JP2004217798A - 1-butene-based polymer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a 1-butene-based polymer having a wide molecular weight distribution and corresponding to high-speed molding; and to provide a method for producing the polymer. <P>SOLUTION: The 1-butene-based polymer satisfies the following conditions (1) to (4): (1) being a crystalline resin the melting point (Tm-P) of which defined by a peak top of a peak observed at the highest temperature in a melting heat-absorbing curve obtained by using a differential scanning calorimeter (DSC), and raising the temperature by 10°C/min after melting the crystal at 190°C for 5 min in a nitrogen atmosphere is not observed or is within a range of 0-100°C; (2) having ≤20 tacticity index (mmmm)/[(mmrr)+(rmmr)]; (3) having 0.1-4.0 dl/g intrinsic viscosity [η]; and (4) having ≥4.0 molecular weight distribution (Mw/Mn) measured by a gel permeation chromatography (GPC). <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００２０】
〔式中、Ｍは周期律表第４族の金属元素を示し、Ｘ^１及びＸ^２はσ結合性の配位子を示し、同一でも異なっていてもよい。
Ｒ^１及びＲ^２は、それぞれ炭化水素基、ハロゲン原子、アルコキシ基、珪素含有炭化水素基、リン含有炭化水素基、窒素含有炭化水素基又は硼素含有炭化水素基を示す。
Ｒ^３〜Ｒ^１０は、それぞれ水素、炭化水素基、ハロゲン原子、アルコキシ基、珪素含有炭化水素基、リン含有炭化水素基、窒素含有炭化水素基又は硼素含有炭化水素基を示す。
Ｅ^１及びＥ^２は、二つの配位子を結合する二価の架橋基であって、炭素数１〜２０の炭化水素基、炭素数１〜２０のハロゲン含有炭化水素基、珪素含有基、ゲルマニウム含有基を示し、互いに同一でも異なっていてもよい。〕
で表される遷移金属化合物、及び（Ｂ）（Ｂ−１）該（Ａ）成分の遷移金属化合物又はその派生物と反応してイオン性の錯体を形成しうる化合物、及び（Ｂ−２）アルミノキサンから選ばれる成分を含有する触媒が挙げられる。
【００２１】
上記一般式（Ｉ）で表される遷移金属化合物において、Ｍは周期律表第４族の金属元素を示し、具体例としてはチタン，ジルコニウム及びハフニウム等が挙げられる。
Ｘ^１及びＸ^２の具体例としては、ハロゲン原子，炭素数１〜２０の炭化水素基，炭素数１〜２０のアルコキシ基及び炭素数１〜２０の珪素含有基等が挙げられる。
ハロゲン原子としては、塩素原子、フッ素原子、臭素原子及びヨウ素原子が挙げられる。
炭素数１〜２０の炭化水素基としては、具体的には、メチル基、エチル基、プロピル基、ブチル基等のアルキル基や、ビニル基、プロペニル基等のアルケニル基；ベンジル基、フェニルエチル基等のアリールアルキル基；フェニル基、トリル基等のアリール基が挙げられる。
なかでも、メチル基、エチル基、プロピル基等のアルキル基や塩素原子基等のハロゲン原子が好ましい。
炭素数１〜２０のアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基が挙げられる。
炭素数６〜２０のアリールオキシ基としては、フェノキシ基、メチルフェノキシ基、フェニルメトキシ基、フェニルエトキシ基等が挙げられる。
炭素数１〜２０の珪素含有基としては、メチルシリル基、フェニルシリル基等のモノ炭化水素置換シリル基；ジメチルシリル基、ジフェニルシリル基等のジ炭化水素置換シリル基；トリメチルシリル基、トリエチルシリル基、トリプロピルシリル基、トリシクロヘキシルシリル基、トリフェニルシリル基、ジメチルフェニルシリル基、メチルフェニルジシリル基、トリトリルシリル基、トリナフチルシリル基等のトリ炭化水素置換シリル基；トリメチルシリルエーテル基等の炭化水素置換シリル基のシリルエーテル基；トリメチルシリルメチル基等のケイ素置換アルキル基；トリメチルシリルフェニル基等のケイ素置換アリール基等が挙げられる。
なかでも、トリメチルシリル基、フェネチルジメチルシリル基等が好ましい。
【００２２】
Ｅ^１及びＥ^２の具体例としては、ジメチルシリレン基，ジフェニルシリレン基，メチルフェニルシリレン基，ジメチルゲルミレン基，テトラメチルジシリレン基，ジフェニルジシリレン基等を挙げることができる。
【００２３】
一般式（Ｉ）で表される遷移金属化合物は、二重架橋型ビスインデン誘導体を配位子とし、配位子間の架橋基はケイ素を含むものが好ましい。
一般式（Ｉ）で表される遷移金属化合物の具体例としては、（１，２’−イソプロピリデン）（２，１’−イソプロピリデン）−ビス（インデニル）ジルコニウムジクロリド，（１，２’−エチレン）（２，１’−エチレン）−ビス（３−メチルインデニル）ジルコニウムジクロリド，（１，２’−ジメチルシリレン）（２，１’−ジメチルシリレン）ビス（３−メチルインデニル）ジルコニウムジクロリド，（１，２’−ジメチルシリレン）（２，１’−ジメチルシリレン）ビス（３−ｎ−ブチルインデニル）ジルコニウムジクロリド，（１，２’−ジメチルシリレン）（２，１’−ジメチルシリレン）ビス（３−ｉ−プロピルインデニル）ジルコニウムジクロリド，（１，２’−ジメチルシリレン）（２，１’−ジメチルシリレン）ビス（３−トリメチルシリルメチルインデニル）ジルコニウムジクロリド，（１，２’−ジメチルシリレン）（２，１’−ジメチルシリレン）ビス（３−フェニルインデニル）ジルコニウムジクロリド，（１，２’−ジメチルシリレン）（２，１’−イソプロピリデン）−ビス（３−メチルインデニル）ジルコニウムジクロリド，（１，２’−ジメチルシリレン）（２，１’−イソプロピリデン）−ビス（３−ｉ−プロピルインデニル）ジルコニウムジクロリド，（１，２’−ジメチルシリレン）（２，１’−イソプロピリデン）−ビス（３−ｎ−ブチルインデニル）ジルコニウムジクロリド，（１，２’−ジメチルシリレン）（２，１’−イソプロピリデン）−ビス（３−トリメチルシリルメチルインデニル）ジルコニウムジクロリド，（１，２’−ジメチルシリレン）（２，１’−イソプロピリデン）−ビス（３−トリメチルシリルインデニル）ジルコニウムジクロリド，（１，２’−ジメチルシリレン）（２，１’−メチレン）−ビス（３−ｉ−プロピルインデニル）ジルコニウムジクロリド，（１，２’−ジメチルシリレン）（２，１’−メチレン）−ビス（３−ｎ−ブチルインデニル）ジルコニウムジクロリド，（１，２’−ジメチルシリレン）（２，１’−メチレン）−ビス（３−トリメチルシリルメチルインデニル）ジルコニウムジクロリド，（１，２’−ジフェニルシリレン）（２，１’−メチレン）−ビス（３−メチルインデニル）ジルコニウムジクロリド等及びこれらの化合物におけるジルコニウムをチタン又はハフニウムに置換したものを挙げることができる。
勿論、これらに限定されるものではない。
【００２４】
次に、（Ｂ）成分のうちの（Ｂ−１）成分としては、上記（Ａ）成分の遷移金属化合物と反応して、イオン性の錯体を形成しうる化合物であれば、いずれのものでも使用できるが、次の一般式（ＩＩ）又は（ＩＩＩ）
（〔Ｌ^１−Ｒ^１２〕^ｋ＋）_ａ（〔Ｚ〕⁻）_ｂ ・・・（ＩＩ）
（〔Ｌ^２〕^ｋ＋）_ａ（〔Ｚ〕⁻）_ｂ ・・・（ＩＩＩ）
（但し、Ｌ^２は、Ｍ^２、Ｒ^１３Ｒ^１４Ｍ^３、Ｒ^１５ _３Ｃ又はＲ^１６Ｍ^３である。）
〔（ＩＩＩ），（ＩＶ）式中、Ｌ^１はルイス塩基、〔Ｚ〕⁻は、非配位性アニオン〔Ｚ^１〕⁻及び〔Ｚ^２〕⁻、ここで〔Ｚ^１〕⁻は複数の基が元素に結合したアニオン、即ち〔Ｍ^１Ｇ^１Ｇ^２・・・Ｇ^ｆ〕⁻（ここで、Ｍ^１は周期律表第５〜１５族元素、好ましくは周期律表第１３〜１５族元素を示す。Ｇ^１〜Ｇ^ｆはそれぞれ水素原子，ハロゲン原子，炭素数１〜２０のアルキル基，炭素数２〜４０のジアルキルアミノ基，炭素数１〜２０のアルコキシ基，炭素数６〜２０のアリール基，炭素数６〜２０のアリールオキシ基，炭素数７〜４０のアルキルアリール基，炭素数７〜４０のアリールアルキル基，炭素数１〜２０のハロゲン置換炭化水素基，炭素数１〜２０のアシルオキシ基，有機メタロイド基、又は炭素数２〜２０のヘテロ原子含有炭化水素基を示す。Ｇ^１〜Ｇ^ｆのうち２つ以上が環を形成していてもよい。ｆは〔（中心金属Ｍ^１の原子価）＋１〕の整数を示す。）、
