JPS63268709A - Production of stereoregular polystyrene - Google Patents
Production of stereoregular polystyreneInfo
- Publication number
- JPS63268709A JPS63268709A JP10178387A JP10178387A JPS63268709A JP S63268709 A JPS63268709 A JP S63268709A JP 10178387 A JP10178387 A JP 10178387A JP 10178387 A JP10178387 A JP 10178387A JP S63268709 A JPS63268709 A JP S63268709A
- Authority
- JP
- Japan
- Prior art keywords
- polystyrene
- formula
- cyclopentadienyl
- catalyst
- compound
- 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
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 18
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 12
- 150000003609 titanium compounds Chemical class 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 238000002425 crystallisation Methods 0.000 abstract description 6
- 230000008025 crystallization Effects 0.000 abstract description 6
- 239000010936 titanium Substances 0.000 abstract description 4
- CYKLGTUKGYURDP-UHFFFAOYSA-L copper;hydrogen sulfate;hydroxide Chemical compound O.[Cu+2].[O-]S([O-])(=O)=O CYKLGTUKGYURDP-UHFFFAOYSA-L 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- JAGHDVYKBYUAFD-UHFFFAOYSA-L cyclopenta-1,3-diene;titanium(4+);dichloride Chemical compound [Cl-].[Cl-].[Ti+4].C1C=CC=[C-]1.C1C=CC=[C-]1 JAGHDVYKBYUAFD-UHFFFAOYSA-L 0.000 abstract 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 abstract 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- -1 titanium trichloride Chemical class 0.000 description 4
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- KSFCHHFBQJDGFF-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C1C=CC=C1.C1C=CC=C1 KSFCHHFBQJDGFF-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- AVUFKWQSSOCDJZ-UHFFFAOYSA-K trichlorotitanium;triethylalumane Chemical compound [Cl-].[Cl-].[Cl-].[Ti+3].CC[Al](CC)CC AVUFKWQSSOCDJZ-UHFFFAOYSA-K 0.000 description 1
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
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
-
- 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
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は立体規則性ポリスチレンを製造する方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing stereoregular polystyrene.
詳しくは、特定のチタン化合物を特定の有機アルミニウ
ム化合物と組合せた触媒を用いることによりスチレンを
重合し、シンジオタクチックポリスチレンを製造する方
法に関する。Specifically, the present invention relates to a method for producing syndiotactic polystyrene by polymerizing styrene using a catalyst in which a specific titanium compound is combined with a specific organoaluminum compound.
（従来の技術）
立体規則性ポリスチレンには立体構造上アイソタクチッ
クポリスチレンとシンジオタクチックポリスチレンの２
種が考えられる。このうちアイソタクチックポリスチレ
ンについては古＜１９５０年代から知られており、例え
ば三塩化チタン−トリエチルアルミニウムを用いる重合
方法により製造することができる。(Prior art) Stereoregular polystyrene has two steric structures: isotactic polystyrene and syndiotactic polystyrene.
Species can be considered. Among these, isotactic polystyrene has been known since the 1950s and can be produced, for example, by a polymerization method using titanium trichloride-triethylaluminum.
しかしながら、このアイソタクチックポリスチレンは融
点こそ２４０℃と高いものの、結晶化速度が極めて遅く
且つもろいものであった。However, although this isotactic polystyrene has a high melting point of 240° C., its crystallization rate is extremely slow and it is brittle.
一方、シンジオタクチックポリスチレンについては、融
点が高（且つ結晶化速度も速いことが期待される高分子
化合物であったにも拘らず永らくその存在が知られてい
なかったが、石屋らによって１９８６年に初めて合成に
成功したと報ぜられ、Ｍａｃｒｏａ＋ｏ １ｅｃｕ ｌ
ｅｓ ＋坦、 ２４６５ （１９８６）においてその
構造解析が発表され、さらに第３５回（１９８６年）高
分子学会年次大会において結晶化速度も速く工業的に価
値が高いことも報告されている。On the other hand, although syndiotactic polystyrene is a polymer compound with a high melting point (and is expected to have a fast crystallization rate), its existence was unknown for a long time, but Ishiya et al. It was reported that the first successful synthesis of Macroa+o 1ecu l
Its structural analysis was announced in ES + Tan, 2465 (1986), and it was also reported at the 35th (1986) Annual Conference of the Society of Polymer Science that it has a fast crystallization rate and is of high industrial value.
