JP3553233B2 - Method for producing polyolefin - Google Patents

Description

［式中、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９は個別に水素または炭素数１〜１０ の炭化水素基を示し、その炭化水素基の任意の２つは共同して環状炭化水素基を形成することができる。］
一般式（３）に示す炭化水素基には、メチル、エチル、プロピル、ブチル、ｔ−ブチル、ヘキシル、オクチルなどのアルキル基、フェニルなどのアリール基、メトキシ、エトキシ、プロポキシなどのアルコキシ基、フェノキシなどのアリールオキシ基、ベンジルなどのアラルキル基が包含される。また、一般式（３）のの炭化水素基の任意の２つが共同して環状炭化水素基を形成した場合、その骨格としてはシクロヘプタトリエン、アリールおよびそれらの縮合環がある。
一般式（３）で示される環状炭化水素化合物のなかで、好適なものとしては、シクロペンタジエン、インデン、アズレンなどの外、これらに炭素数１〜１０のアルキル、アリール、アラルキル、アルコキシまたはアリールオキシが置換した各誘導体などがある。
一般式（３）の環状炭化水素化合物が、アルキレン基（その炭素数は通常２〜８、好ましくは２〜３）を介して結合（架橋）した化合物も、本発明の成分（３）として好適に用いられる。
【００１５】
環状炭化水素基を有する有機ケイ素化合物は、下記の一般式（４）で表すことができる。
（Ｃｐ）_ｒ ＳｉＲ^１０ _ｓ Ｘ^３ _{４−ｒ−ｓ}
ここで、Ｃｐは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、置換インデニル基で例示される前記環状炭化水素基を示し、Ｒ^１０はメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、オクチル基などのアルキル基；ビニル基、アリル基などのアルケニル基；メトキシ基、エトキシ基、プロポキシ基、ブトキシ基などのアルコキシ基；フェニル基、トリル基、キシリル基などのアリール基；フェノキシ基などのアリールオキシ基；ベンジル基、フェネチル基、スチリル基、ネオフィル基などのアラルキル基で例示されるような、炭素数１〜２４、好ましくは１〜１２の炭化水素残基または水素を示す。この炭化水素残基は、必ずしも直鎖状（ノルマル）である必要はなく、分岐鎖状（ｉｓｏ−、ｓｅｃ−、ｔｅｒｔ−、ｎｅｏ−など）であって差し支えない。Ｘ^３ はフッ素、ヨウ素、塩素または臭素などのハロゲン原子を示し、ｒ およびｓ は０＜ｒ ≦４、０≦ｓ ≦３の範囲であり、好ましくは１≦ｒ ＋ｓ ≦４である。
【００１６】
本発明の成分（３）として使用可能な有機環状炭化水素化合物には、次のような化合物が包含される。
シクロペンタジエン、メチルシクロペンタジエン、エチルシクロペンタジエン、ｔ−ブチルシクロペンタジエン、ヘキシルシクロペンタジエン、オクチルシクロペンタジエン、１，２−ジメチルシクロペンタジエン、１，３−ジメチルシクロペンタジエン、１，２，４−トリメチルシクロペンタジエン、１，２，３，４−テトラメチルシクロペンタジエン、ペンタメチルシクロペンタジエンなどの置換シクロペンタジエン、インデン、４−メチルインデン、４，７−ジメチルインデン、４，５，６，７−テトラハイドロインデンなどの置換インデン、シクロヘプタトリエン、メチルシクロヘプタトリエンなどの置換シクロヘプタトリエン、シクロオクタテトラエン、メチルシクロオクタテトラエンなどの置換シクロオクタテトラエン、アズレン、メチルアズレン、エチルアズレン、フルオレン、メチルフルオレンなどの置換フルオレンのような炭素数７〜２４のシクロポリエン又は置換シクロポリエン、
【００１７】
モノシクロペンタジエニルシラン、ジシクロペンタジエニルシラン、トリシクロペンタジエニルシラン、テトラシクロペンタジエニルシラン、モノシクロペンタジエニルモノメチルシラン、モノシクロペンタジエニルモノエチルシラン、モノシクロペンタジエニルジメチルシラン、モノシクロペンタジエニルジエチルシラン、モノシクロペンタジエニルトリメチルシラン、モノシクロペンタジエニルトリエチルシラン、モノシクロペンタジエニルモノメトキシシラン、モノシクロペンタジエニルモノエトキシシラン、モノシクロペンタジエニルモノフェノキシシラン、モノシクロペンタジエニルモノメチルモノクロロシラン、モノシクロペンタジエニルモノエチルモノクロロシラン、モノシクロペンタジエニルモノメチルジクロロシラン、モノシクロペンタジエニルモノエチルジクロロシラン、モノシクロペンタジエニルトリクロロシラン、ジシクロペンタジエニルモノメチルシラン、ジシクロペンタジエニルモノエチルシラン、ジシクロペンタジエニルジメチルシラン、ジシクロペンタジエニルジエチルシラン、ジシクロペンタジエニルメチルエチルシラン、ジシクロペンタジエニルジプロピルシラン、ジシクロペンタジエニルエチルプロピルシラン、ジシクロペンタジエニルジフェニルシラン、ジシクロペンタジエニルフェニルメチルシラン、ジシクロペンタジエニルメチルクロロシラン、ジシクロペンタジエニルエチルクロロシラン、ジシクロペンタジエニルジクロロシラン、ジシクロペンタジエニルモノメトキシシラン、ジシクロペンタジエニルモノエトキシシラン、ジシクロペンタジエニルモノメトキシモノクロロシラン、ジシクロペンタジエニルモノエトキシモノクロロシラン、トリシクロペンタジエニルモノメチルシラン、トリシクロペンタジエニルモノエチルシラン、トリシクロペンタジエニルモノメトキシシラン、トリシクロペンタジエニルモノエトキシシラン、トリシクロペンタジエニルモノクロロシラン、３−メチルシクロペンタジエニルシラン、ビス３−メチルシクロペンタジエニルシラン、３−メチルシクロペンタジエニルメチルシラン、１，２−ジメチルシクロペンタジエニルシラン、１，３−ジメチルシクロペンタジエニルシラン、１，２，４−トリメチルシクロペンタジエニルシラン、１，２，３，４−テトラメチルシクロペンタジエニルシラン、ペンタメチルシクロペンタジエニルシラン、
