JPH03200812A - Syndiotactic poly-3-methylbutene-1 - Google Patents
Syndiotactic poly-3-methylbutene-1Info
- Publication number
- JPH03200812A JPH03200812A JP33822089A JP33822089A JPH03200812A JP H03200812 A JPH03200812 A JP H03200812A JP 33822089 A JP33822089 A JP 33822089A JP 33822089 A JP33822089 A JP 33822089A JP H03200812 A JPH03200812 A JP H03200812A
- Authority
- JP
- Japan
- Prior art keywords
- methylbutene
- measured
- syndiotactic poly
- poly
- peaks
- 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.)
- Granted
Links
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 title claims abstract description 21
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 3
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims abstract 6
- 229920000642 polymer Polymers 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 6
- 230000000379 polymerizing effect Effects 0.000 abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 abstract description 5
- 150000003624 transition metals Chemical class 0.000 abstract description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 abstract description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 abstract description 3
- PDBMBIIQRMIHJS-UHFFFAOYSA-L [Cl-].[Cl-].C(C)(C)[Zr+2]C1=C(C=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 Chemical compound [Cl-].[Cl-].C(C)(C)[Zr+2]C1=C(C=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 PDBMBIIQRMIHJS-UHFFFAOYSA-L 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 abstract 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 6
- -1 polypropylene Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- JZLGCOIWVSVSHR-UHFFFAOYSA-N C(C)(C)[Zr]C1=C(C=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 Chemical compound C(C)(C)[Zr]C1=C(C=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 JZLGCOIWVSVSHR-UHFFFAOYSA-N 0.000 description 1
- KUNZSLJMPCDOGI-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2] Chemical compound [Cl-].[Cl-].[Hf+2] KUNZSLJMPCDOGI-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はシンジオタクチックポリ３−メチルブテン−１
に関する。詳しくは、高シンジオタクテイシテイ−を有
する３−メチルブテン−１の重合体に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to syndiotactic poly3-methylbutene-1
Regarding. Specifically, the present invention relates to a polymer of 3-methylbutene-1 having high syndiotacticity.
アイソタクチックポリ３−メチルブテン−１及びアタク
チックポリ３−メチルブテン−１については、高融点の
ポリマーとして知られているがシンジオタクチックポリ
３−メチルブテン−１については知られていなかった。Isotactic poly-3-methylbutene-1 and atactic poly-3-methylbutene-1 are known as polymers with high melting points, but syndiotactic poly-3-methylbutene-1 has not been known.
Ｊ、＾、Ｅ１１ＥＮらによって（Ｊ、４ｍ、Ｃｈｅｍ、
Ｓｏｃ、 、 １９８１Ｌ １１０、６２５５−６２５
６）は遷移金属当たりの活性が良好であり、しかも得ら
れるポリマーのシンジオタクテイシテイ−が高いポリプ
ロピレンを製造する方法が開示されたが、シンジオタク
チックなポリ３−メチルブテン−１についてはその存在
が従来知られておらずその台底は極めて興味深いもので
ある。by J,^,E11EN et al. (J,4m,Chem,
Soc, 1981L 110, 6255-625
6) disclosed a method for producing polypropylene with good activity per transition metal and high syndiotacticity of the obtained polymer, but the existence of syndiotactic poly-3-methylbutene-1 was has not been previously known, and its origin is extremely interesting.
本発明者らは上記問題を解決してシンジオタクチックな
ポリ３−メチルブテン−１ついて鋭意探索し特定の重合
法によってタフティシティ−の高いシンジオタクチック
ポリ３−メチルブテン−１が得られることを見出し本発
明を完成した。The present inventors have solved the above problem and have conducted extensive searches for syndiotactic poly-3-methylbutene-1, and have discovered that syndiotactic poly-3-methylbutene-1 with high toughness can be obtained by a specific polymerization method. Heading The invention has been completed.
即ち、本発明は１．２．４− トリクロロベンゼン溶液
で測定した’ ”Ｃ−ＮＭＲで−、テトラメチルシラン
を基準として約１８．９．２９．６．３３．１．３９．
２ｐｐ園の実質的に４本のピークがそれぞれ約２：ｆ：
１：１のピーク強度比で観測されゲルパーミェーション
クロマトグラフィーで測定した分子量が１０００以上で
ある実質的にシンジオタクチックなポリ３−メチルブテ
ン−１である。That is, the present invention provides a 1.2.4-C-NMR measured with a trichlorobenzene solution, about 18.9.29.6.33.1.39. based on tetramethylsilane.
Substantially four peaks of 2pp garden each have approximately 2:f:
It is a substantially syndiotactic poly-3-methylbutene-1 which is observed with a peak intensity ratio of 1:1 and has a molecular weight of 1000 or more as measured by gel permeation chromatography.
本発明のシンジオタクチックポリ３−メチルブテン−１
について以下に製造方法の一例を示して説明する。Syndiotactic poly3-methylbutene-1 of the present invention
An example of a manufacturing method will be shown and explained below.
