JP2854884B2 - Propylene copolymer - Google Patents
Propylene copolymerInfo
- Publication number
- JP2854884B2 JP2854884B2 JP20288089A JP20288089A JP2854884B2 JP 2854884 B2 JP2854884 B2 JP 2854884B2 JP 20288089 A JP20288089 A JP 20288089A JP 20288089 A JP20288089 A JP 20288089A JP 2854884 B2 JP2854884 B2 JP 2854884B2
- Authority
- JP
- Japan
- Prior art keywords
- propylene
- ethylene
- polymerization
- copolymer
- absorption
- 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 - Lifetime
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はプロピレンの共重合体に関する。詳しくは、
プロピレンのメチル基の立体構造が特定のものであるプ
ロピレンとエチレンの共重合体に関する。Description: TECHNICAL FIELD The present invention relates to a propylene copolymer. For more information,
The present invention relates to a copolymer of propylene and ethylene, wherein the steric structure of the propylene methyl group is specific.
エチレンとプロピレンの共重合体としては、従来より
種々の構造のものが知られており、触媒系によって、エ
チレンとプロピレンの連鎖分布が異なるだけでなくメチ
ル基の立体構造が異なるものが知られている。しかしな
がらメチル基の立体構造としては、プロピレン分子の３
個のならびでみるトリアッドでmm、mrが多い構造のもの
は知られていたがrrが多い構造のものは知られていなか
った。Conventionally, copolymers of ethylene and propylene have been known to have various structures, and depending on the catalyst system, not only different chain distributions of ethylene and propylene but also different steric structures of methyl groups are known. I have. However, the three-dimensional structure of the methyl group is
Triads with a lot of mm and mr were known, but those with a lot of rr were not known.
プロピレンの連鎖の立体構造は、共重合体の物性に反
映すると同時に、共重合体を他の重合体と混合して用い
ると従来の構造の共重合体とはその効果が異なることも
期待される。従ってプロピレン分子の３個のならびでみ
るトリアッドでrrが多い構造の共重合体の開発が望まれ
ている。The three-dimensional structure of the propylene chain reflects the physical properties of the copolymer, and it is expected that the effect of the copolymer will be different from that of the copolymer having the conventional structure when the copolymer is used in combination with other polymers. . Therefore, it is desired to develop a copolymer having a triad and a large rr structure in which three propylene molecules are arranged.
本発明者らは上記、従来とは異なる構造の共重合体に
ついて鋭意探索し本発明を完成した。The present inventors have conducted extensive searches for a copolymer having a structure different from that of the related art, and completed the present invention.
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13C−NMRで、テトラメチルシランを基準として
20.3〜20.0ppmに観測されるラセミ構造に帰属されるピ
ーク強度がメチル基による全ピーク強度の0.5以上であ
りエチレン含量が20〜80wt％であるシンジオタクチック
構造を有するプロピレンの共重合体である。That is, the present invention, 13 C-NMR measured in 1,2,4-trichlorobenzene solution, based on tetramethylsilane
It is a copolymer of propylene having a syndiotactic structure in which the peak intensity attributed to the racemic structure observed at 20.3 to 20.0 ppm is 0.5 or more of the total peak intensity due to the methyl group and the ethylene content is 20 to 80 wt%. .
本発明のプロピレン−エチレン共重合体を製造するに
用いる触媒としては、例えばJ.Am.Chem.Soc.,1988,110,
6255−6256に記載された化合物が例示できるが、異なる
構造であってもプロピレンの単独重合体を製造した時、
得られる重合体のシンジオタクチックペンタッド分率
（A.ZambelliらMacromolecules vol 6 687（1973），同
vol 8 925（1975））が0.7以上程度の比較的シンジオタ
クティシティーが高い重合体を与える触媒系であれば利
用可能であり、例えば、非対称な配分子を有する遷移金
属化合物とアルミノキサンとからなる触媒系が有効であ
る。Examples of the catalyst used for producing the propylene-ethylene copolymer of the present invention include, for example, J. Am. Chem. Soc., 1988, 110,
Compounds described in 6255-6256 can be exemplified, but when a homopolymer of propylene is produced even with a different structure,
Syndiotactic pentad fraction of the resulting polymer (A. Zambelli et al., Macromolecules vol 6 687 (1973);
vol 8 925 (1975)) can be used as long as it is a catalyst system that gives a polymer having a relatively high syndiotacticity of about 0.7 or more. For example, it is composed of a transition metal compound having an asymmetric dimer and an aluminoxane. A catalyst system is effective.