【００１８】
モノインデニルシラン、ジインデニルシラン、トリインデニルシラン、テトラインデニルシラン、モノインデニルモノメチルシラン、モノインデニルモノエチルシラン、モノインデニルジメチルシラン、モノインデニルジエチルシラン、モノインデニルトリメチルシラン、モノインデニルトリエチルシラン、モノインデニルモノメトキシシラン、モノインデニルモノエトキシシラン、モノインデニルモノフェノキシシラン、モノインデニルモノメチルモノクロロシラン、モノインデニルモノエチルモノクロロシラン、モノインデニルモノメチルジクロロシラン、モノインデニルモノエチルジクロロシラン、モノインデニルトリクロロシラン、ジインデニルモノメチルシラン、ジインデニルモノエチルシラン、ジインデニルジメチルシラン、ジインデニルジエチルシラン、ジインデニルメチルエチルシラン、ジインデニルジプロピルシラン、ジインデニルエチルプロピルシラン、ジインデニルジエフェニルシラン、ジインデニルフェニルメチルシラン、ジインデニルメチルクロロシラン、ジインデニルエチルクロロシラン、ジインデニルジクロロシラン、ジインデニルモノメトキシシラン、ジインデニルモノエトキシシラン、ジインデニルモノメトキシモノクロロシラン、ジインデニルモノエトキシモノクロロシラン、トリインデニルモノメチルシラン、トリインデニルモノエチルシラン、トリインデニルモノメトキシシラン、トリインデニルモノエトキシシラン、トリインデニルモノクロロシラン、３−メチルインデニルシラン、ビス３−メチルインデニルシラン、３−メチルインデニルメチルシラン、１，２−ジメチルインデニルシラン、１，３−ジメチルインデニルシラン、１，２，４−トリメチルインデニルシラン、１，２，３，４−テトラメチルインデニルシラン、ペンタメチルインデニルシラン等がある。好ましくはシクロペンタジエン、置換シクロペンタジエン、インデン、置換インデンなど。
【００１９】
また、上記した各化合物のいずれかが、アルキレン基（その炭素数は通常２〜８、好ましくは２〜３）を介して結合した化合物も、本発明の成分（３）として使用でき、そのような化合物には、例えば、ビスインデニルエタン、ビス（４，５，６，７−テトラハイドロ−１−インデニル）エタン、１，３−プロパンジエニルビスインデン、１，３−プロパンジエニルビス（４，５，６，７−テトラハイドロ）インデン、プロピリレンビス（１−インデン）、イソプロピリレン（１−インデニル）シクロペンタジエン、ジフェニルメチレン（９−フルオレニル）シクロペンタジエン、イソプロピリレンシクロペンタジエニル−１−フルオレンなどがある。
【００２０】
本発明の成分（４）は、分子中に１〜１００個、好ましくは１〜５０個のＡｌ−Ｏ−Ａｌ結合を有している変性有機アルミニウム化合物である。このような変性有機アルミニウム化合物は、通常、有機アルミニウム化合物と水とを不活性炭化水素溶媒中で反応させて得られる反応生成物である。不活性炭化水素溶媒としては、脂肪族炭化水素（例えば、ペンタン、ヘキサン、ヘプタン等）、脂環族炭化水素（例えば、シクロヘキサン、メチルシクロヘキサン等）および芳香族炭化水素（例えば、ベンゼン、トルエン、キシレン等）が使用できるが、脂肪族炭化水素又は芳香族炭化水素を使用することが好ましい。
変性有機アルミニウム化合物の調製に用いる有機アルミニウム化合物は、下記の一般式（５）で示すことができる。
Ｒ^１１ _ｔ ＡｌＸ^４ _３−ｔ （５）
［式中、Ｒ^１１は炭素数１〜１８、好ましくは１〜１２のアルキル基、アルケニル基、アリール基、アラルキル基等の炭化水素基を、Ｘ^４ は水素原子又はハロゲン原子を示し、ｔは１≦ｔ≦３の整数を示す］
なかでも、トリアルキルアルミニウムが好ましい。トリアルキルアルミニウムのアルキル基は、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基等のいずれでも差し支えないが、メチル基であることが特に好ましい。
水と有機アルミニウム化合物との反応比（水／Ａｌモル比）は、０．２５／１〜１．２／１ 、特に、０．５／１ 〜１／１ であることが好ましく、反応温度は通常−７０ 〜１００ ℃、好ましくは−２０ 〜２０℃の範囲にある。反応時間は通常５分〜２４時間、好ましくは１０分〜５時間の範囲で選ばれる。反応に要する水としては、所謂水が使用できる外、硫酸銅水和物、硫酸アルミニウム水和物等に含まれる結晶水を利用することもできる。
なお、上記した変性有機アルミニウム化合物のうち、アルキルアルミニウムと水とを反応させて得られるものは、通常アルミノキサンと呼ばれ、特にメチルアルミノキサン（もしくはメチルアルミノキサンから実質的になるもの）は、本発明の成分（４）として好適である。
もちろん、本発明の成分（４）として、上記した各変性有機アルミニウム化合物の２種以上を組み合わせて使用することもでき、また前記変性有機アルミニウム化合物を前述の不活性炭化水素溶媒に溶液または分散させた溶液としたものを用いても良い。
【００２１】
本発明の成分（５）としては、無機物担体および／または粒子状ポリマー担体が使用される。無機物担体は、本発明の触媒を調製する段階において、本来の形状を保持している限り、粉末状、粒状、フレーク状、箔状、繊維状などいずれの形状であっても差し支えないが、いずれの形状であっても、最大直径は通常５〜２００μｍ、好ましくは１０〜１５０μｍの範囲のものが適している。また、無機物担体は多孔性であることが好ましく、通常、その表面積は３０〜１０００ｍ^２／ｇ、細孔容積は０．１〜３ｃｍ^３／ｇの範囲にある。