製造するに用いる触媒としては例えば、上記文献に記載
された化合物が例示できる。具体的にはイソプロピル（
シクロペンタジェニル−１−フルオレニル）ハフニウム
ジクロリド、あるいはイソプロピル（シクロペンタジェ
ニル−］−フルオレニル）ジルコニウムジクロリドなど
が遷移金属触媒として例示され、またアルミノキサンと
しては、ＲＲ
（式中Ｒは炭素数ｌ〜３の炭化水素残基。）で表される
化合物、特にＲがメチル基であるメチルアルミノキサン
でｎが５以上好ましくは１０以上のものが利用される。Examples of catalysts used in the production include the compounds described in the above-mentioned documents. Specifically, isopropyl (
Examples of transition metal catalysts include cyclopentadienyl-1-fluorenyl) hafnium dichloride and isopropyl(cyclopentagenyl-]-fluorenyl)zirconium dichloride, and examples of aluminoxane include RR (where R is the number of carbon atoms Hydrocarbon residues of 3), particularly methylaluminoxane in which R is a methyl group and n is 5 or more, preferably 10 or more, are used.
上記遷移金属触媒に対するアルミノキサンの使用割合と
しては１０〜１００００００モル倍、通常５０〜５００
０モル倍である。これらの触媒系の他に、上記遷移金属
触媒をアルキル化したものと硼素の化合物（例えば特開
平１−５０１９５０．１−５０２０３６など）を組み合
わせた触媒系などが利用できる。また３−メチルブテン
−１を重合してポリ３−メチルブテン−１を製造する重
合条件については特に制限はなく不活性媒体を用いる溶
媒重合法、或いは実質的に不活性媒体の存在しない３−
メチルブテン−１を重合媒体とする塊状重合法、気相重
合Ｎ法も利用できる０重合部度としては一１００〜２０
０°Ｃ１重合圧力としては常圧〜１０ｋｇ／ｃｉｉ−Ｇ
で行うのが一般的である。好ましくは一１００〜１００
°Ｃ１常圧〜５ ｋｇ／ ｃｄである。The ratio of aluminoxane to the above transition metal catalyst is 10 to 1,000,000 times by mole, usually 50 to 500 times
It is 0 mole times. In addition to these catalyst systems, a catalyst system in which an alkylated transition metal catalyst is combined with a boron compound (for example, JP-A-1-501950.1-502036) can be used. There are no particular restrictions on the polymerization conditions for polymerizing 3-methylbutene-1 to produce poly-3-methylbutene-1, and a solvent polymerization method using an inert medium, or a 3-methylbutene-1 method in which an inert medium is not substantially present is used.
The bulk polymerization method using methylbutene-1 as the polymerization medium and the gas phase polymerization N method can also be used.The polymerization degree is 1100 to 20.
0°C1 polymerization pressure is normal pressure ~ 10kg/cii-G
It is common to do so. Preferably -100 to 100
°C1 normal pressure to 5 kg/cd.
上記条件で重合することにより比較的シンジオタクテイ
シテイ−の高いポリ３−メチルブテン−１を製造するこ
とができる。さらに必要に応し精製してアタクチックな
成分を除去することもできるが、上記条件で重合するこ
とで簡単にシンジオタクチックティシティ−の高いポリ
３−メチルブテン−１が得られる０分子量は通常１００
０以上であるのがポリマーとしての特性を出す上で好ま
しく、測定は例エバ、ゲルパーξエージタンクロマトグ
ラフで１３５°Ｃの１．２．４−１−リクロロトルエン
溶液で測定したポリプロピレン換算の数平均分子量とし
て算出される。ポリマーとしての物性という点では１０
０００以上の分子量であることである。By polymerizing under the above conditions, poly-3-methylbutene-1 having relatively high syndiotacticity can be produced. Further, if necessary, it is possible to perform purification to remove atactic components, but poly-3-methylbutene-1 with high syndiotacticity can be easily obtained by polymerizing under the above conditions.The molecular weight is usually 100.
It is preferable that the number is 0 or more in order to exhibit the properties as a polymer, and the measurement is performed using an EVA, Gelper ξ age tank chromatograph in a 1.2.4-1-lichlorotoluene solution at 135°C in terms of polypropylene. Calculated as average molecular weight. 10 in terms of physical properties as a polymer
The molecular weight is 000 or more.
以下に実施例を示しさらに本発明を説明する。The present invention will be further explained with reference to Examples below.
