JP3076007B2 - Synthetic method of syndiotactic vinyl-based aromatic polymer - Google Patents
Synthetic method of syndiotactic vinyl-based aromatic polymerInfo
- Publication number
- JP3076007B2 JP3076007B2 JP09264124A JP26412497A JP3076007B2 JP 3076007 B2 JP3076007 B2 JP 3076007B2 JP 09264124 A JP09264124 A JP 09264124A JP 26412497 A JP26412497 A JP 26412497A JP 3076007 B2 JP3076007 B2 JP 3076007B2
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polymer
- based aromatic
- vinyl
- syndiotactic
- syndiotactic vinyl
- 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 - Fee Related
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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
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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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)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高圧かつ／または
不活性ガスの超臨界状態において、チタン化合物とメチ
ルアルミオキサンとから成る触媒を介在させ、ビニル基
芳香族単量体、特にスチレンを重合し、シンジオタクチ
ック重合体を合成する方法に関する。The present invention relates to a method for producing a vinyl-based aromatic monomer, particularly styrene, in a supercritical state under high pressure and / or inert gas with a catalyst comprising a titanium compound and methylaluminoxane interposed therebetween. The present invention relates to a method for polymerizing and synthesizing a syndiotactic polymer.
【０００２】[0002]
【従来の技術】１９８６年、Ｎ．イシハラ、Ｔ．セイミ
ガ、Ｍ．クラモトそしてＭ. ウオイは、巨大分子、19、
pp.2464-2465（1986）において、シンジオタクチックポ
リスチレンを合成することができる Ti 化合物とメチル
アルミオキサンから成る触媒機能を発表した。その重合
は、例えば反応温度、Al/Ti の触媒／助触媒の分子比、
そして単量体／触媒比などの異なる反応環境下で異なる
平均分子量、異なる多分散系で生じる。ポリスチレンの
シンジオタクチック化に影響を及ぼす主たる要因は、
Ｎ．イシハラ等による巨大分子、21、pp.3356-3360、欧
州特許 EP210,615および EP224,096に開示されているよ
うに、Ti（IV）及びTi（III ）から成るZiegler-Natta
型触媒が知られている。しかしながら、Ziegler-Natta
型触媒が用いられる重合は、通常、比較的低温低圧で起
こり、近大気圧下で起こるシンジオタクチックポリスチ
レン合成であり、U.S.特許5,066,741 、U.S.特許5,206,
197 およびWO88/10275に開示されている。2. Description of the Related Art Ishihara, T. Seimiga, M.P. Kuramoto and M. Woi are macromolecules, 19,
In pp.2464-2465 (1986), a catalyst function consisting of a Ti compound and methylaluminoxane, which can synthesize syndiotactic polystyrene, was announced. The polymerization can be carried out, for example, by the reaction temperature, the Al / Ti
It occurs with different average molecular weights and different polydispersions under different reaction environments such as monomer / catalyst ratio. The main factors affecting the syndiotacticization of polystyrene are:
N. Ziegler-Natta consisting of Ti (IV) and Ti (III) as disclosed in Ishihara et al., 21, pp. 3356-3360, European Patents EP210,615 and EP224,096.
Type catalysts are known. However, Ziegler-Natta
Polymerization in which a type catalyst is used is a syndiotactic polystyrene synthesis that usually occurs at relatively low temperature and low pressure, and occurs at near atmospheric pressure, and is disclosed in US Patent 5,066,741, US Patent 5,206,
197 and WO 88/10275.
【０００３】一般に、トルエンは、シンジオタクチック
ポリスチレン合成に用いられる最もありふれた溶剤であ
るが、重合時に増殖を抑える連鎖反応剤として働く。[0003] In general, toluene is the most common solvent used in syndiotactic polystyrene synthesis, but acts as a chain reactant to suppress growth during polymerization.