本発明の無機物担体としては、金属、金属酸化物、金属塩化物、金属炭酸塩，炭素物質、またはこれらの混合物が使用可能であり、これらは通常２００〜９００℃で空気中または窒素、アルゴン等の不活性ガス中で焼成して用いられる。
無機物担体に用いることができる好適な金属としては、例えば、鉄、アルミニウム、ニッケルなどが挙げられる。
金属酸化物としては周期律表第Ｉ族〜第ＶＩＩＩ族から選ばれる元素の単独酸化物または複酸化物が挙げられ、例えばＳｉＯ_２、Ａｌ_２Ｏ_３、ＭｇＯ、ＣａＯ、Ｂ_２Ｏ_３、ＴｉＯ_２、ＺｒＯ_２、Ｆｅ_２Ｏ_３、Ａｌ_２Ｏ_３・ＭｇＯ、Ａｌ_２Ｏ_３・ＣａＯ、 Ａｌ_２Ｏ_３・ＳｉＯ_２、Ａｌ_２Ｏ_３・ＭｇＯ・ＣａＯ、Ａｌ_２Ｏ_３・ＭｇＯ・ＳｉＯ_２、Ａｌ_２Ｏ_３・ＣｕＯ、Ａｌ_２Ｏ_３・Ｆｅ_２Ｏ_３、Ａｌ_２Ｏ_３・ＮｉＯ、ＳｉＯ_２・ＭｇＯなどの天然または合成の各種複酸化物を例示する事ができる。ここで上記の式は分子式ではなく、組成のみを表すものであり、本発明において用いられる複酸化物の構造および成分比率は特に限定されるものではない。また、本発明において用いる金属酸化物は、少量の水分を吸収していても差し支えなく、少量の不純物を含有していても差し支えない。
金属塩化物としては、例えば、アルカリ金属、アルカリ土類金属の塩化物が好ましく、具体的にはＭｇＣｌ_２、ＣａＣｌ_２などが特に好適である。金属炭酸塩としてはアルカリ金属、アルカリ土類金属の炭酸塩が好ましく、具体的には、炭酸マグネシウム、炭酸カルシウム、炭酸バリウムなどが挙げられる。
炭素質物としては、例えば、カーボンブラック、活性炭などが挙げられる。
以上の無機物担体はいずれも本発明に好適に用いることができるが、特に金属酸化物、シリカ、アルミナなどの使用が好ましい。
【００２２】
粒子ポリマー担体としては、触媒調製時および重合反応時において、溶融などせずに固体状を保つものである限り、熱可塑性樹脂、熱硬化性樹脂のいずれもが使用でき、その粒径は通常５〜２０００μｍ、好ましくは１０〜１００μｍの範囲のものが望ましい。これらポリマー担体の分子量は、当該ポリマーが触媒調製時および重合反応時において固体状物質として存在できる程度であれば、特に限定されることはなく、低分子量のものから超高分子量のものまで任意に使用可能である。
粒子ポリマー担体の具体例を摘記すると、粒子状のエチレン重合体、エチレン・α−オレフィン共重合体、プロピレン重合体または共重合体、ポリ１−ブテンなどで代表される各種のポリオレフィン（好ましくは炭素数２〜１２）、ポリエステル、ポリアミド、ポリ塩化ビニル、ポリメタクリル酸メチル、ポリアクリル酸メチル、ポリスチレン、ポリノルボルネンのほか、各種の天然高分子およびこれらの混合物が例示できる。
【００２３】
上記した無機物担体および粒子状ポリマー担体は、そのまま、本発明の成分（５）として使用できるが、その使用に先立ち、これらの担体を、トリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウム、トリｎ−ヘキシルアルミニウム、ジメチルアルミニウムクロライド、ジエチルアルミニウムクロライド、ジエチルモノエトキシアルミニウムなどの有機アルミニウム化合物とか、Ａｌ−Ｏ−Ａｌ結合を含む変性有機アルミニウム化合物（この化合物については前述の成分（４）において例示された化合物と同様のものである）とか、あるいはシラン化合物などに接触させることからなる予備処理を施すことができる。
無機物担体について言えば、これをアルコール、アルデヒドのような活性水素含有化合物、エステル、エーテルなどの電子供与性化合物、テトラアルコキシシリケート、トリアルコキシアルミニウム、遷移金属テトラアルコキシドなどのアルコキサイド機含有化合物などに、予め接触させてから成分（５）として使用する方法も好ましく用いられる。
接触処理方法としては、通常窒素またはアルゴンなどの不活性雰囲気中、一般にベンゼン、トルエン、キシレン、エチルベンゼンなどの芳香族炭化水素（通常炭素数は６〜１２）、ヘプタン、ヘキサン、デカン、ドデカン、シクロヘキサンなどの脂肪族あるいは脂環族炭化水素（通常５〜１２）等の液状不活性炭化水素の存在下、攪拌下または非攪拌下に、担体を予備処理用化合物と接触させる方法が挙げられる。この接触は、通常−１００℃〜２００℃、好ましくは−５０℃〜１００℃の温度にて、３０分〜５０時間、好ましくは１時間〜２４時間行うことが望ましい。
なお、この接触反応は、前記した予備処理用化合物が可溶な溶媒、すなわちベンゼン、トルエン、キシレン、エチルベンゼンなどの芳香族炭化水素（通常炭素数は６〜１２）中で行うことが好ましく、この場合は、接触反応後、溶媒を除去することなく、これをそのまま本発明の接触成分の調製に供することができる。また、当該の接触反応生成物に、予備処理用化合物が不溶もしくは難溶の液状不活性炭化水素（例えば、予備処理用化合物が変性有機アルミニウム化合物の場合は、ペンタン、ヘキサン、デカン、ドデカン、シクロヘキサンなどの脂肪族あるいは脂環族炭化水素）を添加し、固体成分として成分（５）を析出させて乾燥させるか、あるいは予備処理時の溶媒溶液である芳香族炭化水素の一部または全部を、乾燥等の手段により除去した後、成分（５）を固体成分として取り出すこともできる。
予備処理に供する無機物担体および／または粒子状ポリマー担体と、予備処理用化合物との割合は、本発明の目的を損なわない限り特に制限はないが、通常は担体１００ｇに対して１〜１００００ミリモル、好ましくは５〜１５００ミリモル（ただし、変性アルミニウム化合物においてはＡｌ原子濃度）の範囲内で選ばれる。
【００２４】
本発明のオレフィン類重合用触媒は、前述の通り、成分（１）、成分（２）、成分（３）、成分（４）、さらに所望により成分（５）を相互に接触することにより得られるが、これらの成分の接触順序は特に限定されない。例えば、成分（１）〜成分（４）を接触させて本発明の触媒を得る場合については、