（発明が解決しようとする問題点）
このシンジオタクチックポリスチレンの合成法について
は、Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ＋坦、 ２４６５
（１９８６）において単にチタン化合物と有機アルミニ
ウム化合物とのみしか開示されておらず詳細は不明であ
る。(Problems to be Solved by the Invention) Regarding the method for synthesizing this syndiotactic polystyrene, see Macromolecules + Tan, 2465.
(1986) only discloses a titanium compound and an organoaluminum compound, and the details are unclear.
さらにまた、通常のチタン化合物、例えば三塩化チタン
などと通常の有機アルミニウム化合物、例えばトリアル
キルアルミニウムなどとを用いる方法ではシンジオタク
チックポリスチレンはほとんど得られず、結晶化速度が
遅く且つもろいアイソタクチックポリスチレンが主に得
られてしまうという問題点があった。 ″
（問題点を解決するための手段）
本発明者らは上記の問題点を解決すべく鋭意研究を重ね
た結果、シクロペンタジェニル基を有する特定のチタン
化合物ならびに特定のアルモキサンを触媒に用いること
により、高い立体規則性を持つシンジオタクチックポリ
スチレンを得ることを発見し、本発明に到達した。Furthermore, syndiotactic polystyrene is hardly obtained by a method using a normal titanium compound, such as titanium trichloride, and a normal organoaluminum compound, such as trialkylaluminum, and the crystallization rate is slow and the brittle isotactic polystyrene is not obtained. There was a problem that polystyrene was mainly obtained. ″ (Means for solving the problem) As a result of intensive research in order to solve the above problems, the present inventors have found that a specific titanium compound having a cyclopentadienyl group and a specific alumoxane are used as a catalyst. The inventors have discovered that syndiotactic polystyrene with high stereoregularity can be obtained by this method, and have arrived at the present invention.
すなわち本発明は、
（Ａ）一般式〇ｐ、ＴｉＸ、（式中、Ｃｐはシクロペン
タジェニル基、Ｘはハロゲン原子を表わす）で示される
チタン化合物と
（式中、Ｒはメチル基またはエチル基を表わし、１≦ｎ
≦４０である）で示されるアルモキサンで表わされるす
くなくとも１種とからなる触媒を用いることを特徴とす
る立体規則性ポリスチレンの製造方法に係わるものであ
る。That is, the present invention provides a titanium compound represented by (A) the general formula 〇p, TiX, (wherein Cp is a cyclopentadienyl group and X is a halogen atom) and (wherein, R is a methyl group or an ethyl represents a group, 1≦n
The present invention relates to a method for producing stereoregular polystyrene, characterized by using a catalyst comprising at least one type of alumoxane represented by the formula (≦40).
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
（Ａ）に用いられるチタン化合物としては・例えば、ビ
ス（シクロペンタジェニル）チタニウムジクロライド、
ビス（シクロペンタジェニル）チタニウムジクロライド
などが挙げられ、好ましくはビス（シクロペンタジェニ
ル）チタニウムジクロライドが用いられる。このチタン
成分はへキサン等により炭化水素懸濁液として用いる事
もできるが、好ましくはトルエン等により炭化水素溶液
として用いられる。As the titanium compound used in (A), for example, bis(cyclopentagenyl) titanium dichloride,
Examples include bis(cyclopentagenyl) titanium dichloride, and preferably bis(cyclopentagenyl) titanium dichloride is used. Although this titanium component can be used as a hydrocarbon suspension using hexane or the like, it is preferably used as a hydrocarbon solution using toluene or the like.