本発明の共重合体を製造するに好適な触媒系としては
上記文献に記載されたイソプロピル（シクロペンタジエ
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（シクロペンタジエニル−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、 一般式、 （式中Ｒは炭素数１〜３の炭化水素残基。）で表される
化合物が例示でき特に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。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50〜5000モル倍
である。また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
存在しない塊状重合法、気相重合法も利用できる。As a catalyst system suitable for producing the copolymer of the present invention, isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride or isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride described in the above-mentioned literature is used. And the aluminoxane has a general formula: (Wherein R is a hydrocarbon residue having 1 to 3 carbon atoms). Examples thereof include methylaluminoxane wherein R is a methyl group and n is 5 or more, preferably 10 or more. The use ratio of the aluminoxane to the transition metal catalyst is 10 to 100,000,000 times, usually 50 to 5000 times. The polymerization conditions are not particularly limited, and a solvent polymerization method using an inert medium, a bulk polymerization method substantially free of an inert medium, and a gas phase polymerization method can be used.
重合温度としては−100〜200℃、重合圧力としては常
圧〜100kg/cm2−Ｇで行うのが一般的である。好ましく
は−100〜100℃で、常圧〜50kg/cm2である。Generally, the polymerization is carried out at a temperature of -100 to 200 ° C. and at a pressure of normal pressure to 100 kg / cm 2 -G. Preferably, the temperature is from -100 to 100 ° C, and the pressure is from normal pressure to 50 kg / cm 2 .
本発明において、重要なエチレンとプロピレンの重合
割合がエチレン含量で20〜80wt％となるように単量体の
重合系への導入量を制御すること、そして共重合体の1,
2,4−トリクロロベンゼン溶液で測定した13C−NMRで、
テトラメチルシランを基準として20.3〜20.0ppmに観測
されるラセミ構造に帰属されるピーク強度がメチル基に
よる全ピーク強度の0.5以上であるように重合温度等を
制御することが必要である。In the present invention, the amount of monomer introduced into the polymerization system is controlled so that the polymerization ratio of ethylene and propylene becomes 20 to 80% by weight in terms of ethylene content.
By 13 C-NMR measured with 2,4-trichlorobenzene solution,
It is necessary to control the polymerization temperature and the like so that the peak intensity attributed to the racemic structure observed at 20.3 to 20.0 ppm based on tetramethylsilane is 0.5 or more of the total peak intensity due to the methyl group.
以下に実施例を示しさらに本発明を説明する。 Hereinafter, the present invention will be described with reference to Examples.