〈１〉成分（１）、（２）、（３）、（４）を同時に加える方法。
〈２〉成分（１）、（２）、（３）を同時に接触させ、次ぎに成分（４）を接触 させる方法。
（以下、同時に接触させる場合を｛｝で、順次接触させる場合を→で表す。例えば、上記〈２〉の場合は｛（１）（２）（３）｝→（４）で表示される。）
〈３ 〉｛（１）（２）（４）｝→（３）
〈４〉｛（１）（３）（４）｝→（２）
〈５〉｛（２）（３）（４）｝→（１）
〈６〉｛（１）（２）｝→｛（３）（４）｝
〈７〉｛（１）（３）｝→｛（２）（４）｝
〈８〉｛（１）（４）｝→｛（２）（３）｝
〈９〉｛（１）（２）｝→（３）→（４）
〈１０〉｛（１）（２）｝→（４）→（３）
〈１１〉｛（１）（３）｝→（２）→（４）
〈１２〉｛（１）（３）｝→（４）→（２）
〈１３〉｛（１）（４）｝→（２）→（３）
〈１４〉｛（１）（４）｝→（３）→（２）
〈１５〉｛（２）（３）｝→（１）→（４）
〈１６〉｛（２）（３）｝→（４）→（１）
〈１７〉｛（２）（４）｝→（１）→（３）
〈１８〉｛（２）（４）｝→（３）→（１）
〈１９〉｛（３）（４）｝→（１）→（２）
〈２０〉｛（３）（４）｝→（２）→（１）
〈２１〉（３）→（（１）（２）｝→（４）
〈２２〉（４）→（（１）（２）｝→（３）
〈２３〉（２）→（（１）（３）｝→（４）
〈２４〉（４）→（（１）（３）｝→（２）
〈２５〉（２）→｛（１）（４）｝→（３）
〈２６〉（３）→｛（１）（４）｝→（２）
〈２７〉（１）→｛（２）（３）｝→（４）
〈２８〉（４）→｛（２）（３）｝→（１）
〈２９〉（１）→｛（２）（４）｝→（３）
〈３０〉（３）→｛（２）（４）｝→（１）
〈３１〉（１）→｛（３）（４）｝→（２）
〈３２〉（２）→｛（３）（４）｝→（１）
などの接触順序が挙げられる。これらの接触順序の中で、〈１〉〈２〉〈５〉 〈７〉〈１１〉〈１５〉〈２３〉〈２７〉が好ましく用いられる。
４成分の接触方法も任意であるが、通常は窒素またはアルゴンなどの不活性雰囲気中、ヘプタン、ヘキサン、ベンゼン、トルエン、キシレンなどの不活性炭化水素溶媒の存在下、通常−１００℃〜２００℃、好ましくは−５０℃〜１５０℃の温度にて、成分（１）、成分（２）、成分（３）および成分（４）を、５分〜２５０時間、好ましくは３０分〜２４時間接触させる方法が採用される。不活性炭化水素溶媒中にて各成分を接触させる場合、生成触媒は、全接触反応終了後、溶液状態にてそのまま重合に供してもよいし、また、もし可能であれば、析出、乾燥などの手段により、固体触媒成分として一旦取り出した後、重合に用いてもよい。もちろん、各成分の接触反応は複数回行ってもよい。
【００２５】
また、成分（１）〜成分（５）を接触させて本発明の触媒を得る場合は、例えば
〈３３〉上記〈１〉〜〈３２〉の接触順序で成分（１）〜（４）の反応生成物を調製 し、それを成分（５）と接触反応させる方法。（｛（１）（２）（３） （４）｝→（５）と記す）
〈３４〉（５）→（４）→｛（１）（２）（３）｝
〈３５〉（５）→（４）→｛（１）（２）｝→（３）
〈３６〉（５）→（４）→｛（１）（３）｝→（２）
〈３７〉（５）→（４）→｛（２）（３）｝→（１）
〈３８〉（５）→（４）→（３）→｛（１）（２）｝
〈３９〉（５）→（４）→（２）→｛（１）（３）｝
〈４０〉（５）→（４）→（１）→｛（２）（３）｝
〈４１〉（５）→（４）→（１）→（２）→（３）
〈４２〉（５）→（４）→（１）→（３）→（２）
〈４３〉（５）→（４）→（２）→（３）→（１）
〈４４〉（５）→（４）→（２）→（１）→（３）
〈４５〉（５）→（４）→（３）→（１）→（２）
〈４６〉（５）→（４）→（３）→（２）→（１）
〈４７〉（５）→（１）→｛（２）（３）（４）｝
〈４８〉（５）→（１）→｛（２）（３）｝→（４）
〈４９〉（５）→（１）→｛（２）（４）｝→（３）
〈５０〉（５）→（１）→｛（３）（４）｝→（２）
〈５１〉（５）→（１）→（４）→｛（２）（３）｝
〈５２〉（５）→（１）→（３）→｛（２）（４）｝
〈５３〉（５）→（１）→（２）→｛（３）（４）｝
〈５４〉（５）→（１）→（２）→（３）→（４）
〈５５〉（５）→（１）→（２）→（４）→（３）
〈５６〉（５）→（１）→（３）→（２）→（４）
〈５７〉（５）→（１）→（３）→（４）→（２）
〈５８〉（５）→（１）→（４）→（２）→（３）
〈５９〉（５）→（１）→（４）→（３）→（２）
〈６０〉（５）→（２）→｛（１）（３）（４）｝
〈６１〉（５）→（３）→｛（１）（２）（４）｝
などが採用可能である。
これらの接触順序の中で、〈３３〉〈３４〉〈４７〉が好ましく用いられる。
成分（１）〜（５）の接触は、通常、窒素またはアルゴンなどの不活性雰囲気中、一般にベンゼン、トルエン、キシレン、エチルベンゼンなどの芳香族炭化水素、ヘプタン、ヘキサン、デカン、ドデカン、シクロヘキサンなどの脂肪族あるいは脂環族炭化水素等の液状不活性炭化水素の存在下、攪拌下または非攪拌下に行われる。特に、成分（１）〜（４）が可溶な溶媒、すなわち、ベンゼン、トルエン、キシレン、エチルベンゼンなどの芳香族炭化水素中で行うことが好ましい。この接触は通常−１００〜２００℃、好ましくは−５０〜１５０℃の温度にて、５分〜２５０時間、好ましくは３０分〜２４時間行うことが望ましい。
成分（１）〜（５）の接触に際しては、上記した通り、ある種の成分が可溶な芳香族炭化水素溶媒と、ある種の成分が不溶ないしは難溶な脂肪族または脂環族炭化水素溶媒とがいずれも使用可能であるが、特に、成分（１）〜（４）が可溶な芳香族炭化水素を溶媒として使用することが望ましい。そして、各成分同士の接触反応を段階的に行う場合にあっては、前段で用いた可溶性の芳香族炭化水素溶媒を何等除去することなく、これをそのまま後段の接触反応の溶媒に用いてもよい。また，可溶性溶媒を使用した前段の接触反応後、ある種の成分が不溶もしくは難溶な液状不活性炭化水素（例えば、ペンタン、ヘキサン、デカン、ドデカン、シクロヘキサンなどの脂肪族あるいは脂環族炭化水素）を添加して、所望生成物を固形物として取り出した後に、この所望生成物の後段の接触反応を、上記した不活性炭化水素溶媒のいずれかを使用して実施することもできる。本発明では各成分の接触反応を複数回行うことを妨げない。