〔Ｚ^２〕⁻は、酸解離定数の逆数の対数（ｐＫａ）が−１０以下のブレンステッド酸単独又はブレンステッド酸及びルイス酸の組合わせの共役塩基、又は一般的に超強酸と定義される酸の共役塩基を示す。又、ルイス塩基が配位していてもよい。
又、Ｒ^１２は、水素原子，炭素数１〜２０のアルキル基，炭素数６〜２０のアリール基，アルキルアリール基又はアリールアルキル基を示し、Ｒ^１３及びＲ^１４はそれぞれシクロペンタジエニル基，置換シクロペンタジエニル基，インデニル基又はフルオレニル基、Ｒ^１５は炭素数１〜２０のアルキル基，アリール基，アルキルアリール基又はアリールアルキル基を示す。
Ｒ^１６は、テトラフェニルポルフィリン，フタロシアニン等の大環状配位子を示す。
ｋは、〔Ｌ^１−Ｒ^１２〕，〔Ｌ^２〕のイオン価数で１〜３の整数、ａは１以上の整数、ｂ＝（ｋ×ａ）である。
Ｍ^２は、周期律表第１〜３、１１〜１３、１７族元素を含むものであり、Ｍ^３は、周期律表第７〜１２族元素を示す。〕
で表されるものを好適に使用することができる。
【００２５】
ここで、Ｌ^１の具体例としては、アンモニア，メチルアミン，アニリン，ジメチルアミン，ジエチルアミン，Ｎ−メチルアニリン，ジフェニルアミン，Ｎ，Ｎ−ジメチルアニリン，トリメチルアミン，トリエチルアミン，トリ−ｎ−ブチルアミン，メチルジフェニルアミン，ピリジン，ｐ−ブロモ−Ｎ，Ｎ−ジメチルアニリン，ｐ−ニトロ−Ｎ，Ｎ−ジメチルアニリン等のアミン類、トリエチルホスフィン，トリフェニルホスフィン，ジフェニルホスフィン等のホスフィン類、テトラヒドロチオフェン等のチオエーテル類、安息香酸エチル等のエステル類、アセトニトリル，ベンゾニトリル等のニトリル類等を挙げることができる。
【００２６】
Ｒ^１２の具体例としては水素，メチル基，エチル基，ベンジル基，トリチル基等を挙げることができ、Ｒ^１３，Ｒ^１４の具体例としては、シクロペンタジエニル基，メチルシクロペンタジエニル基，エチルシクロペンタジエニル基，ペンタメチルシクロペンタジエニル基等を挙げることができる。
Ｒ^１５の具体例としては、フェニル基，ｐ−トリル基，ｐ−メトキシフェニル基等を挙げることができ、Ｒ^１６の具体例としてはテトラフェニルポルフィン，フタロシアニン，アリル，メタリル等を挙げることができる。
又、Ｍ^２の具体例としては、Ｌｉ，Ｎａ，Ｋ，Ａｇ，Ｃｕ，Ｂｒ，Ｉ，Ｉ_３等を挙げることができ、Ｍ^３の具体例としては、Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｚｎ等を挙げることができる。
【００２７】
又、〔Ｚ^１〕⁻、即ち〔Ｍ^１Ｇ^１Ｇ^２・・・Ｇ^ｆ〕において、Ｍ^１の具体例としてはＢ，Ａｌ，Ｓｉ，Ｐ，Ａｓ，Ｓｂ等、好ましくはＢ及びＡｌが挙げられる。
又、Ｇ^１，Ｇ^２〜Ｇ^ｆの具体例としては、ジアルキルアミノ基として、ジメチルアミノ基，ジエチルアミノ基等、アルコキシ基又はアリールオキシ基としてメトキシ基，エトキシ基，ｎ−ブトキシ基，フェノキシ基等、炭化水素基としてメチル基，エチル基，ｎ−プロピル基，イソプロピル基，ｎ−ブチル基，イソブチル基，ｎ−オクチル基，ｎ−エイコシル基，フェニル基，ｐ−トリル基，ベンジル基，４−ｔ−ブチルフェニル基，３，５−ジメチルフェニル基等、ハロゲン原子としてフッ素，塩素，臭素，ヨウ素，ヘテロ原子含有炭化水素基としてｐ−フルオロフェニル基，３，５−ジフルオロフェニル基，ペンタクロロフェニル基，３，４，５−トリフルオロフェニル基，ペンタフルオロフェニル基，３，５−ビス（トリフルオロメチル）フェニル基，ビス（トリメチルシリル）メチル基等、有機メタロイド基としてペンタメチルアンチモン基、トリメチルシリル基，トリメチルゲルミル基，ジフェニルアルシン基，ジシクロヘキシルアンチモン基，ジフェニル硼素等が挙げられる。
【００２８】
又、非配位性のアニオン、即ち、ｐＫａが−１０以下のブレンステッド酸単独又はブレンステッド酸及びルイス酸の組合わせの共役塩基〔Ｚ^２〕⁻の具体例としては、トリフルオロメタンスルホン酸アニオン（ＣＦ_３ＳＯ_３）⁻，ビス（トリフルオロメタンスルホニル）メチルアニオン，ビス（トリフルオロメタンスルホニル）ベンジルアニオン，ビス（トリフルオロメタンスルホニル）アミド，過塩素酸アニオン（ＣｌＯ_４）⁻，トリフルオロ酢酸アニオン（ＣＦ_３ＣＯ_２）⁻，ヘキサフルオロアンチモンアニオン（ＳｂＦ_６）⁻，フルオロスルホン酸アニオン（ＦＳＯ_３）⁻，クロロスルホン酸アニオン（ＣｌＳＯ_３）⁻，フルオロスルホン酸アニオン／５−フッ化アンチモン（ＦＳＯ_３／ＳｂＦ_５ ）⁻，フルオロスルホン酸アニオン／５−フッ化砒素（ＦＳＯ_３／ＡｓＦ_５）⁻，トリフルオロメタンスルホン酸／５−フッ化アンチモン（ＣＦ_３ＳＯ_３／ＳｂＦ_５）⁻等を挙げることができる。
【００２９】
このような前記（Ａ）成分の遷移金属化合物と反応してイオン性の錯体を形成するイオン性化合物、即ち（Ｂ−１）成分の化合物の具体例としては、テトラキス（ペンタフルオロフェニル）硼酸トリエチルアンモニウム，テトラキス（ペンタフルオロフェニル）硼酸トリ−ｎ−ブチルアンモニウム，テトラキス（ペンタフルオロフェニル）硼酸トリフェニルアンモニウム，テトラキス（ペンタフルオロフェニル）硼酸テトラ−ｎ−ブチルアンモニウム，テトラキス（ペンタフルオロフェニル）硼酸テトラエチルアンモニウム，テトラキス（ペンタフルオロフェニル）硼酸ベンジル（トリ−ｎ−ブチル）アンモニウム，テトラキス（ペンタフルオロフェニル）硼酸メチルジフェニルアンモニウム，テトラキス（ペンタフルオロフェニル）硼酸トリフェニル（メチル）アンモニウム，テトラキス（ペンタフルオロフェニル）硼酸メチルアニリニウム，テトラキス（ペンタフルオロフェニル）硼酸ジメチルアニリニウム，テトラキス（ペンタフルオロフェニル）硼酸トリメチルアニリニウム，テトラキス（ペンタフルオロフェニル）硼酸メチルピリジニウムが挙げられる。
この（Ｂ−１）成分である、該（Ａ）成分の遷移金属化合物と反応してイオン性の錯体を形成しうる化合物は一種用いてもよく、また二種以上を組み合わせて用いてもよい。
【００３０】
一方、（Ｂ−２）成分のアルミノキサンとしては、一般式（ＩＶ）
【００３１】
【化２】

【００３２】
（式中、Ｒ^１１は、炭素数１〜２０、好ましくは１〜１２のアルキル基，アルケニル基，アリール基，アリールアルキル基等の炭化水素基又はハロゲン原子を示し、ｗは平均重合度を示し、通常２〜５０、好ましくは２〜４０の整数である。
尚、各Ｒ^１１は同じでも異なっていてもよい。）
で示される鎖状アルミノキサン、及び一般式（Ｖ）
【００３３】
【化３】

【００３４】
（式中、Ｒ^１１及びｗは前記一般式（ＩＶ）におけるものと同じである。）
で示される環状アルミノキサンを挙げることができる。
これらのアルミノキサンは一種用いてもよく、二種以上を組み合わせて用いてもよい。
【００３５】
（Ａ）触媒成分と（Ｂ）触媒成分との使用割合は、（Ｂ）触媒成分として（Ｂ−１）化合物を用いた場合には、モル比で好ましくは１０：１〜１：１００、より好ましくは２：１〜１：１０の範囲が望ましく、上記範囲を逸脱する場合は、単位質量ポリマー当りの触媒コストが高くなり、実用的でない。
又、（Ｂ−２）化合物を用いた場合には、モル比で好ましくは１：１〜１：１００００００、より好ましくは１：１０〜１：１００００の範囲が望ましい。
この範囲を逸脱する場合は、単位質量ポリマーあたりの触媒コストが高くなり、実用的でない。
又、触媒成分（Ｂ）としては（Ｂ−１）成分，（Ｂ−２）成分を単独又は二種以上組み合わせて用いることもできる。
【００３６】
又、１−ブテン系重合体を製造する際の重合用触媒は、上記（Ａ）成分及び（Ｂ）成分に加えて（Ｃ）成分として有機アルミニウム化合物を用いることができる。
ここで、（Ｃ）成分の有機アルミニウム化合物としては、一般式（ＶＩ）
Ｒ^１８ _ｖＡｌＪ_３−ｖ ・・・（ＶＩ）
〔式中、Ｒ^１８は炭素数１〜１０のアルキル基、Ｊは水素原子、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基又はハロゲン原子を示し、ｖは１〜３の整数である〕
で示される化合物が用いられる。
前記一般式（ＶＩ）で示される化合物の具体例としては、トリメチルアルミニウム，トリエチルアルミニウム，トリイソプロピルアルミニウム，トリイソブチルアルミニウム，ジメチルアルミニウムクロリド，ジエチルアルミニウムクロリド，メチルアルミニウムジクロリド，エチルアルミニウムジクロリド，ジメチルアルミニウムフルオリド，ジイソブチルアルミニウムヒドリド，ジエチルアルミニウムヒドリド，エチルアルミニウムセスキクロリド等が挙げられる。
【００３７】
これらの有機アルミニウム化合物は一種用いてもよく、二種以上を組合せて用いてもよい。