実施例１ 内容積５のオートクレーブにプロピレン1500g、25
℃での分圧として10kg/cm2相当のエチレンを加え、つい
で常法に従って合成したイソプロピルシクロペンタジエ
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
ジエニル−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（有）製メチルアルミノキサン（重合
度16.1）1.36gをトルエン50mlに溶解し、25℃で圧入し
たエチレンを追加して22kg/cm2−Ｇに保って15分間重合
した。重合後、未反応のモノマーをパージしてポリマー
を取り出し80℃で減圧乾燥して80gのポリマーを得た。
13C−NMRによって分析したところエチレン含量は48.5wt
％であり、メチル基の吸収としては20.3〜20.0ppmに大
きく２本強い吸収が観測され、22〜19ppmに観測される
全メチル基の吸収に対して0.65の吸収強度比であった。
またメチレン基の吸収により算出したプロピレン−プロ
ピレンの連鎖の割合は0.30、プロピレン−エチレンの割
合が0.43、エチレン−エチレンの割合が0.27でありラン
ダム性が良好であった。Example 1 1500 g of propylene was added to an autoclave having an internal volume of 5
℃ the partial pressure of 10 kg / cm 2 equivalent of ethylene in addition, then isopropyl lithiated isopropyl cyclopentadienyl-1-fluorene synthesized in a conventional manner, was obtained by reacting with zirconium tetrachloride (Shikuropentaji (Enyl-1-fluorenyl) zirconium dichloride
10 mg and 1.36 g of methylaluminoxane (manufactured by Toyo Akzo Co., Ltd. (polymerization degree: 16.1)) were dissolved in 50 ml of toluene, and ethylene was added under pressure at 25 ° C., and polymerization was carried out for 15 minutes while maintaining the pressure at 22 kg / cm 2 -G. After the polymerization, unreacted monomers were purged, and the polymer was taken out and dried at 80 ° C. under reduced pressure to obtain 80 g of a polymer.
When analyzed by 13 C-NMR, the ethylene content was 48.5 wt.
%, The absorption of the methyl group was large at 20.3 to 20.0 ppm, and two strong absorptions were observed, and the absorption intensity ratio was 0.65 with respect to the absorption of all the methyl groups observed at 22 to 19 ppm.
In addition, the ratio of propylene-propylene chains calculated by absorption of methylene groups was 0.30, the ratio of propylene-ethylene was 0.43, and the ratio of ethylene-ethylene was 0.27, indicating good randomness.
また135℃テトラリン溶液で測定した極限粘度（以下
ηと記す）は0.32であり、135℃1,2,4−トリクロロベン
ゼン溶液で測定した重量平均分子量と数平均分子量の比
（以下、MW/MNと記す）は2.2であった。The intrinsic viscosity (hereinafter referred to as η) measured at 135 ° C. tetralin solution is 0.32, and the ratio of the weight average molecular weight to the number average molecular weight measured at 135 ° C. 1,2,4-trichlorobenzene solution (hereinafter MW / MN) Was 2.2.
実施例２ 内容積５のオートクレーブにプロピレン1500g、25
℃での分圧が5kg/cm2となるようにエチレンを加え、イ
ソプロピル（シクロペンタジエニル−１−フルオレニ
ル）ジルコニウムジクロリド10mgと重合度約15のメチル
アルミノキサン1.36gを25℃で圧入した。エチレンを追
加して25℃で17kg/cm2−Ｇとなる様にエチレンを追加し
ながら15分間重合した。ついで未反応のプロピレンをパ
ージした後、パウダーを取り出し80℃で減圧乾燥したと
ころポリマー62gを得た。実施例１と同様に物性を測定
したところηは0.47、エチレン含量26.4wt％、20.2及び
20.1ppmに２本強い吸収が観測され22〜19ppmに観測され
る全メチル基の吸収に対して0.85の吸収強度比であり、
またメチレン基の吸収から算出したプロピレン−プロピ
レンの連鎖の割合は0.39、プロピレン−エチレンの割合
が0.51、エチレン−エチレンの割合が0.10でありランダ
ム性が良好であった。Example 2 1500 g of propylene and 25 g
Ethylene was added so that the partial pressure at 5 ° C. was 5 kg / cm 2, and 10 mg of isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride and 1.36 g of methylaluminoxane having a degree of polymerization of about 15 were injected at 25 ° C. Polymerization was carried out for 15 minutes at 25 ° C. while adding ethylene so as to obtain 17 kg / cm 2 -G at 25 ° C. Then, after unreacted propylene was purged, the powder was taken out and dried at 80 ° C. under reduced pressure to obtain 62 g of a polymer. When the physical properties were measured in the same manner as in Example 1, η was 0.47, the ethylene content was 26.4 wt%, 20.2 and
Two strong absorptions are observed at 20.1 ppm, and the absorption intensity ratio is 0.85 with respect to the absorption of all methyl groups observed at 22 to 19 ppm,
The proportion of propylene-propylene chains calculated from the absorption of methylene groups was 0.39, the proportion of propylene-ethylene was 0.51, and the proportion of ethylene-ethylene was 0.10, indicating good randomness.