【００２６】
本発明の触媒を調製する際の成分（１）〜（４）または成分（１）〜（５）の使用割合は、成分（１）１モルに対して、成分（２）を通常０．０１〜１０００モル、好ましくは０．１〜１００モル、さらに好ましくは０．５〜５０モルの範囲で、成分（３）を通常０．０１〜１０００モル、好ましくは０．１〜１００モル、さらに好ましくは０．５〜５０モルの範囲で、成分（４）を通常１〜１０，０００モル、好ましくは５〜１０００モル、さらに好ましくは１０〜５００モルの範囲で使用する。また、成分（５）を併用する場合の使用割合は、成分（５）１ｇに対し、成分（１）が通常５ミリモル以下、望ましくは０．０００１〜５ミリモル、好ましくは０．００１〜０．５ミリモル、さらに好ましくは０．０１〜０．１ミリモルの割合とするのが望ましい。
成分（１）〜（４）または成分（１）〜（５）を相互に接触させることにより得られる本発明の触媒は、所望により、Ｃ−Ｘ結合（Ｘ：フッ素等のハロゲン）を有するハロゲン化炭化水素化合物、ハロゲン化含酸素炭化水素化合物、ハロゲン・炭素化合物やスルフィド類、ならびに成分（２）に該当しないボラン類、ボレート類と併用してもよい。
【００２７】
本発明の重合方法では、上記触媒の存在下、飽和炭化水素化合物および芳香族炭化水素化合物から選ばれる１種または２種以上の炭化水素化合物の存在下に、オレフィン類を重合または共重合させるが、重合反応系内に共存させる炭化水素化合物には、常温（通常25℃程度）、常圧において、液状またはガス状であるものを用いる。本発明は、この炭化水素化合物を特定量存在させることによって、生成重合体の分子量を減少させ得るのが特徴である。
分子量の減少に関与せしめる飽和炭化水素化合物は、通常、炭素数１〜２４、好ましくは、炭素数１〜１２の鎖状炭化水素（直鎖状であるか、分岐鎖状であるかを問わない）および環状炭化水素のいずれでもよく、また芳香族化合物は、通常、炭素数６〜２４、好ましくは、炭素数６〜１２のものである。
具体的には、メタン、エタン、プロパン、ｎ−ブタン、イソブタン、２，２ジメチルプロパン、ｎ−ペンタン，イソペンタン，シクロペンタン、ｎ−ヘキサン、２−メチルペンタン、３−メチルペンタン、２，２−ジメチルブタン、２，３−ジメチルブタン、シクロヘキサン、メチルシクロペンタン、ｎ−ヘプタン、２−メチルヘキサン、３−メチルヘキサン、２，２−ジメチルペンタン、２，３−ジメチルペンタン、２，４−ジメチルペンタン、３，３−ジメチルペンタン、２，２，３−トリメチルブタン、シクロヘプタン、メチルシクロヘキサン、エチルシクロペンタン、ｎ−オクタン、２−メチルヘプタン、３−メチルヘプタン、２，２−ジメチルヘキサン、２，４−ジメチルヘキサン、２，５−ジメチルヘキサン、３，４−ジメチルヘキサン、２，２，４−トリメチルペンタン、２，３，４−リメチルペンタン、シクロオクタン、エチルシクロヘキサン、ｎ−ノナン、ｎ−デカン、シクロデカン、ｎ−ウンデカン、ｎ−ドデカン、ｎ−トリデカン、ｎ−テトラデカン、ｎ−ペンタデカンなどの脂肪族あるいは脂環族の飽和炭化水素、およびエチルベンゼン、トルエン、キシレン、メシチレンなどの芳香族炭化水素が、分子量の減少の目的で使用される。中でも、メタン、エタン、プロパン、２，２−ジメチルプロパン、ｎ−ペンタン、ｎ−ヘキサン、シクロヘキサン、ｎ−ヘプタン、ｎ−オクタン、シクロオクタン、ｎ−デカン、トルエン、キシレンなどを使用するのが好ましい。これらの化合物は２種類以上混合して用いることも可能である。
分子量の減少に関与せしめる炭化水素化合物の使用量は、触媒１ｇに対して、０．００１〜１００モル、好ましくは０．００５〜５０モル、さらに好ましくは０．０１〜１０モルの範囲で選択される。
【００２８】
本発明の方法では、オレフィン類が単独重合または共重合せしめられる。本発明でいうオレフィン類には、α−オレフィン類、環状オレフィン類、ジエン類、トリエン類が包含される。
α−オレフィン類には、炭素数２〜１２、好ましくは２〜８のものが包含され、具体的には、エチレン、プロピレン、ブテン−１、ヘキセン−１、４−メチルペンテン−１等が例示される。α−オレフィン類は単独重合させることができるほか、２種類以上のα−オレフィンを共重合させることもでき、その共重合は交互共重合、ランダム共重合、ブロック共重合のいずれであっても差し支えない。α−オレフィン類の共重合には、エチレンとプロピレン、エチレンとブテン−１、エチレンとヘキセン−１、エチレンと４−メチルペンテン−１のように、エチレンと炭素数３〜１２、好ましくは３〜８のα−オレフィンとを共重合する場合、プロピレンとブテン−１、プロピレンと４−メチルペンテン−１、プロピレンと４−メチルブテン−１、プロビレンとヘキセン−１、プロピレンとオクテン−１のように、プロピレンと炭素数３〜１２、好ましくは３〜８のα−オレフィンとを共重合する場合が含まれる。エチレン又はプロピレンと他のα−オレフィンとを共重合させる場合、当該他のα−オレフィンの量は全モノマ−の９０モル％以下の範囲で任意に選ぶことができるが、一般的には、エチレン共重合体にあっては、４０モル％以下，好ましくは３０モル％以下、さらに好ましく２０モル％以下であり、プロピレン共重合体にあっては、１〜９０モル％、好ましくは５〜９０モル％、さらに好ましくは１０〜７０モル％の範囲で選ばれる。