次に、（Ｂ）に用いられるアルモキサンについて説明す
る。本発明に用いられるアルモキサンは表される環状の
ものであってもよく、その併用でもよい、Ｒとしてはメ
チル基またはエチル基が挙げられるが特にメチル基が好
ましい、ｎは１ないし４０の範囲から選ばれるが、５以
上であることが好ましい、このアルモキサンを合成する
には公知の方法、例えばトリアルキルアルミニウムに当
量の水を徐々に加えて加水分解する方法、あるいは硫酸
銅水和物、硫酸アルミニウム水和物などの結晶水によっ
てトリアルキルアルミニウムをゆっくりと加水分解する
方法が挙げられ、好ましくは後者の方法が用いられる。Next, the alumoxane used in (B) will be explained. The alumoxane used in the present invention may be a cyclic one as shown, or a combination thereof may be used. R may be a methyl group or an ethyl group, but a methyl group is particularly preferred. n is in the range of 1 to 40. The alumoxane, which is selected but preferably 5 or more, can be synthesized by known methods, such as a method in which an equivalent amount of water is gradually added to trialkylaluminum and hydrolyzed, or copper sulfate hydrate, aluminum sulfate Examples include a method of slowly hydrolyzing trialkylaluminium with water of crystallization such as hydrate, and preferably the latter method is used.
次に重合に関して説明する。Next, polymerization will be explained.
本発明の触媒を用いる重合方法としては特に制限はなく
、スラリー重合、溶液重合など通常用いられる重合形式
より選べばよい。具体的には例えば触媒を不活性炭化水
素溶媒、例えばヘキサン、ヘプタンのごとき脂肪族炭化
水素、シクロヘキサン、メチルシクロヘキサンのごとき
脂環式炭化水素、ベンゼン、トルエンのごとき芳香族炭
化水素とともに反応器に導入し、不活性ガス雰囲気下に
スチレンを加え、室温ないし９０℃の温度条件で重合を
行うことができる。The polymerization method using the catalyst of the present invention is not particularly limited, and may be selected from commonly used polymerization methods such as slurry polymerization and solution polymerization. Specifically, for example, a catalyst is introduced into a reactor together with an inert hydrocarbon solvent, such as an aliphatic hydrocarbon such as hexane or heptane, an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane, or an aromatic hydrocarbon such as benzene or toluene. Then, styrene is added under an inert gas atmosphere, and polymerization can be carried out at a temperature of room temperature to 90°C.
（発明の効果）
本発明により高度に立体規則性をもつシンジオタクチッ
クポリスチレンを合成することが可能となった。(Effects of the Invention) The present invention has made it possible to synthesize highly stereoregular syndiotactic polystyrene.
さらにまた、本発明に用いられるビス（シクロペンタジ
ェニル）チタニウムシバライド、およびアルモキサン合
成に用いられるトリアルキルアルモニウム、硫酸銅水和
物などの原料は入手が容易であり工業的利用という見地
からも価値が高い。Furthermore, the raw materials such as bis(cyclopentagenyl) titanium cybaride used in the present invention, trialkylamonium used in alumoxane synthesis, and copper sulfate hydrate are easily available, and from the viewpoint of industrial use. is also of high value.
（実施例）
以下、本発明の実施例を示すが、本発明はこれらの実施
例によって何ら制限されるものではない。(Examples) Examples of the present invention will be shown below, but the present invention is not limited to these Examples in any way.
なお、実施例中、メチルエチルケトン不溶部（χ）とは で定義した。In addition, in the examples, what is the methyl ethyl ketone insoluble portion (χ)? Defined by .
（実施例１）
（１）アルモキサンの合成
アルモキサンの合成は特開昭５８−１９３０９号公報実
施例１に準じて、窒素気流下で次の通り実施した。(Example 1) (1) Synthesis of alumoxane Alumoxane was synthesized as follows under a nitrogen stream according to Example 1 of JP-A-58-19309.
３７、５ ｇ （０，１５ｍｏｌ）のＣｕ５Ｏ，，５Ｈ
ｚＯ（０，７５ｍｏｌのＨ２Ｏに相当する）を２５０ｍ
１のトルエンに懸濁させ、５０ｍ１（０，５２＋＊ｏｌ
）のトリメチルアルミニウムを加え、２０℃で２４時間
反応させた。37.5 g (0.15 mol) of Cu5O,,5H
zO (corresponding to 0.75 mol H2O) at 250 m
1 of toluene, 50ml (0,52+*ol
) was added, and the mixture was reacted at 20° C. for 24 hours.