前記（Ａ）触媒成分と（Ｃ）触媒成分との使用割合は、モル比で好ましくは１：１〜１：１００００、より好ましくは１：５〜１：２０００、更に好ましくは１：１０ないし１：１０００の範囲が望ましい。
該（Ｃ）触媒成分を用いることにより、遷移金属当たりの重合活性を向上させることができるが、あまり多いと有機アルミニウム化合物が無駄になると共に、重合体中に多量に残存し、好ましくない。
本発明においては、触媒成分の少なくとも一種をＳｉＯ_２，Ａｌ_２Ｏ_３等の担体に担持して用いることができる。
該担体の種類については特に制限はなく、無機酸化物担体、それ以外の無機担体及び有機担体のいずれも用いることができるが、特に、無機酸化物担体又はそれ以外の無機担体が好ましい。
【００３８】
無機酸化物担体としては、具体的には、ＳｉＯ_２，Ａｌ_２Ｏ_３，ＭｇＯ，ＺｒＯ_２，ＴｉＯ_２，Ｆｅ_２Ｏ３ ，Ｂ_２Ｏ３ ，ＣａＯ，ＺｎＯ，ＢａＯ，ＴｈＯ_２やこれらの混合物、例えば、シリカアルミナ，ゼオライト，フェライト，グラスファイバー等が挙げられる。
これらの中では、特にＳｉＯ_２，Ａｌ_２Ｏ_３が好ましい。
尚、上記無機酸化物担体は、少量の炭酸塩，硝酸塩，硫酸塩等を含有してもよい。
【００３９】
本発明の１−ブテン系重合体は、上記触媒を用いて、１−ブテンを単独重合、又は１−ブテン並びにエチレン及び／又は炭素数３〜２０のα−オレフィン（但し、１−ブテンを除く）とを共重合させることににより製造することができる。重合溶媒を用いる場合、例えば、ベンゼン，トルエン，キシレン，エチルベンゼン等の芳香族炭化水素、シクロペンタン，シクロヘキサン，メチルシクロヘキサン等の脂環式炭化水素、ペンタン，ヘキサン，ヘプタン，オクタン等の脂肪族炭化水素、クロロホルム，ジクロロメタン等のハロゲン化炭化水素等を用いることができる。
これらの溶媒は一種を単独で用いてもよく、二種以上のものを組み合わせてもよい。
尚、重合方法によっては無溶媒で行うことができる。
重合に際しては、前記重合用触媒を用いて予備重合を行うことができる。
予備重合は、固体触媒成分に、例えば、少量のオレフィンを接触させることにより行うことができるが、その方法に特に制限はなく、公知の方法を用いることができる。
予備重合に用いるオレフィンについては特に制限はなく、例えば、エチレン、炭素数３〜２０のα−オレフィン、又はこれらの混合物等を挙げることができるが、該重合において用いるオレフィンと同じオレフィンを用いることが有利である。
又、予備重合温度は、通常−２０〜２００℃、好ましくは−１０〜１３０℃、より好ましくは０〜８０℃である。
予備重合においては、溶媒として、不活性炭化水素，脂肪族炭化水素，芳香族炭化水素，モノマー等を用いることができる。
これらの中で特に好ましいのは脂肪族炭化水素である。
又、予備重合は無溶媒で行ってもよい。
予備重合においては、予備重合生成物の極限粘度〔η〕（１３５℃デカリン中で測定）が０．２デシリットル／ｇ以上、特に０．５デシリットル／ｇ以上、触媒中の遷移金属成分１ミリモル当たりに対する予備重合生成物の量が１〜１００００ｇ、特に１０〜１０００ｇとなるように条件を調整することが望ましい。
【００４０】
本発明の１−ブテン系重合体の製造方法における重合形式については、特に制限はなく、溶液重合、スラリー重合、気相重合、バルク重合等のいずれにも適用可能であり、更に、重合方式としては回分式重合や連続式重合のどちらであってもよい。
【００４１】
【実施例】
以下に、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれらの実施例により何ら制限されるものではない。
【００４２】
本発明の１−ブテン系重合体のメソペンタッド分率（ｍｍｍｍ）、ラセミトリアッド分率（ｒｒ）、９０−２×（ｒｒ）、１，４−異常挿入量、立体規則性指数（ｍｍｍｍ）／〔（ｍｍｒｒ）＋（ｒｍｍｒ）〕、極限粘度〔η〕、ｌｏｇη^＊、分子量分布（Ｍｗ／Ｍｎ）、融点（Ｔｍ−Ｐ）及び（Ｔｍ−Ｄ）、融解吸熱量（ΔＨ−Ｐ）及び（ΔＨ−Ｄ）は、明細書本文中に記載した方法により測定した。
【００４３】
実施例１
（１）（１，２’−ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（３−トリメチルシリルメチル−インデニル）ジルコニウムジクロリドの合成
▲１▼（１，２’−ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（インデン）の合成
窒素気流下、１Ｌ三つ口フラスコに、ＴＨＦ１００ｍＬとＭｇ５．０ｇ（２０６ｍｍｏｌ）を加えた。
次に、１，２−ジブロモエタン０．１ｍＬを加え、攪拌し、Ｍｇを活性化した。
３０分間攪拌後、溶媒を抜き出し、新たにＴＨＦ１００ｍＬを添加した。
更に、２−ブロモインデン１０．０ｇ（５１．３ｍｍｏｌ）のＴＨＦ２５０ｍＬ溶液を２時間かけて滴下した。
滴下終了後、室温で２時間攪拌した後、−７８℃に冷却し、ジクロロジメチルシラン６．２ｍＬ（５１．３ｍｍｏｌ）のＴＨＦ１００ｍＬ溶液を１時間で滴下した。
１５時間攪拌後、溶媒を留去し、残渣をヘキサン３００ｍＬで抽出し、溶媒を留去することにより、２−クロロメチルシリルインデン９．６ｇ（４６．２ｍｍｏｌ）を得た。（収率９０％）
次に、窒素気流下、１Ｌ三つ口フラスコに、ＴＨＦ４００ｍＬと２−クロロメチルシリルインデン９．６ｇを加え−７８℃に冷却し、ＬｉＮ（トリメチルシリル）_２のＴＨＦ溶液（１．０Ｍ）を４６．２ｍＬ（４６．２ｍｍｏｌ）滴下した。
室温で１５時間攪拌後、溶媒を留去し、ヘキサン３００ｍＬで抽出し、溶媒を留去することにより、（１，２’−ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（インデン）２．５ｇ（７．２ｍｍｏｌ）を得た。（収率３１％）
^１Ｈ−ＮＭＲ（９０ＭＨｚ，ＣＤＣｌ_３）の測定値
δ：−０．６９，０．７３（１２Ｈ，ジメチルシリレン），３．６６（４Ｈ，−ＣＨ_２−），７．１７（８Ｈ，Ａｒ−Ｈ）
▲２▼（１，２’−ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（３−トリメチルシリルメチルインデニル）ジルコニウムジクロライドの合成
シュレンク瓶に、前記（１，２’−ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（インデン）２．５ｇ（７．２ｍｍｏｌ）とエーテル１００ｍＬを添加した。
−７８℃に冷却し、ｎ−ＢｕＬｉ（ヘキサン溶液１．６Ｍ）９．０ｍＬ（１４．８ｍｍｏｌ）を添加した後、室温で１２時間攪拌した。
溶媒を留去し、得られた固体をヘキサン２０ｍＬで洗浄することにより、リチウム塩を定量的に得た。
シュレンク瓶に、（１，２’−ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（インデン）のリチウム塩（６．９７ｍｍｏｌ）をＴＨＦ５０ｍＬに溶解し、−７８℃に冷却した。
次に、ヨードメチルトリメチルシラン２．１ｍＬ（１４．２ｍｍｏｌ）をゆっくりと滴下し、室温で１２時間攪拌した。
溶媒を留去し、エーテル５０ｍＬを添加して、飽和塩化アンモニウム溶液で洗浄した。
分液後、有機相を乾燥し、溶媒を除去し、（１，２’−ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（３−トリメチルシリルメチルインデン）３．０４ｇ（５．９ｍｍｏｌ）を得た。（収率８４％）
窒素気流下において、シュレンク瓶に、前記の（１，２’−ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（３−トリメチルシリルメチルインデン）を３．０４ｇ（５．９ｍｍｏｌ）とエーテル５０ｍＬを添加した。
−７８℃に冷却し、ｎ−ＢｕＬｉ（ヘキサン溶液１．５４Ｍ）７．６ｍＬ（１１．８ｍｍｏｌ）を添加した後、室温で１２時間攪拌した。
溶媒を留去し、得られた固体をヘキサン４０ｍＬで洗浄することにより、リチウム塩のエーテル付加体３．０６ｇ（５．１ｍｍｏｌ）を得た。（収率８６％）
^１Ｈ−ＮＭＲ（９０ＭＨｚ，ＴＨＦ−ｄ_８）の測定値
δ：０．０４（ｓ，１８Ｈ，トリメチルシリル），０．４８（ｓ，１２Ｈ，ジメチルシリレン），１．１０（ｔ，６Ｈ，メチル），２．５９（ｓ，４Ｈ，メチレン），３．３８（ｑ，４Ｈ，メチレン），６．２〜７．７（ｍ，８Ｈ，Ａｒ−Ｈ）
窒素気流下で、前記のリチウム塩のエーテル付加体をトルエン５０ｍＬに溶解した。
−７８℃に冷却し、予め−７８℃に冷却した四塩化ジルコニウム１．２ｇ（５．１ｍｍｏｌ）のトルエン懸濁液２０ｍＬを滴下した。
滴下後、室温で６時間攪拌し、反応溶液の溶媒を留去した。
得られた残渣をジクロロメタンにより再結晶化したところ、（１，２’−ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（３−トリメチルシリルメチルインデニル）ジルコニウムジクロライド０．９ｇ（１．３３ｍｍｏｌ）を得た。（収率２６％）
^１Ｈ−ＮＭＲ（９０ＭＨｚ，ＣＤＣｌ_３）の測定値
δ：０．０（ｓ，１８Ｈ，トリメチルシリル），１．０２，１．１２（ｓ，１２Ｈ，ジメチルシリレン），２．５１（ｄｄ，４Ｈ，メチレン），７．１−７．６（ｍ，８Ｈ，Ａｒ−Ｈ）