環状オレフィンとしては、炭素数３〜２４、好ましくは３〜１８のものが本発明で使用可能であり、これには、例えば、シクロペンテン、シクロブテン、シクロペンテン、シクロヘキセン、３−メチルシクロヘキセン、シクロオクテン、シクロデセン、シクロドデセン、テトラシクロデセン、オクタシクロデセン、ジシクロペンタジエン，ノルボルネン、５−メチル−２−ノルボルネン、５−エチル−２−ノルボルネン、５−イソブチル−２−ノルボルネン、５，６−ジメチル−２−ノルボルネン、５，５，６−トリメチル−２−ノルボルネン、エチリデンノルボルネンなどが包含される。環状オレフィンは前記のα−オレフィンと共重合せしめるのが通例であるが、その場合、環状オレフィンの量は共重合体の５０モル％以下，通常は１〜５０モル％、好ましくは２〜５０モル％の範囲にある。
原料単量体として使用可能なジエン類及びトリエン類は、炭素数４〜２６、好ましくは６〜２６のポリエンである。具体的には、ブタジエン、１，３−ペンタジエン、１，４−ペンタジエン、１，３−ヘキサジエン、１，４−ヘキサジエン、１，５−ヘキサジエン、１，３−シクロヘキサジエン、１，４−シクロヘキサジエン、１，９−デカジエン、１，１３−テトラデカジエン、２，６−ジメチル−１，５−ヘプタジエン、２−メチル−２，７−オクタジエン、２，７−ジメチル−２，６−オクタジエン、２，３ジメチルブタジエン、エチリデンノルボルネン、ジシクロペンタジエン、イソプレン、１，３，７−オクタトリエン、１，５，９−デカトリエンなどが例示される。本発明で鎖式ジエン又はトリエンを単量体に使用する場合、上記したα−オレフィンと共重合させるのが通例であるが、その共重合体中の鎖式ジエン及び／又はトリエンの含有量は、一般に、０．１〜５０モル％、好ましくは０．２〜１０モル％の範囲にある。
【００２９】
本発明の重合反応は、実質的に気相状態で、かつ、実質的に酸素、水などを絶った状態で遂行せしめられる。重合条件は温度２０〜２００℃、好ましくは５０〜１２０℃、圧力常圧〜７０kg/cm²G 、好ましくは常圧〜２０kg/cm²G の範囲にあり、重合時間としては５分〜２０時間、好ましくは３０分〜１０時間が採用されるのが普通である。また、分子量の減少を目的として反応系内に添加された飽和炭化水素および／または芳香族炭化水素は、重合反応条件下でガス状であっても、液状であってもよいが、これが液状である場合には、反応物中に分散していることが望ましい。
生成重合体の分子量の低減には、重合反応開始前および／又は重合開始後に、適量の飽和炭化水素化合物および／または芳香族炭化水素化合物を、反応器に供給することにより行われる。反応器への供給方法は、触媒の供給に先立って、反応器内の不純物を除去するために供給するスカベンジャーと同伴させる方法、原料単量体と同伴させる方法、あるいは単独で供給する方法のいずれでもよく、スカベンジャーと原料単量体との両方に同伴させて反応器に張り込んでもよい。また，実質的に重合が開始された後でも不活性ガスおよび／またはオレフィン類と同伴させ、反応器に供給することも可能である。
なお、スカベンジャーとしては、トリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウムなどの有機アルミニウム、前記変性有機アルミニウム化合物、分岐アルキルを含有する変性有機アルミニウムなどが使用できる。また、本発明の特徴の一つは、重合反応系内に飽和炭化水素および／または芳香族炭化水素を反応系内に共存させることによって、生成重合体の分子量を調節可能ならしめる点にあるが、このことは、重合条件（温度、圧力、触媒使用量、水素分圧など）の調節によって生成重合体の分子量を減少させる手段の採用を、本発明が排除していることを意味しない。さらにまた、本発明は、個々の重合条件がことなる２段以上の反応段を使用する多段重合方式にも、支障なく適用することができる。
【００３０】
【実施例】
以下に本発明を実施例及び比較例によって具体的に説明するが、本発明はこれらの例によってなんら限定されるものではない。
なお、実施例及び比較例で得られた重合体の物性測定は次の方法で行った。
メルトフローレート（ＭＦＲ）
ＡＳＴＭ Ｄ １２３８−５７Ｔ １９０℃，２．１６ｋｇ荷重に基づき測定した。
数平均分子量（Ｍｎ）
ゲルパーミエイションクロマトグラフィ（ウォーターズ製、モデル形式１５０−Ｃ型）にて、溶媒にオルソジクロロベンゼンを使用し、測定温度を１３５℃として算出した。
実施例１
（Ａ）触媒の調製
窒素雰囲気下で、電磁誘導攪拌機および冷却管を取り付けた１００ｍｌ三口フラスコに精製トルエン１０ｍｌを加え、ついでテトラプロポキシジルコニウム０．１１ｇと１，２−ビスインデニルエタン０．１ｇおよびトリイソブチルアルミニウム０．７ｇを加え、加熱環流条件下で２時間攪拌反応させた。次ぎに、メチルアルミノキサンのトルエン溶液（シェリング社製、濃度３．１ｍｍｏｌＡｌ／ｍｌ）１１ｍｌを加え，室温で１時間攪拌反応させた。
（Ｂ）重合
攪拌機を付した容量３Ｌのステンレススチール製オートクレーブを窒素置換し、そこに酸洗浄および３００℃で熱処理された海砂２００ｇを導入し、８０℃で減圧で十分に乾燥した。次ぎに上記触媒溶液を２ｍｌを加え、その後、ヘキサン３．９ｍｌ（３０ｍｍｏｌ）を張り込み、エチレンと１−ブテン（ブテン／エチレン＝０．２）の混合ガスを連続的に供給しつつ、全圧を９Ｋｇｆ／ｃｍ^２Ｇに維持して８０℃で２時間の重合を行った。触媒 効率は１３４ｋｇ／ｇＺｒで、ＭＦＲは４．５ｇ／１０ｍｉｎ、Ｍｎは３９８００であった。
実施例２
実施例１において重合の際に供給するヘキサン量を１．３ｍｌ（１０ｍｍｏｌ）に変えたこと以外は実施例１と同様に重合を行った。触媒効率は１３０ｋｇ／ｇＺｒでＭＦＲは３．５ｇ／１０ｍｉｎ、Ｍｎは４７２００であった。
比較例１
実施例１において重合の際にヘキサンを供給せずに重合したこと以外は実施例１と同様に行った。触媒効率は１３２ｋｇ／ｇＺｒでＭＦＲは３．０ｇ／１０ｍｉｎ、Ｍｎは５２３００であった。