比較例１ 塩化マグネシウム20gと四塩化チタン7ml、フタル酸ジ
イソブチル6ml、を40時間共粉砕し、ついで共粉砕物を
沸騰トルエンで処理したものを遷移金属触媒として用い
た。上記遷移金属触媒10mg、ジフェニルジメトキシシラ
ン0.03ml、トリエチルアルミニウム0.10mlを用い実施例
１と同様に重合した。但し、エチレン分圧は5kg/cm2、
水素3N重合温度50℃で15分間重合を行った。重合体の
ηは1.84、エチレン含量41wt％、20.3〜20.0ppmには吸
収はなく21.7、21.5ppmに観測された吸収は全メチル基
の吸収に対して0.49の吸収強度比であった。またメチレ
ン基の吸収より算出したプロピレン−プロピレンの連鎖
は0.33、プロピレン−エチレンの連鎖は0.34、エチレン
−エチレンの連鎖は0.34とブロック性の高いものであっ
た。またMW/MNは6.1であった。Comparative Example 1 20 g of magnesium chloride, 7 ml of titanium tetrachloride, and 6 ml of diisobutyl phthalate were co-ground for 40 hours, and the co-ground material treated with boiling toluene was used as a transition metal catalyst. Polymerization was carried out in the same manner as in Example 1 using 10 mg of the above transition metal catalyst, 0.03 ml of diphenyldimethoxysilane, and 0.10 ml of triethylaluminum. However, ethylene partial pressure is 5kg / cm 2 ,
Polymerization was carried out at a hydrogen 3N polymerization temperature of 50 ° C. for 15 minutes. The η of the polymer was 1.84, the ethylene content was 41 wt%, no absorption was observed in 20.3 to 20.0 ppm, and the absorption observed at 21.7 and 21.5 ppm was an absorption intensity ratio of 0.49 to the absorption of all methyl groups. The propylene-propylene chain calculated from the absorption of the methylene group was 0.33, the propylene-ethylene chain was 0.34, and the ethylene-ethylene chain was 0.34, indicating a high block property. MW / MN was 6.1.
本発明の共重合体は全く新規なものであり種々の用途
にその可能性が期待でき工業的に極めて価値がある。The copolymer of the present invention is completely novel, and its potential is expected for various uses and is extremely valuable industrially.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C08F 10/00 - 10/14 C08F 210/00 - 210/18 C08F 4/60 - 4/70──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 6 , DB name) C08F 10/00-10/14 C08F 210/00-210/18 C08F 4/60-4/70
Claims (1)
た13C−NMRで、テトラメチルシランを基準として20.3〜
20.0ppmに観測されるラセミ構造に帰属されるピーク強
度がメチル基による全ピーク強度の0.5以上でありエチ
レン含量が20〜80wt％であるシンジオタクチック構造を
有するプロピレンの共重合体。(1) A 13 C-NMR measured with a 1,2,4-trichlorobenzene solution, wherein 20.3 to
A propylene copolymer having a syndiotactic structure, wherein the peak intensity attributed to the racemic structure observed at 20.0 ppm is 0.5 or more of the total peak intensity due to the methyl group, and the ethylene content is 20 to 80 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20288089A JP2854884B2 (en) | 1989-08-07 | 1989-08-07 | Propylene copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20288089A JP2854884B2 (en) | 1989-08-07 | 1989-08-07 | Propylene copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0366712A JPH0366712A (en) | 1991-03-22 |
| JP2854884B2 true JP2854884B2 (en) | 1999-02-10 |
Family
ID=16464733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20288089A Expired - Lifetime JP2854884B2 (en) | 1989-08-07 | 1989-08-07 | Propylene copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2854884B2 (en) |
-
1989
- 1989-08-07 JP JP20288089A patent/JP2854884B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0366712A (en) | 1991-03-22 |
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