反応の間にメタンガスの発生が認められた。反応後に硫
酸銅をろ別し、ろ液からトルエンを除くと、１３．０ｇ
（理想値の４４％）のメチルアルモキサンが得られた。Evolution of methane gas was observed during the reaction. After the reaction, copper sulfate was filtered and toluene was removed from the filtrate, resulting in 13.0g
(44% of the ideal value) of methylalumoxane was obtained.
ベンゼンで凝固点降下法によって測定した分子量は６４
０、平均オリゴマー化度は１１であった。Molecular weight determined by freezing point depression method in benzene is 64
0, and the average degree of oligomerization was 11.
（２）スチレンの重合
不活性ガスで置換した内容積１００ｍ１のガラス製耐圧
ビンに、トルエン４０層１と上記（１）で得られたメチ
ルアルモキサンｌＱｍｍｏｌおよびビス（シクロペンタ
ジェニル）チタニウムジクロライドＯ，ＯＯ５ｍｍｏｌ
を加えた。次にスチレン１０ｍ１を加え５０℃で６時間
重合反応を行った。反応終了後、反応物を塩酸−メタノ
ールに投入することで反応を停止し、生成ポリマーをろ
別、乾燥した。(2) Polymerization of styrene In a glass pressure-resistant bottle with an internal volume of 100 m1 and purged with an inert gas, 40 layers of toluene, 1 Q mmol of methylalumoxane obtained in (1) above, and bis(cyclopentadienyl)titanium dichloride O ,OO5mmol
added. Next, 10 ml of styrene was added and a polymerization reaction was carried out at 50° C. for 6 hours. After the reaction was completed, the reaction product was poured into hydrochloric acid-methanol to stop the reaction, and the resulting polymer was filtered and dried.
この結果得られたポリスチレンは０．７３ｇであった。The resulting polystyrene weighed 0.73 g.
このポリスチレンのメチルエチルケトン不溶部（％）は
９０％であって、この不溶部の立体規則性は”Ｃ−ＮＭ
Ｒスペクトル解析の結果、第１図に示す通り９９％以上
シンジオタクチック構造であった。The methyl ethyl ketone insoluble area (%) of this polystyrene is 90%, and the stereoregularity of this insoluble area is "C-NM
As a result of R spectrum analysis, as shown in FIG. 1, 99% or more had a syndiotactic structure.
（比較例Ｉン
実施例１ （２）において有機アルミニウム化合物とし
てメチルアルモキサンの代りにトリメチルアルミニウム
１０ｍｍｏｌを用いた以外は実施例１（２）と同様にし
て重合反応を行ったが、ポリマーは得られなかった。(Comparative Example I) A polymerization reaction was carried out in the same manner as in Example 1 (2) except that 10 mmol of trimethylaluminum was used instead of methylalumoxane as the organoaluminum compound in Example 1 (2). I couldn't.
（比較例２）
実施例１ （２）において有機アルミニウム化合物とし
てメチルアルモキサンの代りにトリメチルアルミニウム
２．５ ｍｍｏＬチタン化合物としてビス（シクロペン
タジェニル）チタニウムジクロライドの代りに三塩化チ
タン２５０ｍｇを用いた以外は実施例１ （２）と同様
にして重合反応を行った。(Comparative Example 2) In Example 1 (2), 2.5 mmol of trimethylaluminum was used instead of methylalumoxane as the organoaluminum compound, and 250 mg of titanium trichloride was used instead of bis(cyclopentagenyl)titanium dichloride as the titanium compound. The polymerization reaction was carried out in the same manner as in Example 1 (2) except for this.
この結果得られたポリスチレンは４．５ｇであった。The resulting polystyrene weighed 4.5 g.
このポリスチレンのメチルエチルケトン不溶部（％）は
８３％であったが、この不溶部の立体規則性は”Ｃ−Ｎ
ＭＲスペクトル解析の結果、第２図に示す通りほぼアイ
ソタクチック構造であった。The methyl ethyl ketone insoluble area (%) of this polystyrene was 83%, but the stereoregularity of this insoluble area was "C-N
As a result of MR spectrum analysis, as shown in FIG. 2, it was found to have an almost isotactic structure.