【００４４】
（２）重合
加熱乾燥した１Ｌオートクレーブに、ヘプタン１６０ｍＬ、１−ブテン２００ｍＬ、トリイソブチルアルミニウム０．５ｍｍｏｌ、水素０．０３ＭＰａを導入した。
その後、２０ｍＬのヘプタンに、アルベマール社製メチルアルミノキサン０．５ｍｍｏｌを分散させたもの、２０ｍＬのヘプタンに、上記錯体（１，２’―ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（３−トリメチルシリルインデニル）ジルコニウムジクロリド０．５μｍｏｌを溶解させたものを加えた。
攪拌しながら温度を４０℃に昇温し、５分間攪拌した。
その後、水素を更に０．０７ＭＰａ加え、温度を５５℃まで昇温し、３５分間攪拌した。
そして、メタノール３ｍＬを加え脱圧後、重合溶液を減圧乾燥することにより１−ブテン重合体を得た。
得られた重合体の樹脂特性評価結果を表１及び図１〔極限粘度ｌｏｇ〔η〕（横軸）−流動性ｌｏｇη＊（縦軸）との関係〕に示す。
【００４５】
実施例２
加熱乾燥した１Ｌオートクレーブに、ヘプタン１６０ｍＬ、１−ブテン２００ｍＬ、トリイソブチルアルミニウム０．５ｍｍｏｌ、水素０．０３ＭＰａを導入した。
その後、２０ｍＬのヘプタンに、アルベマール社製メチルアルミノキサン０．５ｍｍｏｌを分散させたもの、２０ｍＬのヘプタンに、上記錯体（１，２’―ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（３−トリメチルシリルインデニル）ジルコニウムジクロリド０．５μｍｏｌを溶解させたものを加えた。
攪拌しながら、２５℃で３分間攪拌した。
その後、水素を更に０．０５ＭＰａ加え、温度を６０℃まで昇温し、１５分間攪拌した。
そして、メタノール３ｍＬを加え脱圧後、重合溶液を減圧乾燥することにより１−ブテン重合体を得た。
得られた重合体の樹脂特性評価結果を表１及び図１に示す。
【００４６】
実施例３
加熱乾燥した１Ｌオートクレーブに、ヘプタン１６０ｍＬ、１−ブテン２００ｍＬ、トリイソブチルアルミニウム０．５ｍｍｏｌ、水素０．０３ＭＰａを導入した。
その後、２０ｍＬのヘプタンに、アルベマール社製メチルアルミノキサン０．５ｍｍｏｌを分散させたもの、２０ｍＬのヘプタンに、上記錯体（１，２’―ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（３−トリメチルシリルインデニル）ジルコニウムジクロリド０．５μｍｏｌを溶解させたものを加えた。
攪拌しながら、２５℃で８分間攪拌した。
その後、水素を更に０．０５ＭＰａ加え、温度を７０℃まで昇温し、１５分間攪拌した。
そして、メタノール３ｍＬを加え脱圧後、重合溶液を減圧乾燥することにより１−ブテン重合体を得た。
得られた重合体の樹脂特性評価結果を表１及び図１に示す。
【００４７】
実施例４
加熱乾燥した１Ｌオートクレーブに、ヘプタン１６０ｍＬ、１−ブテン２００ｍＬ、トリイソブチルアルミニウム０．５ｍｍｏｌ、水素０．０３ＭＰａを導入した。
その後、２０ｍＬのヘプタンに、アルベマール社製メチルアルミノキサン０．５ｍｍｏｌを分散させたもの、２０ｍＬのヘプタンに、上記錯体（１，２’―ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（３−トリメチルシリルインデニル）ジルコニウムジクロリド０．５μｍｏｌを溶解させたものを加えた。
攪拌しながら、温度を５０℃に昇温し、５分間攪拌した。
その後、水素を更に０．０７ＭＰａ加え、温度を６０℃まで昇温し、１５分間攪拌した。
そして、メタノール３ｍＬを加え脱圧後、重合溶液を減圧乾燥することにより１−ブテン重合体を得た。
得られた重合体の樹脂特性評価結果を表１及び図１に示す。
【００４８】
比較例１
加熱乾燥した１Ｌオートクレーブに、ヘプタン１６０ｍＬ、１−ブテン２００ｍＬ、トリイソブチルアルミニウム０．５ｍｍｏｌ、水素０．０１ＭＰａを導入した。
その後、２０ｍＬのヘプタンに、アルベマール社製メチルアルミノキサン０．２５ｍｍｏｌを分散させたもの、２０ｍＬのヘプタンに、上記錯体（１，２’―ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（３−トリメチルシリルインデニル）ジルコニウムジクロリド０．２５μｍｏｌを溶解させたものを加えた。
攪拌しながら、温度を６０℃に昇温し、５分間攪拌した。
そして、メタノール３ｍＬを加え脱圧後、重合溶液を減圧乾燥することにより１−ブテン重合体を得た。
得られた重合体の樹脂特性評価結果を表１及び図１に示す。
【００４９】
比較例２
加熱乾燥した１Ｌオートクレーブに、ヘプタン１６０ｍＬ、１−ブテン２００ｍＬ、トリイソブチルアルミニウム０．５ｍｍｏｌ、水素０．０３ＭＰａを導入した。
その後、２０ｍＬのヘプタンに、アルベマール社製メチルアルミノキサン０．２５ｍｍｏｌを分散させたもの、２０ｍＬのヘプタンに、上記錯体（１，２’―ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（３−トリメチルシリルインデニル）ジルコニウムジクロリド０．２５μｍｏｌを溶解させたものを加えた。
攪拌しながら、温度を６０℃に昇温し、５分間攪拌した。
そして、メタノール３ｍＬを加え脱圧後、重合溶液を減圧乾燥することにより１−ブテン重合体を得た。
得られた重合体の樹脂特性評価結果を表１及び図１に示す。
【００５０】
比較例３
加熱乾燥した１Ｌオートクレーブに、ヘプタン１６０ｍＬ、１−ブテン２００ｍＬ、トリイソブチルアルミニウム０．５ｍｍｏｌ、水素０．０３ＭＰａを導入した。
その後、２０ｍＬのヘプタンにアルベマール社製メチルアルミノキサン０．５０ｍｍｏｌを分散させたもの、２０ｍＬのヘプタンに、上記錯体（１，２’―ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（３−トリメチルシリルインデニル）ジルコニウムジクロリド０．５０μｍｏｌ）を溶解させたものを加えた。
攪拌しながら、温度を６０℃に昇温し、３０分間攪拌した。
そして、メタノール３ｍＬを加え脱圧後、重合溶液を減圧乾燥することにより１−ブテン重合体を得た。
得られた重合体の樹脂特性評価結果を表１及び図１に示す。
【００５１】
比較例４
加熱乾燥した１Ｌオートクレーブに、ヘプタン１６０ｍＬ、１−ブテン２００ｍＬ、トリイソブチルアルミニウム０．５ｍｍｏｌ、水素０．０３ＭＰａを導入した。
その後、２０ｍＬのヘプタンに、アルベマール社製メチルアルミノキサン０．５０ｍｍｏｌを分散させたもの、２０ｍＬのヘプタンに、上記錯体（１，２’―ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（３−トリメチルシリルインデニル）ジルコニウムジクロリド０．５０μｍｏｌを溶解させたものを加えた。
攪拌しながら、温度を６０℃に昇温し、６０分間攪拌した。
そして、メタノール３ｍＬを加え脱圧後、重合溶液を減圧乾燥することにより１−ブテン重合体を得た。
得られた重合体の樹脂特性評価結果を表１及び図１に示す。
【００５２】
比較例５
加熱乾燥した１Ｌオートクレーブに、ヘプタン１６０ｍＬ、１−ブテン２００ｍＬ、トリイソブチルアルミニウム０．５ｍｍｏｌ、水素０．０３ＭＰａを導入した。
その後、２０ｍＬのヘプタンに、アルベマール社製メチルアルミノキサン０．５ｍｍｏｌを分散させたもの、２０ｍＬのヘプタンに、上記錯体（１，２’―ジメチルシリレン）（２，１’−ジメチルシリレン）−ビス（３−トリメチルシリルインデニル）ジルコニウムジクロリド０．５μｍｏｌを溶解させたものを加えた。
攪拌しながら、温度を５０℃に昇温し、５分間攪拌した。
その後、温度を６０℃まで昇温し１５分間攪拌した。
そして、メタノール３ｍＬを加え脱圧後、重合溶液を減圧乾燥することにより１−ブテン重合体を得た。
得られた重合体の樹脂特性評価結果を表１及び図１に示す。
実施例１、２及び４は、比較例１及び５に比べて同等の極限粘度ｌｏｇ〔η〕（分子量）であるにもかかわらず、流動性の指標ｌｏｇη＊が低く、流動性がよいことが分かる。
【００５３】
【表１】

【００５４】
【発明の効果】
本発明の１−ブテン系重合体は、特定のメタロセン触媒と特定の重合方法を組み合わせることにより、分子量分布が広がり、射出やシート、フィルム等の高速成形に対応できる。
【図面の簡単な説明】
【図１】図１は、実施例１〜４及び比較例１〜５の極限粘度ｌｏｇ〔η〕（横軸）−流動性ｌｏｇη＊（縦軸）との関係を示す図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a 1-butene polymer, and more particularly, to a 1-butene polymer having a wide molecular weight distribution and capable of coping with high-speed molding, and a method for producing the same.
