナジウム含有触媒成分とハロゲン化有機アルミ
ニウム化合物触媒成分からなる触媒の存在下インデンを
重合することを特徴とするポリインデンの製造方法。(1) A method for producing polyindene, which comprises polymerizing indene in the presence of a catalyst consisting of a vanadium-containing catalyst component and a halogenated organic aluminum compound catalyst component.
JP32527687A 1987-12-24 1987-12-24 Polymerization of indene Pending JPH01167314A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP32527687A JPH01167314A (en) 1987-12-24 1987-12-24 Polymerization of indene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP32527687A JPH01167314A (en) 1987-12-24 1987-12-24 Polymerization of indene

Publications (1)

Publication Number Publication Date
JPH01167314A true JPH01167314A (en) 1989-07-03

Family

ID=18175003

Family Applications (1)

Application Number Title Priority Date Filing Date
JP32527687A Pending JPH01167314A (en) 1987-12-24 1987-12-24 Polymerization of indene

Country Status (1)

Country Link
JP (1) JPH01167314A (en)

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