JPH03139506A - Polycyclopentene and its production - Google Patents
Polycyclopentene and its productionInfo
- Publication number
- JPH03139506A JPH03139506A JP27577889A JP27577889A JPH03139506A JP H03139506 A JPH03139506 A JP H03139506A JP 27577889 A JP27577889 A JP 27577889A JP 27577889 A JP27577889 A JP 27577889A JP H03139506 A JPH03139506 A JP H03139506A
- Authority
- JP
- Japan
- Prior art keywords
- polycyclopentene
- cyclopentene
- aluminoxane
- transition metal
- highly stereoregular
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 7
- 239000003446 ligand Substances 0.000 claims abstract description 5
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims abstract 6
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract description 2
- 229910052735 hafnium Inorganic materials 0.000 abstract 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- -1 cyclopentadienyl-1-fluorenyl Chemical group 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- BVZSSAHHPUDVFT-UHFFFAOYSA-N C(C)(C)[Zr](C1=CC=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 Chemical compound C(C)(C)[Zr](C1=CC=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 BVZSSAHHPUDVFT-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- PGOXJIBERNIRFR-UHFFFAOYSA-L [Cl-].[Cl-].C(C)(C)[Hf+2]C1=C(C=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 Chemical group [Cl-].[Cl-].C(C)(C)[Hf+2]C1=C(C=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 PGOXJIBERNIRFR-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005406 washing Methods 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
Landscapes
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はポリシクロペンテンおよびその製造方法に関す
る。詳しくは、高度に立体規則性のポリシクロペンテン
およびその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to polycyclopentene and a method for producing the same. Specifically, the present invention relates to highly stereoregular polycyclopentene and a method for producing the same.
［従来技術〕
可溶性の遷移金属触媒とアルミノキサンからなる触媒を
用いてシクロペンテンを重合することで結晶性のポリシ
クロペンテンが得られることは賀。[Prior Art] It is known that crystalline polycyclopentene can be obtained by polymerizing cyclopentene using a catalyst consisting of a soluble transition metal catalyst and aluminoxane.
Ｋａｓｉｎｓｋｙらによって発見された（ Ｔｒａｎｓ
ｉｔｉｏｎＭｅｔａｌ ａｎｄ ＯｒｇａｎｏｍｅＬａ
ｌｌ＋ｃｓ ａｓ ＣａＬａ１ｙｓＬ ｆｏｒＯｒｅｆ
ｌｎ Ｐｏ１ｙ＊ｅｒｉｚａＬｉｏｎ ２９１ 〜
３０１（１９８Ｂ）Ｉ！ｄｓ、 Ｈ。Discovered by Kasinsky et al. (Trans
itionMetal and OrganomeLa
ll+cs as CaLa1ysL forOref
lnPoly*erizaLion 291 ~
301 (198B) I! ds, H.
Ｋａｓｉｎｓｋｙ）＊上記報告によれば、対称な互いに
結合した配位子を有する触媒でシクロペンテンを重合す
るとトランス体とシス体の混合した構造のポリシクロペ
ンテンが得られるとされている。Kasinsky)*According to the above report, it is said that when cyclopentene is polymerized with a catalyst having symmetrical and mutually bonded ligands, polycyclopentene having a mixed structure of trans and cis isomers is obtained.
ポリシクロペンテンの結合がトランス体とシス体の混合
ではなく一方の構造のみであればさらに物性が優れてい
ることが期待される。If polycyclopentene has only one structure, rather than a mixture of trans and cis forms, it is expected that the physical properties will be even better.
本発明者らは上記問題を解決して高度に立体規則性のポ
リシクロペンテンついて鋭意探索し特定の重合法によっ
て規則性の高い結合をしたポリシクロペンテンが得られ
ることを見出し本発明を完成した。The present inventors have solved the above-mentioned problems and have searched intensively for highly stereoregular polycyclopentene, and have found that polycyclopentene with highly regular bonds can be obtained by a specific polymerization method, and have completed the present invention.