【０００４】[0004]
【発明が解決しようとする課題】本発明の主な目的は、
シンジオタクチックビニル基芳香族重合体を多量に合成
することにある。本発明の他の目的は、シンジオタクチ
ックビニル基芳香族重合反応でトルエンを溶剤として用
いることの欠点を克服し、シンジオタクチックビニル基
芳香族重合体を合成することにある。SUMMARY OF THE INVENTION The main object of the present invention is to:
It is to synthesize a large amount of a syndiotactic vinyl group aromatic polymer. Another object of the present invention is to overcome the drawbacks of using toluene as a solvent in a syndiotactic vinyl group aromatic polymerization reaction and to synthesize a syndiotactic vinyl group aromatic polymer.
【０００５】[0005]
【課題を解決するための手段】本発明は、TiCpXYZ とメ
チルアルミオキサンとから成る触媒を用いたビニル基芳
香族単量体を重合するシンジオタクチックビニル基芳香
族重合体の合成方法に関する。ここで、Cpは、シクロペ
ンタジエニルであり、X 、Y 及びZ は、独立したハロゲ
ンまたは−ORまたは−NR2である。また、R は脂肪族、
シクロ脂肪族または１から１２の炭素を有する芳香族炭
化水素である。また本発明は、３．４４７×１０ 6 Ｎ／
ｍ 2 （５００psi ）より高圧の不活性ガスのもとで行わ
れる。SUMMARY OF THE INVENTION The present invention relates to a method for synthesizing a syndiotactic vinyl-based aromatic polymer which polymerizes a vinyl-based aromatic monomer using a catalyst comprising TiCpXYZ and methylaluminoxane. Here, Cp is cyclopentadienyl, and X 1, Y 2 and Z 3 are each independently halogen or —OR or —NR 2 . R is aliphatic,
Cycloaliphatic or aromatic hydrocarbons having 1 to 12 carbons. The present invention also provides 3.447 × 10 6 N /
performed under high-pressure inert gas from the m 2 (500psi).
【０００６】圧力上昇に伴い反応率が増すという２衝突
理論に基づいて、高圧は本発明の重合過程に有利に働
く。高圧かつ／または超臨界状態での不活性ガスは、本
発明の高圧状態における不活性溶剤として用いられる。
本発明の高圧状態に用いられる適切なガスは、N2、He、
Ne、Ar及びKrであるが、これらに限らない。High pressures favor the polymerization process of the present invention, based on the two collision theory that the reaction rate increases with increasing pressure. The inert gas under high pressure and / or supercritical state is used as the inert solvent under high pressure in the present invention.
Suitable gases used in the high pressure state of the present invention are N 2 , He,
Ne, Ar and Kr, but are not limited to these.
【０００７】[0007]
【発明の実施の形態】本発明では、ビニル基芳香族単量
体の重合に関して、不活性ガスの高圧かつ／または超臨
界状態で、チタン化合物とメチルアルミオキサンから成
る触媒を介在させ、シンジオタクチック重合体を合成す
る。本発明のビニル基芳香族重合体は一般式化１で示さ
れる。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the polymerization of a vinyl group aromatic monomer is carried out under a high pressure and / or supercritical state of an inert gas with a catalyst comprising a titanium compound and methylaluminoxane interposed therebetween. Synthesize an tactic polymer. The vinyl group aromatic polymer of the present invention is represented by the general formula 1.