実施例３
（Ａ）固体触媒の調製
窒素雰囲気下で、電磁誘導攪拌機および冷却管を取り付けた５００ｍｌ三口フラスコに精製トルエン１００ｍｌを加え、ついでテトラプロポキシジルコニウム２．０ｇとメチルシクロペンタジエン１．９ｇおよびトリエチルアルミニウム２．１ｇを加え加熱還流条件下で２時間攪拌反応させた。
次ぎに、メチルアルミノキサンのトルエン溶液（シェリング社製、濃度３．１ｍｍｏｌＡｌ／ｍｌ）１９５ｍｌを加え，室温で１時間攪拌反応させた。
窒素雰囲気下で、電磁誘導攪拌機および冷却管を取り付けた１Ｌ三口フラスコに、予め５００℃で７時間焼成処理したシリカ（富士デビソン製 ＃９５２）１５０ｇを入れ、フラスコを１５０℃まで加熱して１時間減圧乾燥を行った。乾燥終了後、フラスコを室温まで冷却し、ここに上記で得られた触媒成分溶液を添加し，常温で１時間反応させた。次いで、フラスコを４０℃まで昇温し、得られたスラリー溶液を６０分間減圧乾燥して溶媒を除去することにより、流動性の良い固体触媒２０１ｇを得た。
（Ｂ）重合
攪拌機を付した容量３Ｌのステンレススチール製オートクレーブを窒素置換した後、オートクレーブ内を７５℃まで昇温した。続いて、重合系内のスカベンジを行うためトリエチルアルミニウムのトルエン希釈溶液（１ｍｍｏｌ／ｍｌ）を０．３ｍｌ添加した後、ヘキサン３．９ｍｌ（３０ｍｍｏｌ）を添加し、エチレンとブテン−１の混合ガス（ブテン−１／エチレンモル比０．１５）を８Ｋｇｆ／ｃｍ^２Ｇとなるように張り込み、上記で得られた固体触媒を１００ｍｇ（Ｚｒ ＝０．２７ｍｇ）供給して重合を開始し、エチレンとブテン−１の混合ガス（ブテン−１／エチレンモル比０．０５）を連続的に供給しつつ、全圧を９Ｋｇｆ／ｃｍ^２Ｇに維持して２時間の重合を行った。重合終了後，余剰のガスを排出し、 冷却して内容物を取り出し、白色ポリマ−４５ｇを得た。このときの触媒効率は１６６Ｋｇ／ｇＺｒであった。この白色ポリマーのＭＦＲを測定したところ、１．２ｇ／１０ｍｉｎであり、Ｍｎは６７３００であった。
実施例４
実施例３において使用する固体触媒量を１０７ｍｇ（Ｚｒ＝０．２９ｍｇ）とし、添加するヘキサン量を１．３ｍｌ（１０ｍｍｏｌ）とした以外は実施例３と同様に実験を行った。
重合終了後、余剰のガスを排出し、冷却して内容物を取り出し、白色ポリマ−４８ｇを得た。触媒効率は１６６Ｋｇ／ｇＺｒであった。この白色ポリマーのＭＦＲを測定したところ、０．９７ｇ／１０ｍｉｎであり、Ｍｎは７０８００であった。
実施例５
実施例３において、使用する固体触媒量を９８ｍｇ（Ｚｒ＝０．２７ｍｇ）とし、添加するヘキサン量を０．２６ｍｌ（２ｍｍｏｌ）とした以外は実施例３と同様に実験を行った。
重合終了後、余剰のガスを排出し、冷却して内容物を取り出し、白色ポリマ−４６ｇを得た。触媒効率は１７０Ｋｇ／ｇＺｒであった。この白色ポリマーのＭＦＲを測定したところ、０．９０ｇ／１０ｍｉｎであり、Ｍｎは７２３００であった。
比較例２
実施例３において使用する固体触媒量を１１１ｍｇ（Ｚｒ＝０．３０ｍｇ）とし、炭化水素成分を添加しなかったこと以外は実施例３と同様に実験を行った。
重合終了後、余剰のガスを排出し、冷却して内容物を取り出し、白色ポリマ−５０ｇを得た。触媒効率は１６７Ｋｇ／ｇＺｒであった。この白色ポリマーのＭＦＲを測定したところ，０．８５ｇ／１０ｍｉｎであり、Ｍｎは７５３００であった。
実施例６
（Ａ）固体触媒の調製
窒素雰囲気下で、電磁誘導攪拌機および冷却管を取り付けた５００ｍｌ三口フラスコに精製トルエン１００ｍｌを加え、ついでテトラプロポキシジルコニウム２．０ｇとインデン５．６ｇおよびトリイソブチルアルミニウム９．２ｇを加え加熱還流条件下で２時間攪拌反応させ、遷移金属触媒成分を調製した。次ぎに、メチルアルミノキサンのトルエン溶液（シェリング社製、濃度３．１ｍｍｏｌＡｌ／ｍｌ）１９５ｍｌを加え、室温で１時間攪拌反応させた。
窒素雰囲気下で、電磁誘導攪拌機および冷却管を取り付けた１Ｌ三口フラスコに、予め５００℃で７時間焼成処理したシリカ（富士デビソン製 ＃９５２）１５０ｇを入れ、フラスコを１５０℃まで加熱して１時間減圧乾燥を行った。
乾燥終了後、フラスコを室温まで冷却し、上記で得られた触媒成分溶液を添加し、常温で１時間反応させた。次いで、フラスコを４０℃まで昇温し、得られたスラリー溶液を６０分間減圧乾燥して溶媒を除去することにより、流動性の良い固体触媒１９９ｇを得た。
（Ｂ）重合
攪拌機を付した容量３Ｌのステンレススチール製オートクレーブを窒素置換した後、オートクレーブ内を７５℃まで昇温した。続いて、重合系内のスカベンジを行うためトリエチルアルミニウムのトルエン希釈溶液（１ｍｍｏｌ／ｍｌ）を０．３ｍｌ添加した後、固体触媒を１０６ｍｇ（Ｚｒ＝０．２９ｍｇ）供給した。次いでシクロヘキサン５．４ｍｌ（５０ｍｍｏｌ）を、エチレンとブテン−１の混合ガス（ブテン−１／エチレンモル比０．１５）９Ｋｇｆ／ｃｍ^２Ｇととも に張り込み重合を開始した。重合開始後、エチレンとブテン−１の混合ガス（ブテン−１／エチレンモル比０．０５）を連続的に供給しつつ、全圧を９Ｋｇｆ／ｃｍ^２Ｇに維持して２時間の重合を行った。重合終了後、余剰のガスを排出し、 冷却して内容物を取り出し、白色ポリマ−４３ｇを得た。このときの触媒効率は１４８Ｋｇ／ｇＺｒであった。この白色ポリマーのＭＦＲを測定したところ、８．５ｇ／１０ｍｉｎであり、Ｍｎは３６５００であった。
実施例７
実施例６において、使用する固体触媒量を１１１ｍｇ（Ｚｒ＝０．３０ｍｇ）とし、メチルシクロペンタンを５．６ｍｌ（５０ｍｍｏｌ）添加した以外は実施例６と同様に実験を行った。
重合終了後、余剰のガスを排出し、冷却して内容物を取り出し、白色ポリマ−４５ｇを得た。触媒効率は１５０Ｋｇ／ｇＺｒであった。この白色ポリマーのＭＦＲを測定したところ、８．３ｇ／１０ｍｉｎであり、Ｍｎは３６９００であった。