即ち、本発明は１，２．４− ）リクロ口ベンゼン溶液
で測定した”Ｃ−ＮＭＲで、テトラメチルシランを基準
として実質的に約３０．８．３８．５．４６．７ＰＰ蒙
の３本のピークのみが観測される高度に立体規則性のポ
リシクロペンテンである０本発明はまたその好ましい製
造方法に関し、非対称な配位子を含有する遷移金属化合
物とアルミノキサンからなる触媒を用いてシクロペンテ
ンを重合することを特徴とする高度に立体規則性のポリ
シクロペンテンの製造方法である。That is, the present invention provides 1,2.4-) C-NMR measured with a dichlorobenzene solution, which is substantially 30.8.38.5.46.7 PP based on tetramethylsilane. The present invention also relates to a preferred method for the preparation of cyclopentene, which is a highly stereoregular polycyclopentene in which only a peak of 0 is observed. This is a method for producing highly stereoregular polycyclopentene.
本発明の高度に立体規則性のポリシクロペンテンについ
て、以下に製造方法の一例を示して説明する。The highly stereoregular polycyclopentene of the present invention will be explained below by showing an example of a manufacturing method.
製造するに用いる触媒としては例えば、Ｊ、Ａ、ＩｒＩ
ｆＵＮらによって報告されてし）る（Ｊ、＾−，Ｃｈｅ
曽、Ｓｏｃ、 ＋ １９８８、１１０．６２５５−６２
５６）触媒が例示される。Examples of catalysts used in the production include J, A, IrI
fUN et al. (J, ^-, Che
Tseng, Soc, + 1988, 110.6255-62
56) Examples include catalysts.
非対称な配位子を有する遷移金属化合物としては例えば
、上記文献に記載された化合物が例示できる。Ｒ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−１−フルオレニル）ジルコニウ
ムジクロリドなどが例示され、またアルミノキサンとし
ては、ＲＲ
（式中Ｒは炭素数１〜３の炭化水素残括、）で表される
化合物、特にＵがメチル基であるメチルアルミノキサン
でｎが５以」二好ましくはＩＯ以−Ｌのものが利用され
る。上記遷移金属触媒に対するアルミノキサンの使用割
合どしてはｌＯ〜１０００（１００モル倍、通常５０〜
５０００モル倍である。またシフ［１ペンテンを重合し
てポリシクロペンテンを製造する重合条件については特
に制限はな（、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シクロペンテンを重合
媒体とする塊状重合法、気相重合法も利用できる。ｆｒ
ｒ合温度としては一１ＯＯ〜２００℃、重合圧力として
は常圧〜１０ｋｇ／ｃ艷−Ｇで行うのが一般的である。Examples of transition metal compounds having asymmetric ligands include the compounds described in the above-mentioned documents. The R-isomer is isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride, or isopropyl (
Examples include cyclopentadienyl-1-fluorenyl) zirconium dichloride, and examples of aluminoxane include compounds represented by RR (wherein R is a hydrocarbon residue having 1 to 3 carbon atoms), especially where U is a methyl group. A methylaluminoxane in which n is 5 or more, preferably IO or more is used. The ratio of aluminoxane to the above transition metal catalyst is 10 to 1000 (100 mol times, usually 50 to
It is 5,000 times more mole. There are no particular restrictions on the polymerization conditions for producing polycyclopentene by polymerizing Schiff [1 pentene (e.g., a solvent polymerization method using an inert medium, or a bulk polymerization method using cyclopentene as a polymerization medium substantially free of an inert medium). Polymerization method and gas phase polymerization method can also be used.fr
Generally, the polymerization temperature is -100°C to 200°C, and the polymerization pressure is normal pressure to 10kg/kg/g.
好ましくは、−１００〜１００℃、常圧〜５ｋｇ／ｃ１
ｇである。Preferably -100 to 100°C, normal pressure to 5 kg/c1
It is g.