【０００８】[0008]
【化１】 Embedded image
【０００９】ここで、R1は、水素、ハロゲン、あるいは
炭素、酸素、窒素、硫黄、燐またはけい素を含む置換基
であり、n は、１から５である。好ましくは、R1は、ハ
ロゲン、メチル基またはエチル基であり、n は１であ
る。さらに好ましくは、R1はハロゲンである。本発明に
おける重合反応は、反応媒体として働く不活性ガス及び
有機溶剤遊離体の超臨界流動状態で理想的に実行され
る。しかしながら、本発明で用いられる触媒は不安定で
あり、大気中で酸化され易いため、溶液の形で利用され
る。それにもかかわらず、本発明では、触媒用の有機溶
剤は、最少量で用いられる。本発明の原理で用いられる
不活性ガスの圧力は、超臨界状態に至るのに十分なほど
高い値であり、大気圧(1.013×105 N/m2(14.7psi))から
3.447 ×107 N/m2(5000psi) の範囲である。反応圧力と
温度が不活性ガスの臨界点に到達するとき、不活性ガス
は超臨界流動状態となり、反応媒体となる。ここで、N2
は、Tc=-147 ℃（126.2K）、Pc=3.389×106 N/m2(14.7p
si) であり、Heは、Tc=-269.9 ℃（3.31K)、Pc=1.139×
105N／m2(14.7psi) であり、Neは、Tc=-228.8 ℃(44.4
K) 、Pc=2.759×106N／m2(400.3psi)であり、Arは、Tc=
-122.4 ℃(150.8K)、Pc=4.869×106N／m2(706.3psi)で
あり、Krは、Tc=-63.8℃(209.4K)、Pc=5.499×106N／m2
(797.7psi)である。Here, R 1 is hydrogen, halogen, or a substituent containing carbon, oxygen, nitrogen, sulfur, phosphorus or silicon, and n is 1 to 5. Preferably, R 1 is halogen, methyl or ethyl, and n is 1. More preferably, R 1 is halogen. The polymerization reaction in the present invention is ideally carried out in a supercritical fluid state of an inert gas serving as a reaction medium and a free organic solvent. However, the catalyst used in the present invention is unstable and easily oxidized in the atmosphere, so that it is used in the form of a solution. Nevertheless, in the present invention, the organic solvent for the catalyst is used in a minimum amount. The pressure of the inert gas used in the principles of the present invention is high enough to reach a supercritical state, from atmospheric pressure (1.013 × 10 5 N / m 2 (14.7 psi)).
It is in the range of 3.447 × 10 7 N / m 2 (5000 psi). When the reaction pressure and temperature reach the critical point of the inert gas, the inert gas becomes a supercritical fluid state and becomes a reaction medium. Where N 2
Is Tc = -147 ° C (126.2K), Pc = 3.389 × 10 6 N / m 2 (14.7p
si), He is Tc = -269.9 ° C (3.31K), Pc = 1.139 ×
10 5 N / m 2 (14.7 psi), Ne is Tc = −228.8 ° C. (44.4
K), Pc = 2.759 × 10 6 N / m 2 (400.3 psi), and Ar
-122.4 ° C. (150.8K), Pc = 4.869 × 10 6 N / m 2 (706.3 psi), Kr is Tc = -63.8 ° C. (209.4K), Pc = 5.499 × 10 6 N / m 2
(797.7 psi).
【００１０】本発明で用いられるチタン化合物は、一般
式TiCpXYZ である。ここで、Cpは、シクロペンタジエニ
ルであり、X 、Y 及びZ は、ハロゲンまたは−ORまたは
−NR 2 である。また、R は脂肪族、シクロ脂肪族または
１から１２の炭素を有する芳香族炭水素である。チタン
化合物は、市販のものであり、従来のものである。本発
明の後述の実施例において、シクロペンタジエニルチタ
ニウムトリクロライドのチタン化合物を用いた。本発明
で用いられたメチルアルミオキサンは、U.S.特許4,544,
762 におけるカミンスキまたは EPO 210,615におけるイ
シハラにより開示された技術で合成される。また、本発
明の後述の実施例において、アルドリッヒ化学会社のメ
チルアルミオキサンを用いた。The titanium compound used in the present invention is generally
The formula is TiCpXYZ. Here, Cp is cyclopentadienyl
X, Y and Z are halogen or -OR or
−NR TwoIt is. R is aliphatic, cycloaliphatic or
An aromatic hydrocarbon having 1 to 12 carbons. Titanium
The compounds are commercially available and conventional. Departure
In the examples to be described hereinafter, cyclopentadienyl tita
A titanium compound of trinium chloride was used. The present invention
The methylaluminoxane used in U.S. Patent 4,544,
Kaminski at 762 or B at EPO 210,615
Synthesized by the technology disclosed by Shihara. In addition,
In a later example of Ming, the Aldrich Chemical Company
Chiralaluminoxane was used.