[0002]
[Prior art]
In order to improve the productivity of a molded article using a poly (butene-1) -based material, the molding speed has been further increased, and a raw material resin capable of responding to the molding speed has been demanded.
The technology for producing poly (butene-1) is known (for example, see Patent Document 1).
In addition, commercially available poly (butene-1) is produced by a Ziegler-Natta catalyst and is used as a pipe, a sealant, and a resin modifier. ing.
Further, as a sealant material having good low-temperature heat sealability, a metallocene-based propylene-butene random copolymer (for example, see Patent Document 2) or a metallocene-based low-crystalline poly (butene-1) (for example, see Patent Document 3) ) Has been proposed, but because of its narrow molecular weight distribution, it cannot be said that it has moldability sufficient for a molding machine that has been increasingly used in recent years.
[0003]
[Patent Document 1]
Japanese Patent Publication No. 64-81804
[Patent Document 2]
JP-A-8-73531
[Patent Document 3]
JP-A-2002-322213
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a 1-butene polymer having a wide molecular weight distribution and capable of coping with high-speed molding, and a method for producing the same.
[0005]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object, and as a result, by combining a specific metallocene catalyst and a specific polymerization method, it is possible to broaden the molecular weight distribution and respond to high-speed molding. They have found that a butene-based polymer can be obtained, and have completed the present invention.
[0006]
That is, the present invention relates to the following 1-butene-based polymer and a method for producing the same.
1. 1-butene polymer satisfying the following conditions (1) to (4).
(1) Using a differential scanning calorimeter (DSC), melt at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then increase the temperature at 10 ° C./min. Crystalline resin having no melting point (Tm-P) defined as the peak top of the
(2) Stereoregularity index (mmmm) / [(mmrr) + (rmmr)] is 20 or less
(3) Intrinsic viscosity [η] is 0.1 to 4.0 dl / g
(4) The molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) is 4.0 or more.
2. The 1-butene-based polymer according to the above item 1, wherein the 1-butene-based polymer is a homopolymer and the mesopentad fraction (mmmm) is 20 to 90 mol%.
3. 3. The 1-butene polymer according to the above 2, which satisfies the following formula.
(Mmmm) ≦ 90−2 × (rr)
Here, (rr) indicates a racemic triad fraction (mol%).
4. 1 according to any one of claims 1 to 3, wherein 1-butene or 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) are subjected to multistage polymerization. -A method for producing a butene polymer.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
The 1-butene polymer of the present invention is a polymer having a comonomer content of 0 to 10 mol%, preferably 0 to 5 mol%, more preferably 0 to 3 mol%.
When the content of the comonomer exceeds 10 mol%, the amount of the crystal component is greatly reduced, and the heat resistance may be reduced, or poor cutting may be caused at the time of pelletizing.
The melting point (Tm-P) of the 1-butene-based polymer of the present invention is such that the melting point (Tm-P), which is a suitable index for determining the range of the soft resin, is not observed or falls within a range of 0 to 100 ° C. Present, preferably in the range of 0-80 ° C.
The melting point (Tm-P) of the 1-butene polymer can be determined by a differential scanning calorimeter (DSC) measurement.
That is, using a differential scanning calorimeter (DSC-7, manufactured by Perkin-Elmer Co., Ltd.), 10 mg of a sample was previously melted at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then cooled at a rate of 10 ° C./min. After holding for 5 minutes, the melting endotherm obtained by raising the temperature at 10 ° C./min is defined as (ΔH−P).
The peak of the peak observed at the highest temperature in the melting endothermic curve obtained at this time is the melting point (Tm-P).
Such physical properties can be achieved by using the double-bridged metallocene catalyst of the present invention.
When the melting point (Tm-P) is observed, sufficient low-temperature heat sealability cannot be obtained unless it is in the range of 0 to 100 ° C.
[0008]
Further, the 1-butene-based polymer used in the present invention may have a melting point (Tm-D) in the range of 0 to 100 ° C from the viewpoint of softness.
The melting point (Tm-D) is preferably in the range of 0 to 80C.
The melting point (Tm-D) can be determined by DSC measurement.
That is, by using a differential scanning calorimeter (DSC-7, manufactured by Perkin-Elmer Co., Ltd.), a sample of 10 mg was previously held at −10 ° C. for 5 minutes under a nitrogen atmosphere, and then heated at a rate of 10 ° C./min. The obtained melting endotherm is defined as (ΔH−D).
In addition, the peak of the peak observed at the highest temperature in the melting endothermic curve obtained at this time is the melting point (Tm-D).
(Tm-D) is preferably 90 ° C. or less because of excellent flexibility.
(Tm-D) is an index indicating whether or not the material is soft. If this value is large, the elastic modulus is high and the softness is low.
This value can be achieved by using a di-bridged metallocene catalyst.
[0009]
The stereoregularity index (mmmm) / [(mmrr) + (rmmr)] of the 1-butene polymer of the present invention is 20 or less, preferably 18 or less, more preferably 15 or less.
Setting the stereoregularity index (mmmm) / [(mmrr) + (rmmr)] to 20 or less can be achieved by using the double-bridged metallocene catalyst of the present invention.
If this value exceeds 20, the flexibility, the low-temperature heat sealing property, and the hot tack property are reduced.
[0010]
In the present invention, the mesopentad fraction (mmmm) and the abnormal insertion content (1,4 insertion fraction) are described in “Polymer Journal, 16, 717 (1984)” reported by Asakura et al. "Macromol. Chem. Phys., C29, 201 (1989)" reported by Randall et al. It was determined according to the method proposed by Busico et al. In “Macromol. Chem. Phys., 198, 1257 (1997)”.
That is,^ThirteenThe signals of the methylene group and the methine group were measured using C nuclear magnetic resonance spectrum to determine the mesopentad fraction and the abnormal insertion content in the 1-butene polymer molecule.
(^ThirteenMeasurement of C nuclear magnetic resonance spectrum)
A 220 mg sample is collected in a 10 mm diameter NMR sample tube, and 3 mL of a mixed solvent of 1,2,4-trichlorobenzene / deuterated benzene (90/10% by volume) is added.
After uniformly dissolving at 140 ° C using an aluminum block heater,^ThirteenMeasure the CNMR spectrum.
^ThirteenThe CNMR measurement conditions are as follows.
^ThirteenCNMR system JEOL EX400 (400MHz NMR system)
Pulse width 7.5μs (45 degree pulse)
Pulse repetition time 4 seconds
Accumulation 1,000 times
Measurement temperature 130 ° C
In the present invention, the stereoregularity index (mmmm) / [(mmrr + rmmr)] was calculated from the measured values of (mmmm), (mmmr) and (rmmr) by the above method.
The racemic triad fraction (rr) was also calculated by the above method.
[0011]
The 1-butene polymer of the present invention has an intrinsic viscosity [η] of 0.1 to 4.0 dl / g, preferably 0.2 to 3.5 dl / g, more preferably 0.3 to 3.5 dl / g. 3.0 dl / g.
As the method of controlling the intrinsic viscosity [η], the higher the 1-butene concentration, the lower the polymerization temperature, the less the chain transfer agent such as hydrogen or organoaluminum, the higher the intrinsic viscosity [η], the higher the intrinsic viscosity [η]. These conditions are adjusted so as to be in the range of the intrinsic viscosity [η].
Specifically, the molecular weight increases under a combination of a condition in which the 1-butene concentration is high, the polymerization temperature is low, and the chain transfer agent is small, and conversely, the 1-butene concentration is low, the polymerization temperature is high, and the chain transfer agent is large. The combination of conditions results in a lower molecular weight.
If the intrinsic viscosity [η] is less than 0.1, stickiness will increase, and if it exceeds 4.0, fluidity will decrease and moldability may deteriorate.
(Measurement of intrinsic viscosity [η])
It measured at 135 degreeC in tetralin solvent using the VMR-053 type automatic viscometer of Rigo Co., Ltd.
[0012]
The 1-butene polymer of the present invention has a molecular weight distribution (Mw / Mn) of 4.0 to 20, preferably 4.5 to 20, and more preferably, a molecular weight distribution measured by a gel permeation chromatography (GPC) method. Is 5.0 to 20.
Mw indicates a weight average molecular weight, and Mn indicates a number average molecular weight.
If the molecular weight distribution (Mw / Mn) is less than 4.0, the fluidity will be poor and the moldability will be poor.
If it exceeds 20, sticky components may be generated.
[0013]
In order to broaden the molecular weight distribution (Mw / Mn), it is usually necessary to use two-stage or more multi-stage polymerization in which the first-stage polymerization conditions and the second-stage polymerization conditions are changed, and to greatly change the molecular weight of the polymer produced in each stage. There is.
In order to control the molecular weight, it is particularly necessary to control the chain transfer reaction among the polymerization reactions.
As the chain transfer agent, various organoaluminum compounds are known, but the effect is small, and when the amount of the organoaluminum compound is increased during the polymerization, the catalyst residue increases, and the quality such as transparency and hygroscopicity is increased. Hydrogen is preferably used because it has an adverse effect on physical properties, and the higher the hydrogen supply amount (pressure), the lower the molecular weight.
Also, the lower the 1-butene concentration and the higher the polymerization temperature, the higher the chain transfer reaction rate and the lower the molecular weight.
Therefore, as a method for controlling the molecular weight distribution, a polymerization catalyst comprising a (A) transition metal compound represented by the general formula (1) and a compound capable of forming an ionic complex by reacting with the (B) (A) component is described below. In the presence of hydrogen pressure 0-0.5 MPa, polymerization temperature 10-150 [deg.] C., 1-butene concentration 10-100% by mass, and a combination having a large molecular weight or a small molecular weight must be set. .