上記条件で重合することにより比較的高い立体規則性の
ポリシクロペンテンを製造することができる。さらに必
要に応じ精製して規則性の不良な部分を炭化水素溶削で
洗浄して除去することもできるが、上記条件で重合する
ことで簡単に高度に立体規則性のポリシクロペンテンが
得られる。高度に立体規則性とは、例えば約４６．４ｐ
、−に観測されるピークの強度が、４５〜４７ｐｐ購に
観測されるピーク強度の総和の０．７以上、より好まし
くは０．８以上であることである。By polymerizing under the above conditions, polycyclopentene with relatively high stereoregularity can be produced. If necessary, it can be further purified and parts with poor regularity can be removed by washing with hydrocarbon cutting, but highly stereoregular polycyclopentene can be easily obtained by polymerizing under the above conditions. Highly stereoregular, e.g. about 46.4p
, - is 0.7 or more, more preferably 0.8 or more of the sum of the peak intensities observed at 45 to 47 pp.
分子量は通常５００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、測定は例えば、ゲルパーミニ−
シランクロマトグラフで１３５℃の１゜２．４− ）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。より好ましくは１０００
０以上の分子量であることである。It is preferable that the molecular weight is usually 500 or more in order to obtain properties as a polymer.
It is calculated as the number average molecular weight in terms of polypropylene measured using a silane chromatograph in a 1°2.4-)lichlorotoluene solution at 135°C. More preferably 1000
The molecular weight is 0 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 by showing examples below.
実施例１
内容積３００ ｄのフラスコ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１０ｍｇと東洋アクゾ■製
の重合間約１６のメチルアルミノキサン０．６８ｇをシ
クロペンテン２０ｇに加えて３０℃で６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
てポリシクロペンテンを１．５ｇ得た。ウォターズ■製
ＧＩ’Ｃ１５０Ｃゲルパーミェーションクロマトグラフ
ィーで１３５℃で測定し、ポリプロピレン換算で算出し
た数平均分子１４８００ 、重量平均分子量は６８００
であった。Example 1 Isopropylcyclopentadienyl-1-fluorenyl-zirconium obtained by lithiation of isopropylcyclopentadienyl-1,fluorene synthesized according to a conventional method in a flask with an internal volume of 300 d and reacting with zirconium tetrachloride. 10 mg of dichloride and 0.68 g of methylaluminoxane with a polymerization period of about 16 (manufactured by Toyo Akzo ■) were added to 20 g of cyclopentene, polymerized at 30°C for 6 hours, and then poured into a large amount of methanol to dissolve the polycyclopentene as methanol-insoluble. I got 5g. Measured using GI'C150C gel permeation chromatography manufactured by Waters ■ at 135°C, and calculated in terms of polypropylene, with a number average molecular weight of 14,800 and a weight average molecular weight of 6,800.
Met.
また１３５℃テトラリン溶液で測定した極限粘度は０．
１８であった。ＩＣ−ＮＭＲで１２５°Ｃの１．２．４
）リクロロベンゼン溶液で、テトラメチルシランを
Ｏｐｐｍとした時の吸収ピークとして大きくは、約３０
．８．３８．５．４６．７ｐｐｍに３本観測され、他に
２５．８．３１．８．３２．３．３２．４ｐｐ’−に小
さいピークが観測された。Moreover, the intrinsic viscosity measured with a tetralin solution at 135°C is 0.
It was 18. 1.2.4 at 125°C by IC-NMR
) In a dichlorobenzene solution, the absorption peak when tetramethylsilane is set to Oppm is approximately 30
．． Three peaks were observed at 8.38.5.46.7ppm, and another small peak was observed at 25.8.31.8.32.3.32.4pp'-.