【００１１】触媒／助触媒(Ti/Al) の分子比は１：５０
から１：１００００の範囲であるが、好ましくは１：２
５０から１：５０００の範囲である。Tiを含有する触媒
に対するビニル基芳香族重合体の分子比は、１００：１
から５００００００：１の範囲であり、好ましくは４０
００：１から５０００００：１の範囲である。The catalyst / cocatalyst (Ti / Al) molecular ratio is 1:50.
To 1: 10000, but preferably 1: 2
It ranges from 50 to 1: 5000. The molecular ratio of the vinyl-based aromatic polymer to the catalyst containing Ti is 100: 1.
To 5,000,000: 1, preferably 40
The range is from 00: 1 to 500000: 1.
【００１２】重合は、２５℃から１００℃、好ましくは
３０℃から８０℃の範囲で、ある時間内に望ましい重合
体が得られる。一般的な反応時間は５分から数時間の範
囲である。本発明における顕著な点は、合成時間が５分
から１時間の範囲であることである。本発明で重合され
る適切なビニル基芳香族単量体は、一般式化２であるも
のを含む。The polymerization is carried out at a temperature in the range of 25 ° C. to 100 ° C., preferably 30 ° C. to 80 ° C., and a desired polymer is obtained within a certain time. Typical reaction times range from 5 minutes to several hours. What is remarkable in the present invention is that the synthesis time ranges from 5 minutes to 1 hour. Suitable vinyl-based aromatic monomers to be polymerized in the present invention include those of general formula 2:
【００１３】[0013]
【化２】 Embedded image
【００１４】ここで、Ｒ2 は、水素、脂肪族または１か
ら１２炭素を有するシクロ脂肪族炭化水素であり、例え
ばスチレン、ｎ−ブチルスチレン、ｔ−ブチルスチレン
等のスチレンが好ましい。重合前にスチレン単量体を清
浄するため、モレキュラーシーブ（分子ふるい）やハイ
サーフィスエリアアルミナ（高表面積アルミナ）との接
触、脱気等により減圧するディボリティライゼイション
（結合を強化する）技術を用いる。本発明では、重合グ
レードスチレン単量体を無水Al2O3 のカラムを通して清
浄した。Here, R 2 is hydrogen, an aliphatic or a cycloaliphatic hydrocarbon having 1 to 12 carbons, for example, styrene such as styrene, n-butylstyrene and t-butylstyrene is preferable. In order to clean the styrene monomer before polymerization, we use a technology called molecular sieve (molecular sieve) or high surface area alumina (high surface area alumina) to reduce pressure by degassing etc. Used. In the present invention, the polymerization grade styrene monomer was cleaned through a column of anhydrous Al 2 O 3 .