The conditions must be changed such that the hydrogen pressure is set to a difference of 0.01 MPa or more, the polymerization temperature is set to a difference of 10 ° C. or more, and the 1-butene concentration is set to a difference of 10 mass% or more in each polymerization stage.
Since the molecular weight distribution is also affected by the polymerization amount ratio of each polymerization stage, the polymerization amount ratio of each polymerization stage preferably has a difference of 5% by mass or more.
Furthermore, each of the modifying factors may be used alone or in combination. However, in order to make the molecular weight distribution (Mw / Mn) 4.0 or more, it is necessary to combine two or more types of condition modification.
In particular, a combination of changing the hydrogen concentration and the polymerization temperature is preferable.
[0014]
The molecular weight distribution (Mw / Mn) is a value calculated from the mass average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene measured by the GPC method using the following apparatus and conditions.
GPC measuring device
Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C Measurement conditions
Solvent: 1,2,4-trichlorobenzene
Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min
Sample concentration: 2.2 mg / milliliter
Injection volume: 160 microliter
Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver. 1.0)
[0015]
When the 1-butene polymer of the present invention is a homopolymer, the mesopentad fraction (mmmm) is 20 to 90 mol%, preferably 60 to 90 mol%, more preferably 65 to 85 mol%. is there.
This value can be controlled by using a di-bridged metallocene catalyst.
If the mesopentad fraction is less than 20 mol%, sufficient heat sealing strength may not be obtained.
If it exceeds 90 mol%, sufficient low-temperature heat sealability may not be obtained.
[0016]
The 1-butene polymer of the present invention needs to satisfy the following formula.
(Mmmm) ≦ 90−2 × (rr)
Here, (rr) indicates a racemic triad fraction (mol%).
In order for the 1-butene polymer of the present invention to satisfy the above formula, the mesopentad fraction (mmmm) and / or the racemic triad fraction (rr) may be controlled by using a di-bridged metallocene catalyst.
When the 1-butene polymer does not satisfy the above formula, sufficient low-temperature heat sealability may not be satisfied.
[0017]
(Melt viscoelasticity test method)
A test piece (a disk having a diameter of 25 mm and a thickness of 1 mm) was prepared by press molding.
A test was performed using a melt viscoelasticity measurement device manufactured by Rheometric Scientific, and the measurement shape was a plate and cone having a radius of 12.5 mm.
The measurement temperature was 180 ° C., the strain was 20%, the relationship between the angular velocity (ω) and the viscosity was determined, and the viscosity at ω = 10 rad / sec was defined as η *.
The relationship between log [η] (horizontal axis) and log η * (vertical axis) was determined.
From this relation, it is shown that the lower the log η * at the same log [η], the better the fluidity.
[0018]
Examples of the method for producing the 1-butene polymer of the present invention include a method using a di-bridged metallocene catalyst.
The di-bridged metallocene catalyst is a metallocene catalyst obtained by combining a transition metal compound forming a cross-linked structure via two cross-linking groups with a promoter, among metallocene catalysts.
Specifically, (A) general formula (I)
[0019]
Embedded image

[0020]
[Wherein, M represents a metal element belonging to Group 4 of the periodic table;¹And X²Represents a σ-binding ligand, which may be the same or different.
R¹And R²Represents a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a boron-containing hydrocarbon group, respectively.
R³~ R¹⁰Represents a hydrogen, a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a boron-containing hydrocarbon group, respectively.
E¹And E²Is a divalent bridging group that bonds two ligands, and represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, and a germanium-containing group. May be the same or different. ]
(B) (B-1) a compound capable of reacting with the transition metal compound of the component (A) or a derivative thereof to form an ionic complex, and (B-2) A catalyst containing a component selected from aluminoxanes is exemplified.
[0021]
In the transition metal compound represented by the general formula (I), M represents a metal element belonging to Group 4 of the periodic table, and specific examples thereof include titanium, zirconium, and hafnium.
X¹And X²Specific examples include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a silicon-containing group having 1 to 20 carbon atoms.
Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom.
Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an alkenyl group such as a vinyl group and a propenyl group; a benzyl group and a phenylethyl group. And aryl groups such as phenyl and tolyl.
Among them, an alkyl group such as a methyl group, an ethyl group, and a propyl group, and a halogen atom such as a chlorine atom group are preferable.
Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.
Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a methylphenoxy group, a phenylmethoxy group, a phenylethoxy group and the like.
Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon-substituted silyl groups such as methylsilyl and phenylsilyl; dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl; trimethylsilyl, triethylsilyl, Tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methylphenyldisilyl, tritolylsilyl, trinaphthylsilyl and other trihydrocarbon-substituted silyl groups; carbonization of trimethylsilyl ether groups and the like A silyl ether group of a hydrogen-substituted silyl group; a silicon-substituted alkyl group such as a trimethylsilylmethyl group; and a silicon-substituted aryl group such as a trimethylsilylphenyl group.
Among them, a trimethylsilyl group, a phenethyldimethylsilyl group and the like are preferable.
[0022]
E¹And E²Specific examples include a dimethylsilylene group, a diphenylsilylene group, a methylphenylsilylene group, a dimethylgermylene group, a tetramethyldisilylene group, and a diphenyldisilylene group.
[0023]
The transition metal compound represented by the general formula (I) preferably has a double-bridged bisindene derivative as a ligand, and a cross-linking group between the ligands contains silicon.
Specific examples of the transition metal compound represented by the general formula (I) include (1,2′-isopropylidene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′- Ethylene) (2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride , (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) Bis (3-i-propylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis 3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2 , 1′-Isopropylidene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-i-propylindenyl) zirconium dichloride , (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) ) -Bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1, '-Dimethylsilylene) (2,1'-isopropylidene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-i- (Propylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2, 1'-methylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-methylindenyl) zirconium dichloride and the like, and the like Compounds obtained by substituting zirconium in a compound with titanium or hafnium can be mentioned.
Of course, it is not limited to these.
[0024]
Next, as the component (B-1) of the component (B), any compound can be used as long as it can react with the transition metal compound of the component (A) to form an ionic complex. Although it can be used, the following general formula (II) or (III)
([L¹-R¹²]^{k +})_a([Z]⁻)_b                      ... (II)
([L²]^{k +})_a([Z]⁻)_b                                ... (III)
(However, L²Is M², R^ThirteenR¹⁴M³, R^Fifteen ₃C or R¹⁶M³It is. )
[In the formulas (III) and (IV), L¹Is a Lewis base, [Z]⁻Is a non-coordinating anion [Z¹]⁻And [Z²]⁻, Where [Z¹]⁻Is an anion in which a plurality of groups are bonded to an element, ie, [M¹G¹G²... G^f]⁻(Where M¹Represents an element of Groups 5 to 15 of the periodic table, preferably an element of Groups 13 to 15 of the periodic table. G¹~ G^fRepresents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 20 carbon atoms. An aryloxy group, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an organic metalloid group, Or a heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms. G¹~ G^fTwo or more of them may form a ring. f is [(center metal M¹Valence) +1]. ),
[Z²]⁻Is a conjugate base of a Bronsted acid alone or a combination of a Bronsted acid and a Lewis acid having a logarithm (pKa) of the reciprocal of the acid dissociation constant of −10 or less, or a conjugate base of an acid generally defined as a superstrong acid. Show. Further, a Lewis base may be coordinated.
Also, R¹²Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group;^ThirteenAnd R¹⁴Is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group,^FifteenRepresents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group.
R¹⁶Represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine.
k is [L¹-R¹²], [L²Is an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a).
M²Is a group containing elements from Groups 1 to 3, 11 to 13, and 17 of the periodic table;³Represents an element in Groups 7 to 12 of the periodic table. ]
Can be suitably used.
[0025]
Where L¹Specific examples include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine and p-bromo. Amines such as -N, N-dimethylaniline and p-nitro-N, N-dimethylaniline; phosphines such as triethylphosphine, triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiophene; and esters such as ethyl benzoate. And nitriles such as acetonitrile and benzonitrile.
[0026]
R¹²Specific examples of R include hydrogen, methyl, ethyl, benzyl, and trityl.^Thirteen, R¹⁴Specific examples include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group.
R^FifteenSpecific examples of R include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group.¹⁶Specific examples thereof include tetraphenylporphine, phthalocyanine, allyl, methallyl and the like.
Also, M²Are Li, Na, K, Ag, Cu, Br, I, I₃Etc., and M³Specific examples include Mn, Fe, Co, Ni, Zn and the like.
[0027]
Also, [Z¹]⁻, That is, [M¹G¹G²... G^f], M¹Specific examples include B, Al, Si, P, As, Sb and the like, preferably B and Al.
G¹, G²~ G^fSpecific examples include: dimethylamino group, diethylamino group, etc. as dialkylamino group, methoxy group, ethoxy group, n-butoxy group, phenoxy group, etc. as alkoxy group or aryloxy group, and methyl group, ethyl group as hydrocarbon group , N-propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t-butylphenyl, 3,5- Fluorine, chlorine, bromine, iodine as a halogen atom such as a dimethylphenyl group, and p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5-trifluorophenyl as a hydrocarbon group containing a hetero atom Group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, bis Trimethylsilyl) methyl group, pentamethyl antimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexyl antimony group, diphenyl boron, and the like.
[0028]
In addition, a non-coordinating anion, that is, a conjugated base of a Bronsted acid having a pKa of -10 or less alone or a combination of a Bronsted acid and a Lewis acid [Z²]⁻As a specific example of trifluoromethanesulfonic acid anion (CF₃SO₃)⁻, Bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO₄)⁻, Trifluoroacetate anion (CF₃CO₂)⁻, Hexafluoroantimony anion (SbF₆)⁻, Fluorosulfonic acid anion (FSO₃)⁻, Chlorosulfonic acid anion (ClSO₃)⁻, Fluorosulfonic acid anion / 5-antimony fluoride (FSO₃/ SbF₅  )⁻, Fluorosulfonate anion / 5-arsenic fluoride (FSO₃/ AsF₅)⁻, Trifluoromethanesulfonic acid / 5-antimony fluoride (CF₃SO₃/ SbF₅)⁻And the like.