なお公知の方法によってポリシクロペンテンを製造した
（ＴｒａｎｓｉＬｉｏｎ ＭｅＬａｌ ａｎｄ Ｏｒｇ
ａｎｏｓｅＬａｌｌｉｃｓａｓ ＣａｔａｌｙｓＬ
ｒｏｔ ０ｒｅｒｉｎ Ｉ’ｏｌｙｍｅｒｉｚａ
ｔｉｏｎ ２９１ 〜３０１（１９８Ｂ） Ｆ！ｄｓ
、 Ｉｆ、 Ｋａｓｉｎｓｋｙ、特開昭６４−６６２１
（ｉ）、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同様に重合して得ることができ３．
０ｇを得た、同様に”Ｃ−ＮＭＩＩを測定すると約３０
．６、東、８．３２．２．３８．４．４５．６．４５．
７．４Ｇ、６．４６．７に８本の比較的強いピーク観測
された。これらの１１Ｃ−ＮＭＩ？の吸収スペクトルの
測定結果は第１図に示す、またＸ線回折（Ｃｕ−α）の
測定結果を第２図に示す。Note that polycyclopentene was produced by a known method (TransiLion MeLal and Org
anoseLallicsas CatalysL
rot 0rerin I'olymeriza
tion 291 ~ 301 (198B) F! ds
, If, Kasinsky, JP-A-64-6621
(i), 1. It can be obtained by polymerizing in the same manner using 2-ethylenebisindenylzirconium dichloride.3.
Similarly, C-NMII was measured and it was about 30g.
．． 6, East, 8.32.2.38.4.45.6.45.
Eight relatively strong peaks were observed at 7.4G and 6.46.7. These 11C-NMI? The measurement results of the absorption spectrum are shown in FIG. 1, and the measurement results of X-ray diffraction (Cu-α) are shown in FIG.
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、工業的に価偵がある。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で得た本発明のポリシクロペンテン（
ａ）および従来技術で得た規則性の低いシクロペンテン
（ｂ）の” Ｃ−ＮＭＲスペクトルである。
第２図は同じく本発明のポリシクロペンテン（ａ）およ
び従来技術で得た規則性の低いシクロペンテン（ｂ）の
Ｘ線回折スペクトルである。Figure 1 shows the polycyclopentene of the present invention obtained in Example 1 (
Fig. 2 shows the C-NMR spectra of polycyclopentene (a) of the present invention and cyclopentene (b) with low regularity obtained using the conventional technique. It is an X-ray diffraction spectrum of b).
Claims (1)
１＾３Ｃ−ＮＭＲで、テトラメチルシランを基準として
実質的に約３０．８、３８．５、４６．７ｐｐｍの３本
のピークのみが観測される高度に立体規則性のポリシク
ロペンテン。 ２）非対称な配位子を含有する遷移金属化合物とアルミ
ノキサンからなる触媒を用いてシクロペンテンを重合す
ることを特徴とする高度に立体規則性のポリシクロペン
テンの製造方法。[Claims] 1) Measured with 1,2,4-trichlorobenzene solution^
A highly stereoregular polycyclopentene in which substantially only three peaks at about 30.8, 38.5, and 46.7 ppm based on tetramethylsilane are observed in 1^3C-NMR. 2) A method for producing highly stereoregular polycyclopentene, which comprises polymerizing cyclopentene using a catalyst consisting of a transition metal compound containing an asymmetric ligand and aluminoxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27577889A JP2886906B2 (en) | 1989-10-25 | 1989-10-25 | Polycyclopentene and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27577889A JP2886906B2 (en) | 1989-10-25 | 1989-10-25 | Polycyclopentene and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03139506A true JPH03139506A (en) | 1991-06-13 |
| JP2886906B2 JP2886906B2 (en) | 1999-04-26 |
Family
ID=17560271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27577889A Expired - Lifetime JP2886906B2 (en) | 1989-10-25 | 1989-10-25 | Polycyclopentene and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2886906B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7034095B2 (en) | 2002-02-14 | 2006-04-25 | Nippon Petrochemicals Co., Ltd. | Bicyclic conjugated diene polymer and bicyclic conjugated diene copolymer |
-
1989
- 1989-10-25 JP JP27577889A patent/JP2886906B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7034095B2 (en) | 2002-02-14 | 2006-04-25 | Nippon Petrochemicals Co., Ltd. | Bicyclic conjugated diene polymer and bicyclic conjugated diene copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2886906B2 (en) | 1999-04-26 |
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