【００１５】以下に、本発明による実施例及び比較例を
照会しながら詳細を説明する。実施例は、本発明を例証
するのみであって、本発明を制限するものではない。 （実施例１）重合実験は、攪拌オートクレーブを用い
て、バッチ式で行われた。オートクレーブ反応器は、３
００ml容量であって、３００℃で最大6.893 ×107N/m
2(10,000psi)であり、攪拌子と磁気駆動装置を備えてい
る。シンジオタクチック重合体を合成するため、オート
クレーブ反応器のガス抜きを最初に行い、オートクレー
ブ反応器内の空気をアルゴンガスで置換する。その後、
スチレン１００ｇと、４．７mlのトルエンで溶解したCp
TiCl3 を2.4 ×10-5モルと、１６mlのトルエンで溶解し
たメチルアルミオキサン(MAO) を2.4 ×10-2モルとを４
０℃アルゴン大気圧下でオートクレーブにかける。合成
開始のため、CpTiCl3 にMAO を注入するときの反応圧力
を6.893 ×106N/m2(1000psi)に調節する。１時間後、圧
力を弱め、合成反応を酸性化したメタノールを加えるこ
とで終了する。その結果得られる合成体を５００mlのメ
タノールで数回洗浄し、５０℃で２４時間真空乾燥す
る。得られる重合体は、３０．８２ｇであり、シンジオ
タクチック化したものを８７％以上含むポリスチレンを
７３％含んでいる。メチルエチルケトンで８時間沸騰し
て抽出した合成物は、融点２５３℃のメチルエチルケト
ン不溶性ポリスチレンであり、Tgが９９℃であり、平均
分子量が１５５４４１であり、13C-NMR 分析によるとシ
ンジオタクチック化したものが９９％より大であった。
結果を表１に示す。The details will be described below with reference to examples and comparative examples according to the present invention. The examples only illustrate the invention, but do not limit it. (Example 1) The polymerization experiment was performed in a batch system using a stirring autoclave. The autoclave reactor has 3
It has a capacity of 00 ml and a maximum of 6.893 × 10 7 N / m at 300 ° C.
2 (10,000 psi) with stirrer and magnetic drive. To synthesize a syndiotactic polymer, the autoclave reactor is first vented and the air in the autoclave reactor is replaced with argon gas. afterwards,
Cp dissolved in 100 g of styrene and 4.7 ml of toluene
2.4 × 10 −5 mol of TiCl 3 and 2.4 × 10 −2 mol of methylaluminoxane (MAO) dissolved in 16 ml of toluene
Autoclave at 0 ° C. under atmospheric pressure of argon. To start the synthesis, the reaction pressure when injecting MAO into CpTiCl 3 is adjusted to 6.893 × 10 6 N / m 2 (1000 psi). After 1 hour, the pressure is reduced and the synthesis reaction is terminated by adding acidified methanol. The resulting composite is washed several times with 500 ml of methanol and dried under vacuum at 50 ° C. for 24 hours. The resulting polymer weighs 30.82 g and contains 73% of polystyrene containing at least 87% of syndiotactic one. The product extracted by boiling with methyl ethyl ketone for 8 hours is a methyl ethyl ketone insoluble polystyrene having a melting point of 253 ° C., a Tg of 99 ° C., an average molecular weight of 155441, and a syndiotactic according to 13 C-NMR analysis. Was greater than 99%.
Table 1 shows the results.
【００１６】[0016]
【表１】 [Table 1]
【００１７】（実施例２〜実施例２０）表１に示すよう
に、チタンを含む分子比、反応温度及び反応圧力を除き
実施例１の反応手順を本質上繰り返す。 （比較例１〜比較例２）実施例１で説明した反応を大気
圧および反応温度を除きほぼ同じ状態下で進める。結果
は表１に示す。比較例１及び比較例２は、実施例７、実
施例９−実施例１２に比べて合成量が少量である。(Examples 2 to 20) As shown in Table 1, the reaction procedure of Example 1 is essentially repeated except for the molecular ratio containing titanium, the reaction temperature and the reaction pressure. (Comparative Examples 1 and 2) The reaction described in Example 1 proceeds under almost the same conditions except for the atmospheric pressure and the reaction temperature. The results are shown in Table 1. Comparative Examples 1 and 2 have a smaller amount of synthesis than Examples 7 and 9 to 12.
【００１８】上述した本発明の実施例は、すべて単に例
証であり、本発明を制限するものではない。それゆえ本
発明は、その真意から逸脱することなく、他の具体的な
形式で具体化される。The above-described embodiments of the present invention are all merely illustrative and do not limit the present invention. Therefore, the present invention may be embodied in other specific forms without departing from its spirit.