実施例１
内容積３００ ｄのオートクレーブに常法に従って合成
したイソプロピルシクロペンタジェニル−１−フルオレ
ンをリチウム化し、四塩化ジルコニウムと反応すること
で得たイソプロピル（シクロペンタジェニル−１−フル
オレニル）ジルコニウムジクロリド３ｍｇと東洋アクゾ
■製の重合度約１６のメチルアルミノキサン０．３４ｇ
を３−メチルブテン−１２０ｇに加えて５°Ｃで２時間
重合した後、多量のメタノール中に投入してメタノール
不溶分としてポリメチルブテン−１を１．８ｇ得た。ウ
ォターズ■製ＧＰＣＩ５０Ｇゲルパーξニージョンクロ
マトグラフィーで１３５°Ｃで測定し、ポリプロピレン
換算で算出した数平均分子量４８００、重量平均分子量
は１０５００であった。また１３５℃テトラリン溶液で
測定した極限粘度は０．２１であった。 １３Ｃ−ＮＭ
Ｒで１２５℃の１．２゜４ トリクロロベンゼン溶液で
、テトラメチルシランをＯｌｌｌＰＭとした時の吸収ピ
ークとして大きくは、約１８．９．２９．６．３３．１
．３９．２ｐＰ−に４本観測されピーク強度比は約２：
１：ｌ：１であった。Example 1 Isopropyl (cyclopentadienyl-1-fluorenyl) zirconium obtained by lithiation of isopropylcyclopentadienyl-1-fluorene synthesized according to a conventional method in an autoclave with an internal volume of 300 d and reacting with zirconium tetrachloride. 3 mg of dichloride and 0.34 g of methylaluminoxane with a polymerization degree of about 16 manufactured by Toyo Akzo ■
was added to 120 g of 3-methylbutene and polymerized at 5°C for 2 hours, and then poured into a large amount of methanol to obtain 1.8 g of polymethylbutene-1 as a methanol-insoluble matter. It was measured at 135°C using GPCI50G Gelper ξ knee chromatography manufactured by Waters ■, and the number average molecular weight calculated in terms of polypropylene was 4,800 and the weight average molecular weight was 10,500. Further, the intrinsic viscosity measured with a tetralin solution at 135° C. was 0.21. 13C-NM
When tetramethylsilane is OlllPM in a 1.2°4 trichlorobenzene solution at 125°C at R, the absorption peak is approximately 18.9.29.6.33.1
．． Four peaks were observed at 39.2 pP-, and the peak intensity ratio was approximately 2:
The ratio was 1:1:1.
比較例１
アイソタクチックポリ３−メチルブテン−１は同様の方
法で触媒として１．２−エチレンビスインデニルジルコ
ニウムジクロリドを用い・て重合して得ることができ０
．９ｇを得た、同様に”Ｃ−ＮＭＲを測定する（溶解せ
ずゲル状態で測定した。）と約１８．９．２９．９．３
３．２．３９，２に４本のピークが観測できた。このポ
リマーはテトラリンに溶解しなかったため分子量は測定
できなかった。Comparative Example 1 Isotactic poly-3-methylbutene-1 can be obtained by polymerizing in a similar manner using 1,2-ethylenebisindenylzirconium dichloride as a catalyst.
．． 9g was obtained. Similarly, C-NMR was measured (measured in gel state, not dissolved), and the result was approximately 18.9.29.9.3
Four peaks were observed at 3.2.39.2. The molecular weight of this polymer could not be measured because it did not dissolve in tetralin.
本発明の重合体は、単独であるいは他の重合体と混合し
て種々の用途に利用可能であり、工業的に価値がある。The polymer of the present invention can be used for various purposes alone or in combination with other polymers, and is industrially valuable.
第１図は実施例１で得たシンジオタクチックポリ３−メ
チルブテン−１の’ ３Ｃ−ＮＭＲスペクトルである。FIG. 1 is a 3C-NMR spectrum of syndiotactic poly3-methylbutene-1 obtained in Example 1.
Claims (1)
３Ｃ−ＮＭＲで、テトラメチルシランを基準として約１
８．９、２９．６、３３．１、３９．２ｐｐｍに４本観
測されそのピーク強度比は約２：１：１：１であり、ゲ
ルパーミェーションクロマトグラフィーで測定した分子
量が１０００以上である実質的にシンジオタクチックな
ポリ３−メチルブテン−１。Measured with 1,2,4-trichlorobenzene solution ^1^
3C-NMR, about 1 based on tetramethylsilane
Four peaks were observed at 8.9, 29.6, 33.1, and 39.2 ppm, and the peak intensity ratio was approximately 2:1:1:1, and the molecular weight measured by gel permeation chromatography was 1000 or more. A substantially syndiotactic poly-3-methylbutene-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33822089A JP2919522B2 (en) | 1989-12-28 | 1989-12-28 | Syndiotactic poly-3-methylbutene-1 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33822089A JP2919522B2 (en) | 1989-12-28 | 1989-12-28 | Syndiotactic poly-3-methylbutene-1 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03200812A true JPH03200812A (en) | 1991-09-02 |
| JP2919522B2 JP2919522B2 (en) | 1999-07-12 |
Family
ID=18316059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33822089A Expired - Fee Related JP2919522B2 (en) | 1989-12-28 | 1989-12-28 | Syndiotactic poly-3-methylbutene-1 |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2919522B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5446117A (en) * | 1993-08-19 | 1995-08-29 | Queen's University At Kingston | Process for producing amorphous syndiotactic polystyrene |
-
1989
- 1989-12-28 JP JP33822089A patent/JP2919522B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5446117A (en) * | 1993-08-19 | 1995-08-29 | Queen's University At Kingston | Process for producing amorphous syndiotactic polystyrene |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2919522B2 (en) | 1999-07-12 |
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