（実施例２）
実施例１ （２）においてメチルアルモキサンの量を２
０＋ｍｏｌとした以外は、実施例１ （２）と同様にし
て重合反応を行った。この結果得られたポリスチレンは
０．７０ｇであった。(Example 2) In Example 1 (2), the amount of methylalumoxane was 2
A polymerization reaction was carried out in the same manner as in Example 1 (2) except that the amount was 0+mol. The resulting polystyrene weighed 0.70 g.
このポリスチレンのメチルエチルケトン不溶部（％）は
９０％であって、この不溶部の立体規則性は１３Ｃ−Ｎ
ＭＲスペクトル解析の結果、実施例１ （２）と同様で
あった。The methyl ethyl ketone insoluble area (%) of this polystyrene is 90%, and the stereoregularity of this insoluble area is 13C-N
The results of MR spectrum analysis were the same as in Example 1 (2).
第１図は実施例１において、また第２図は比較例２にお
いて得られたポリスチレンのメチルエチルケトン不溶部
ポリマーの１３Ｃ−ＮＭＲスペクトルにおけるベンゼン
環の０１炭素のスペクトルである。なお、Ｍａｋｒｏｍ
ｏｌ 、 Ｃｈｅｗ、 、 １Ｉｆｌ、 ３０５１ （
１９７５）に依れば、第１図のピークはシンジオタクチ
ック構造に、第２図のピークはアイソタクチック構造に
帰属される。
第３図は本発明の態様を示す概略フローシートである。
特許出願人 旭化成工業株式会社
第１図
第２図FIG. 1 shows the spectrum of the 01 carbon of the benzene ring in the 13C-NMR spectrum of the methyl ethyl ketone insoluble polymer of polystyrene obtained in Example 1 and FIG. 2 in Comparative Example 2. In addition, Makrom
ol, Chew, , 1Ifl, 3051 (
(1975), the peaks in FIG. 1 are assigned to a syndiotactic structure, and the peaks in FIG. 2 are assigned to an isotactic structure. FIG. 3 is a schematic flow sheet illustrating aspects of the present invention. Patent applicant: Asahi Kasei Industries, Ltd. Figure 1 Figure 2
Claims (1)
クロペンタジエニル基、Ｘはハロゲン原子を表わす）で
示されるチタン化合物と （Ｂ）一般式▲数式、化学式、表等があります▼および （式中、Ｒはメチル基またはエチル基を表わし、１≦ｎ
≦４０である）で示されるアルモキサンの少なくとも１
種とからなる触媒を用いることを特徴とする立体規則性
ポリスチレンの製造方法。 ２）Ｘが塩素原子である特許請求範囲第１項記載の製造
方法。 ３）Ｒがメチル基である特許請求範囲第１項もしくは第
２項記載の製造方法。[Claims] 1) (A) a titanium compound represented by the general formula Cp_2TiX_2 (in the formula, Cp represents a cyclopentadienyl group and X represents a halogen atom) and (B) a general formula ▲ mathematical formula, chemical formula, table etc. ▼ and (wherein R represents a methyl group or an ethyl group, and 1≦n
≦40)
A method for producing stereoregular polystyrene, the method comprising using a catalyst comprising seeds. 2) The manufacturing method according to claim 1, wherein X is a chlorine atom. 3) The manufacturing method according to claim 1 or 2, wherein R is a methyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10178387A JPS63268709A (en) | 1987-04-27 | 1987-04-27 | Production of stereoregular polystyrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10178387A JPS63268709A (en) | 1987-04-27 | 1987-04-27 | Production of stereoregular polystyrene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63268709A true JPS63268709A (en) | 1988-11-07 |
Family
ID=14309786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10178387A Pending JPS63268709A (en) | 1987-04-27 | 1987-04-27 | Production of stereoregular polystyrene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63268709A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7005465B2 (en) | 2002-08-07 | 2006-02-28 | General Electric | Resin composition for wire and cable coverings |
-
1987
- 1987-04-27 JP JP10178387A patent/JPS63268709A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7005465B2 (en) | 2002-08-07 | 2006-02-28 | General Electric | Resin composition for wire and cable coverings |
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