フロントページの続き (56)参考文献 特開 平１−185302（ＪＰ，Ａ) 特開 平２−102206（ＪＰ，Ａ) 特開 平９−183810（ＪＰ，Ａ) 特表 平１−503788（ＪＰ，Ａ) 特表 平６−510808（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 4/60 - 4/70 C08F 12/00 - 12/36 Continuation of front page (56) References JP-A-1-185302 (JP, A) JP-A-2-102206 (JP, A) JP-A-9-183810 (JP, A) (A) Special table Hei 6-510808 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C08F 4/60-4/70 C08F 12/00-12/36
Claims (5)
成る触媒を介在させ、ビニル基芳香族単量体を重合して
成るシンジオタクチックビニル基芳香族重合体を合成す
る方法であって、 Cpは、シクロペンタジエニルであり、X 、Y およびZ
は、ハロゲン、−ORあるいは−NR2であり、R は、脂肪
族、シクロ脂肪族あるいは１から１２の炭素を有する芳
香族炭化水素であり、３．４４７×１０ 6 Ｎ／ｍ 2 （５００psi ） より高圧の不
活性ガスのもとで合成することを特徴とするシンジオタ
クチックビニル基芳香族重合体の合成方法。1. A method for synthesizing a syndiotactic vinyl-based aromatic polymer obtained by polymerizing a vinyl-based aromatic monomer through a catalyst comprising TiCpXYZ and methylaluminoxane, wherein Cp is , Cyclopentadienyl, X, Y and Z
Is halogen, —OR or —NR 2 , R is aliphatic, cycloaliphatic or aromatic hydrocarbon having 1 to 12 carbons, and is 500 psi (3.447 × 10 6 N / m 2 ). A method for synthesizing a syndiotactic vinyl-based aromatic polymer, which is synthesized under an inert gas at a higher pressure.
構成されるグループから選択されたものであることを特
徴とする請求項１記載のシンジオタクチックビニル基芳
香族重合体の合成方法。2. The syndiotactic vinyl-based aromatic polymer according to claim 1, wherein the inert gas is selected from the group consisting of N 2 , He, Ar and Kr. Synthesis method.
ることを特徴とする請求項１記載のシンジオタクチック
ビニル基芳香族重合体の合成方法。3. The method for synthesizing a syndiotactic vinyl-based aromatic polymer according to claim 1, wherein the inert gas is in a supercritical fluid state.
る前記触媒との分子比は、４０００：１から５００００
０：１の範囲であることを特徴とする請求項１記載のシ
ンジオタクチックビニル基芳香族重合体の合成方法。4. The molecular ratio of the vinyl group aromatic monomer to the Ti-containing catalyst is from 4000: 1 to 50,000.
2. The method for synthesizing a syndiotactic vinyl group aromatic polymer according to claim 1, wherein the ratio is in the range of 0: 1.
行われることを特徴とする請求項１記載のシンジオタク
チックビニル基芳香族重合体の合成方法。5. The method for synthesizing a syndiotactic vinyl-based aromatic polymer according to claim 1, wherein the polymerization is carried out in a temperature range of 25 ° C. to 100 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09264124A JP3076007B2 (en) | 1997-09-29 | 1997-09-29 | Synthetic method of syndiotactic vinyl-based aromatic polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09264124A JP3076007B2 (en) | 1997-09-29 | 1997-09-29 | Synthetic method of syndiotactic vinyl-based aromatic polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11106414A JPH11106414A (en) | 1999-04-20 |
| JP3076007B2 true JP3076007B2 (en) | 2000-08-14 |
Family
ID=17398820
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09264124A Expired - Fee Related JP3076007B2 (en) | 1997-09-29 | 1997-09-29 | Synthetic method of syndiotactic vinyl-based aromatic polymer |
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| Country | Link |
|---|---|
| JP (1) | JP3076007B2 (en) |
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1997
- 1997-09-29 JP JP09264124A patent/JP3076007B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| JPH11106414A (en) | 1999-04-20 |
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