[0029]
Specific examples of the ionic compound which forms an ionic complex by reacting with the transition metal compound of the component (A), that is, triethyl tetrakis (pentafluorophenyl) borate, are examples of the compound of the component (B-1). Ammonium, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate Benzyl (tri-n-butyl) ammonium, tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Examples include phenyl (methyl) ammonium, methylanilinium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, and methylpyridinium tetrakis (pentafluorophenyl) borate. Can be
As the component (B-1), a compound capable of forming an ionic complex by reacting with the transition metal compound of the component (A) may be used alone or in combination of two or more. .
[0030]
On the other hand, as the aluminoxane of the component (B-2), the general formula (IV)
[0031]
Embedded image

[0032]
(Where R¹¹Represents a hydrocarbon group or a halogen atom such as an alkyl group, an alkenyl group, an aryl group, an arylalkyl group or the like having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, w represents an average degree of polymerization, usually 2 to 50, Preferably it is an integer of 2 to 40.
In addition, each R¹¹May be the same or different. )
And a chain aluminoxane represented by the general formula (V):
[0033]
Embedded image

[0034]
(Where R¹¹And w are the same as those in the general formula (IV). )
And a cyclic aluminoxane represented by
These aluminoxanes may be used alone or in a combination of two or more.
[0035]
When the compound (B-1) is used as the catalyst component (B), the molar ratio of the catalyst component (A) to the catalyst component (B) is preferably 10: 1 to 1: 100. Preferably, the ratio is in the range of 2: 1 to 1:10. If the ratio deviates from the above range, the catalyst cost per unit mass of polymer increases, which is not practical.
When the compound (B-2) is used, the molar ratio is preferably in the range of 1: 1 to 1: 1,000,000, and more preferably 1: 10-1: 10000.
If the ratio is out of this range, the cost of the catalyst per unit mass of polymer increases, which is not practical.
Further, as the catalyst component (B), the components (B-1) and (B-2) can be used alone or in combination of two or more.
[0036]
As the polymerization catalyst for producing the 1-butene polymer, an organoaluminum compound can be used as the component (C) in addition to the components (A) and (B).
Here, the organoaluminum compound of the component (C) is represented by the general formula (VI):
R¹⁸ _vAlJ_3-v            ... (VI)
[Wherein, R¹⁸Represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group or a halogen atom having 6 to 20 carbon atoms, and v is an integer of 1 to 3]
The compound shown by is used.
Specific examples of the compound represented by the general formula (VI) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride , Diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.
[0037]
These organoaluminum compounds may be used alone or in combination of two or more.
The molar ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2000, and still more preferably 1:10 to 1: 1. : A range of 1000 is desirable.
By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.
In the present invention, at least one of the catalyst components is SiO 2₂, Al₂O₃Can be used by being supported on a carrier such as
The type of the carrier is not particularly limited, and any of an inorganic oxide carrier, another inorganic carrier and an organic carrier can be used, and an inorganic oxide carrier or another inorganic carrier is particularly preferable.
[0038]
As the inorganic oxide carrier, specifically, SiO 2₂, Al₂O₃, MgO, ZrO₂, TiO₂, Fe₂O3, B₂O3, CaO, ZnO, BaO, ThO₂And mixtures thereof, for example, silica alumina, zeolite, ferrite, glass fiber and the like.
Among these, especially SiO 2₂, Al₂O₃Is preferred.
The inorganic oxide carrier may contain a small amount of carbonate, nitrate, sulfate, or the like.
[0039]
The 1-butene polymer of the present invention is obtained by homopolymerizing 1-butene or 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) using the above catalyst. ) Can be produced by copolymerizing When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane and octane And halogenated hydrocarbons such as chloroform and dichloromethane.
These solvents may be used alone or in a combination of two or more.
In addition, depending on the polymerization method, it can be carried out without a solvent.
In the polymerization, preliminary polymerization can be performed using the polymerization catalyst.
The prepolymerization can be carried out by bringing a small amount of olefin into contact with the solid catalyst component, for example, but the method is not particularly limited, and a known method can be used.
The olefin used for the prepolymerization is not particularly limited, and examples thereof include ethylene, α-olefins having 3 to 20 carbon atoms, and mixtures thereof. The same olefin as the olefin used in the polymerization may be used. It is advantageous.
The pre-polymerization temperature is usually -20 to 200C, preferably -10 to 130C, more preferably 0 to 80C.
In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer, or the like can be used as a solvent.
Particularly preferred among these are aliphatic hydrocarbons.
Further, the prepolymerization may be performed without a solvent.
In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of the prepolymerized product is 0.2 deciliter / g or more, especially 0.5 deciliter / g or more, and per 1 mmol of transition metal component in the catalyst. It is desirable to adjust the conditions so that the amount of the prepolymerized product is 1 to 10,000 g, especially 10 to 1,000 g.
[0040]
The polymerization method in the method for producing a 1-butene polymer of the present invention is not particularly limited, and can be applied to any of solution polymerization, slurry polymerization, gas phase polymerization, bulk polymerization, and the like. May be either batch polymerization or continuous polymerization.
[0041]
【Example】
Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
[0042]
Mesopentad fraction (mmmm), racemic triad fraction (rr), 90-2 × (rr), 1,4-abnormal insertion amount, stereoregularity index (mmmm) / [( mmrr) + (rmmr)], intrinsic viscosity [η], log η^*, Molecular weight distribution (Mw / Mn), melting point (Tm-P) and (Tm-D), melting endotherm (ΔHP) and (ΔH-D) were measured by the methods described in the text of the specification.
[0043]
Example 1
(1) Synthesis of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethyl-indenyl) zirconium dichloride
(1) Synthesis of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (indene)
Under a nitrogen stream, 100 mL of THF and 5.0 g (206 mmol) of Mg were added to a 1 L three-necked flask.
Next, 0.1 mL of 1,2-dibromoethane was added and stirred to activate Mg.
After stirring for 30 minutes, the solvent was extracted, and 100 mL of THF was newly added.
Further, a solution of 10.0 g (51.3 mmol) of 2-bromoindene in 250 mL of THF was added dropwise over 2 hours.
After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, cooled to -78 ° C, and a solution of 6.2 mL (51.3 mmol) of dichlorodimethylsilane in 100 mL of THF was added dropwise over 1 hour.
After stirring for 15 hours, the solvent was distilled off, the residue was extracted with 300 mL of hexane, and the solvent was distilled off to obtain 9.6 g (46.2 mmol) of 2-chloromethylsilylindene. (Yield 90%)
Next, 400 mL of THF and 9.6 g of 2-chloromethylsilylindene were added to a 1 L three-necked flask under a nitrogen stream, and the mixture was cooled to -78 ° C, and LiN (trimethylsilyl) was added.₂Was added dropwise to a THF solution (1.0 M) of 46.2 mL (46.2 mmol).
After stirring at room temperature for 15 hours, the solvent was distilled off, extracted with 300 mL of hexane, and the solvent was distilled off to obtain (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indene). 2.5 g (7.2 mmol) were obtained. (Yield 31%)
¹H-NMR (90 MHz, CDCl₃) Measurements
δ: -0.69, 0.73 (12H, dimethylsilylene), 3.66 (4H, -CH₂−), 7.17 (8H, Ar-H)
(2) Synthesis of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride
To a Schlenk bottle, 2.5 g (7.2 mmol) of (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (indene) and 100 mL of ether were added.
After cooling to −78 ° C. and adding 9.0 mL (14.8 mmol) of n-BuLi (hexane solution 1.6 M), the mixture was stirred at room temperature for 12 hours.
The solvent was distilled off, and the obtained solid was washed with 20 mL of hexane to quantitatively obtain a lithium salt.
In a Schlenk bottle, a lithium salt of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indene) (6.97 mmol) was dissolved in 50 mL of THF, and cooled to −78 ° C.
Next, 2.1 mL (14.2 mmol) of iodomethyltrimethylsilane was slowly added dropwise, followed by stirring at room temperature for 12 hours.
The solvent was distilled off, 50 mL of ether was added, and the mixture was washed with a saturated ammonium chloride solution.
After liquid separation, the organic phase was dried, the solvent was removed, and 3.04 g (5.9 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene). Got. (Yield 84%)
Under a nitrogen stream, 3.04 g (5.9 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) and 50 mL of ether were placed in a Schlenk bottle. Was added.
After cooling to −78 ° C. and adding 7.6 mL (11.8 mmol) of n-BuLi (hexane solution 1.54 M), the mixture was stirred at room temperature for 12 hours.
The solvent was distilled off, and the obtained solid was washed with 40 mL of hexane to obtain 3.06 g (5.1 mmol) of an ether adduct of a lithium salt. (86% yield)
¹H-NMR (90 MHz, THF-d₈) Measurements
δ: 0.04 (s, 18H, trimethylsilyl), 0.48 (s, 12H, dimethylsilylene), 1.10 (t, 6H, methyl), 2.59 (s, 4H, methylene), 3.38 (Q, 4H, methylene), 6.2-7.7 (m, 8H, Ar-H)
Under a nitrogen stream, the above-mentioned ether adduct of a lithium salt was dissolved in 50 mL of toluene.
The mixture was cooled to −78 ° C., and 20 mL of a toluene suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride previously cooled to −78 ° C. was added dropwise.
After the dropwise addition, the mixture was stirred at room temperature for 6 hours, and the solvent of the reaction solution was distilled off.
When the obtained residue was recrystallized from dichloromethane, 0.9 g (1.33 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride was obtained. ) Got. (26% yield)
¹H-NMR (90 MHz, CDCl₃) Measurements
δ: 0.0 (s, 18H, trimethylsilyl), 1.02, 1.12 (s, 12H, dimethylsilylene), 2.51 (dd, 4H, methylene), 7.1-7.6 (m, 8H, Ar-H)
[0044]
(2) polymerization
160 mL of heptane, 200 mL of 1-butene, 0.5 mmol of triisobutylaluminum, and 0.03 MPa of hydrogen were introduced into a heated and dried 1 L autoclave.
Then, 0.5 mmol of methylaluminoxane manufactured by Albemarle Company was dispersed in 20 mL of heptane, and the above complex (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3) was added to 20 mL of heptane. (Trimethylsilylindenyl) zirconium dichloride (0.5 μmol) was added.
The temperature was raised to 40 ° C. while stirring, and the mixture was stirred for 5 minutes.
Thereafter, 0.07 MPa of hydrogen was further added, the temperature was raised to 55 ° C., and the mixture was stirred for 35 minutes.
After adding 3 mL of methanol and depressurizing, the polymerization solution was dried under reduced pressure to obtain a 1-butene polymer.
The results of evaluation of the resin properties of the obtained polymer are shown in Table 1 and FIG. 1 [Relationship with intrinsic viscosity log [η] (horizontal axis) -fluidity log η * (vertical axis)].
[0045]
Example 2
160 mL of heptane, 200 mL of 1-butene, 0.5 mmol of triisobutylaluminum, and 0.03 MPa of hydrogen were introduced into a heated and dried 1 L autoclave.
Then, 0.5 mmol of methylaluminoxane manufactured by Albemarle Company was dispersed in 20 mL of heptane, and the above complex (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3) was added to 20 mL of heptane. (Trimethylsilylindenyl) zirconium dichloride (0.5 μmol) was added.
While stirring, the mixture was stirred at 25 ° C. for 3 minutes.
Thereafter, 0.05 MPa of hydrogen was further added, the temperature was raised to 60 ° C., and the mixture was stirred for 15 minutes.
After adding 3 mL of methanol and depressurizing, the polymerization solution was dried under reduced pressure to obtain a 1-butene polymer.
Table 1 and FIG. 1 show the evaluation results of the resin properties of the obtained polymer.
[0046]
Example 3
160 mL of heptane, 200 mL of 1-butene, 0.5 mmol of triisobutylaluminum, and 0.03 MPa of hydrogen were introduced into a heated and dried 1 L autoclave.
Then, 0.5 mmol of methylaluminoxane manufactured by Albemarle Company was dispersed in 20 mL of heptane, and the above complex (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3) was added to 20 mL of heptane. (Trimethylsilylindenyl) zirconium dichloride (0.5 μmol) was added.
While stirring, the mixture was stirred at 25 ° C for 8 minutes.
Thereafter, 0.05 MPa of hydrogen was further added, the temperature was raised to 70 ° C., and the mixture was stirred for 15 minutes.
After adding 3 mL of methanol and depressurizing, the polymerization solution was dried under reduced pressure to obtain a 1-butene polymer.
Table 1 and FIG. 1 show the evaluation results of the resin properties of the obtained polymer.
[0047]
Example 4
160 mL of heptane, 200 mL of 1-butene, 0.5 mmol of triisobutylaluminum, and 0.03 MPa of hydrogen were introduced into a heated and dried 1 L autoclave.
Then, 0.5 mmol of methylaluminoxane manufactured by Albemarle Company was dispersed in 20 mL of heptane, and the above complex (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3) was added to 20 mL of heptane. (Trimethylsilylindenyl) zirconium dichloride (0.5 μmol) was added.
While stirring, the temperature was raised to 50 ° C., and the mixture was stirred for 5 minutes.
Thereafter, 0.07 MPa of hydrogen was further added, the temperature was raised to 60 ° C., and the mixture was stirred for 15 minutes.
After adding 3 mL of methanol and depressurizing, the polymerization solution was dried under reduced pressure to obtain a 1-butene polymer.
Table 1 and FIG. 1 show the evaluation results of the resin properties of the obtained polymer.
[0048]
Comparative Example 1
160 mL of heptane, 200 mL of 1-butene, 0.5 mmol of triisobutylaluminum, and 0.01 MPa of hydrogen were introduced into the heated and dried 1 L autoclave.
Thereafter, 0.25 mmol of methylaluminoxane manufactured by Albemarle Company was dispersed in 20 mL of heptane, and the above complex (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3) was dispersed in 20 mL of heptane. (Trimethylsilylindenyl) zirconium dichloride (0.25 μmol) was added.
While stirring, the temperature was raised to 60 ° C., and the mixture was stirred for 5 minutes.
After adding 3 mL of methanol and depressurizing, the polymerization solution was dried under reduced pressure to obtain a 1-butene polymer.
Table 1 and FIG. 1 show the evaluation results of the resin properties of the obtained polymer.
[0049]
Comparative Example 2
160 mL of heptane, 200 mL of 1-butene, 0.5 mmol of triisobutylaluminum, and 0.03 MPa of hydrogen were introduced into a heated and dried 1 L autoclave.
Thereafter, 0.25 mmol of methylaluminoxane manufactured by Albemarle Company was dispersed in 20 mL of heptane, and the above complex (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3) was dispersed in 20 mL of heptane. (Trimethylsilylindenyl) zirconium dichloride (0.25 μmol) was added.
While stirring, the temperature was raised to 60 ° C., and the mixture was stirred for 5 minutes.
After adding 3 mL of methanol and depressurizing, the polymerization solution was dried under reduced pressure to obtain a 1-butene polymer.
Table 1 and FIG. 1 show the evaluation results of the resin properties of the obtained polymer.
[0050]
Comparative Example 3
160 mL of heptane, 200 mL of 1-butene, 0.5 mmol of triisobutylaluminum, and 0.03 MPa of hydrogen were introduced into a heated and dried 1 L autoclave.
Then, 0.50 mmol of methylaluminoxane manufactured by Albemarle Company was dispersed in 20 mL of heptane, and the above complex (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3- A solution of trimethylsilylindenyl) zirconium dichloride (0.50 μmol) was added.
While stirring, the temperature was raised to 60 ° C., and the mixture was stirred for 30 minutes.
After adding 3 mL of methanol and depressurizing, the polymerization solution was dried under reduced pressure to obtain a 1-butene polymer.
Table 1 and FIG. 1 show the evaluation results of the resin properties of the obtained polymer.
[0051]
Comparative Example 4
160 mL of heptane, 200 mL of 1-butene, 0.5 mmol of triisobutylaluminum, and 0.03 MPa of hydrogen were introduced into a heated and dried 1 L autoclave.
Thereafter, 0.50 mmol of methylaluminoxane manufactured by Albemarle Company was dispersed in 20 mL of heptane, and the above complex (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3) was dispersed in 20 mL of heptane. (Trimethylsilylindenyl) zirconium dichloride (0.50 μmol) was added.
While stirring, the temperature was raised to 60 ° C., and the mixture was stirred for 60 minutes.
After adding 3 mL of methanol and depressurizing, the polymerization solution was dried under reduced pressure to obtain a 1-butene polymer.
Table 1 and FIG. 1 show the evaluation results of the resin properties of the obtained polymer.
[0052]
Comparative Example 5
160 mL of heptane, 200 mL of 1-butene, 0.5 mmol of triisobutylaluminum, and 0.03 MPa of hydrogen were introduced into a heated and dried 1 L autoclave.
Then, 0.5 mmol of methylaluminoxane manufactured by Albemarle Company was dispersed in 20 mL of heptane, and the above complex (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3) was added to 20 mL of heptane. (Trimethylsilylindenyl) zirconium dichloride (0.5 μmol) was added.
While stirring, the temperature was raised to 50 ° C., and the mixture was stirred for 5 minutes.
Thereafter, the temperature was raised to 60 ° C., and the mixture was stirred for 15 minutes.
After adding 3 mL of methanol and depressurizing, the polymerization solution was dried under reduced pressure to obtain a 1-butene polymer.
Table 1 and FIG. 1 show the evaluation results of the resin properties of the obtained polymer.
In Examples 1, 2 and 4, despite having the same intrinsic viscosity log [η] (molecular weight) as compared with Comparative Examples 1 and 5, the fluidity index log η * is low and the fluidity is good. I understand.
[0053]
[Table 1]

[0054]
【The invention's effect】
The 1-butene polymer of the present invention has a wide molecular weight distribution by combining a specific metallocene catalyst and a specific polymerization method, and can cope with injection and high-speed molding of sheets, films, and the like.
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between intrinsic viscosity log [η] (horizontal axis) -fluidity log η * (vertical axis) of Examples 1 to 4 and Comparative Examples 1 to 5.

Claims (4)

1-butene polymer satisfying the following conditions (1) to (4).
(1) Using a differential scanning calorimeter (DSC), melt at 190 ° C. for 5 minutes in a nitrogen atmosphere, and then increase the temperature at 10 ° C./min. The melting point (Tm-P) defined as the peak top of the peak is not observed, or the crystalline resin (2) stereoregularity index (mmmm) / [(mmrr) + (rmmr) is in the range of 0 to 100 ° C. )] Is 20 or less. (3) The intrinsic viscosity [η] is 0.1 to 4.0 dl / g.
(4) The molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) is 4.0 or more. The 1-butene-based polymer according to claim 1, wherein the 1-butene-based polymer is a homopolymer, and a mesopentad fraction (mmmm) is 20 to 90 mol%. The 1-butene-based polymer according to claim 2, which satisfies the following formula.
(Mmmm) ≦ 90−2 × (rr)
Here, (rr) indicates a racemic triad fraction (mol%). The 1-butene according to any one of claims 1 to 3, wherein 1-butene or 1-butene and ethylene and / or an α-olefin having 3 to 20 carbon atoms (excluding 1-butene) are subjected to multistage polymerization. A method for producing a polymer.

Images