実施例８
実施例６において、使用する固体触媒量を９５ｍｇ（Ｚｒ＝０．２６ｍｇ）とし、イソブタンを２．９ｇ（５０ｍｍｏｌ）添加した以外は実施例６と同様に実験を行った。
重合終了後、余剰のガスを排出し、冷却して内容物を取り出し、白色ポリマ−４０ｇを得た。触媒効率は１５５Ｋｇ／ｇＺｒであった。この白色ポリマーのＭＦＲを測定したところ、８．６ｇ／１０ｍｉｎであり、Ｍｎは３６２００であった。
実施例９
実施例６において、使用する固体触媒量を１１０ｍｇ（Ｚｒ＝０．３０ｍｇ）とし、イソブタンを１．２ｇ（２０ｍｍｏｌ）添加した以外は実施例６と同様に実験を行った。
重合終了後、余剰のガスを排出し、冷却して内容物を取り出し、白色ポリマ−４８ｇを得た。触媒効率は１６０Ｋｇ／ｇＺｒであった。この白色ポリマーのＭＦＲを測定したところ、７．２ｇ／１０ｍｉｎであり、Ｍｎは３７７００であった。
比較例３
実施例６において使用する固体触媒量を１１１ｍｇ（Ｚｒ＝０．３０ｍｇ）とし，炭化水素成分を添加しなかったこと以外は実施例６と同様に実験を行った。
重合終了後，余剰のガスを排出し，冷却して内容物を取り出し，白色ポリマ−４７ｇを得た。触媒効率は１５６Ｋｇ／ｇＺｒであった。この白色ポリマーのＭＦＲを測定したところ，６．５ｇ／１０ｍｉｎであり、Ｍｎは３８３００であった。
実施例１０
（Ａ）固体触媒の調製
窒素雰囲気下で、電磁誘導攪拌機および冷却管を取り付けた５００ｍｌ三口フラスコに精製トルエン１００ｍｌを加え、ついでテトラブトシジルコニウム２．３ｇとシクロペンタジエン３．２ｇおよびトリエチルアルミニウム１３．１ｇを加え加熱還流条件下で２時間攪拌反応させた。次ぎに、メチルアルミノキサンのトルエン溶液（シェリング社製、濃度３．１ｍｍｏｌＡｌ／ｍｌ）１９５ｍｌを加え、室温で１時間攪拌反応させた。
窒素雰囲気下で、電磁誘導攪拌機および冷却管を取り付けた１Ｌ三口フラスコに、予め５００℃で７時間焼成処理したアルミナ１５０ｇを入れ、フラスコを１５０℃まで加熱して１時間減圧乾燥を行った。乾燥終了後、フラスコを室温まで冷却し、上記触媒成分溶液を添加し、常温で１時間反応させた。次いで、フラスコを４０℃まで昇温し、得られたスラリー溶液を６０分間減圧乾燥して溶媒を除去することにより、流動性の良い固体触媒１９０ｇを得た。
（Ｂ）重合
攪拌機を付した容量３Ｌのステンレススチール製オートクレーブを窒素置換した後、オートクレーブ内を７５℃まで昇温した。続いて、重合系内のスカベンジを行うためトリエチルアルミニウムのトルエン希釈溶液（１ｍｍｏｌ／ｍｌ）を０．３ｍｌ添加した後、固体触媒を１０６ｍｇ（Ｚｒ＝０．２９ｍｇ）供給した。次いでｎ−ヘキサン３．９ｍｌ（３０ｍｍｏｌ）を、エチレンとブテン−１の混合ガス（ブテン−１／エチレンモル比０．１５）９Ｋｇｆ／ｃｍ^２Ｇとともに 張り込み重合を開始した。重合開始後、エチレンとブテン−１の混合ガス（ブテン−１／エチレンモル比０．０５）を連続的に供給しつつ、全圧を９Ｋｇｆ／ｃｍ^２Ｇに維持して２時間の重合を行った。重合終了後、余剰のガスを排出し、冷 却して内容物を取り出し、白色ポリマ−４１ｇを得た。このときの触媒効率は１４１Ｋｇ／ｇＺｒであった。この白色ポリマーのＭＦＲを測定したところ、４．３ｇ／１０ｍｉｎであり、Ｍｎは４１２００であった。
比較例４
実施例１０において使用する固体触媒量を１１１ｍｇ（Ｚｒ＝０．３０ｍｇ）とし，炭化水素成分を添加しなかったこと以外は実施例１０と同様に実験を行った。重合終了後，余剰のガスを排出し，冷却して内容物を取り出し，白色ポリマ−４１ｇを得た。触媒効率は１３８Ｋｇ／ｇＺｒであった。この白色ポリマーのＭＦＲを測定したところ，３．１ｇ／１０ｍｉｎであり、Ｍｎは５１２００であった。
実施例１１
（Ａ）固体触媒の調製
窒素雰囲気下で、電磁誘導攪拌機および冷却管を取り付けた５００ｍｌ三口フラスコに精製トルエン１００ｍｌを加え、ついでテトラプロポキシジルコニウム２．０ｇとメチルシクロペンタジエン１．９ｇおよびトリエチルアルミニウム２．１ｇを加え加熱環流条件下で２時間攪拌反応させた。
次ぎに、メチルアルミノキサンのトルエン溶液（シェリング社製、濃度３．１ｍｍｏｌＡｌ／ｍｌ）１９５ｍｌを加え，室温で１時間攪拌反応させた。
窒素雰囲気下で、電磁誘導攪拌機および冷却管を取り付けた１Ｌ三口フラスコに，予め十分乾燥させたスチレン−ジビニルベンゼン共重合体ビーズ（オルガノ社製）１５０ｇを入れ、フラスコを９０℃まで加熱して１時間減圧乾燥を行った。乾燥終了後、フラスコを室温まで冷却し、ここに上記で得られた触媒成分溶液を添加し，常温で１時間反応させた。次いで、フラスコを４０℃まで昇温し、得られたスラリー溶液を６０分間減圧乾燥して溶媒を除去することにより、流動性の良い固体触媒２０１ｇを得た。
（Ｂ）重合
攪拌機を付した容量３Ｌのステンレススチール製オートクレーブを窒素置換した後、オートクレーブ内を７５℃まで昇温した。続いて、重合系内のスカベンジを行うためトリエチルアルミニウムのトルエン希釈溶液（１ｍｍｏｌ／ｍｌ）を０．３ｍｌ添加した後、固体触媒を１０６ｍｇ（Ｚｒ＝０．２９ｍｇ）供給した。次いでエタン０．５Ｌ（２２ｍｍｏｌ）を、エチレンとブテン−１の混合ガス（ブテン−１／エチレンモル比０．１５）９Ｋｇｆ／ｃｍ^２Ｇとともに張り込み 重合を開始した。重合開始後、エチレンとブテン−１の混合ガス（ブテン−１／エチレンモル比０．０５）を連続的に供給しつつ、全圧を９Ｋｇｆ／ｃｍ^２Ｇに 維持して２時間の重合を行った。重合終了後、余剰のガスを排出し、冷却して内容物を取り出し、白色ポリマ−３８ｇを得た。このときの触媒効率は１３０Ｋｇ／ｇＺｒであった。この白色ポリマーのＭＦＲを測定したところ、１．０３ｇ／１０ｍｉｎであり、Ｍｎは６９５００であった。
比較例５
実施例１１において使用する固体触媒量を９８ｍｇ（Ｚｒ＝０．２７ｍｇ）とし、エタンを添加しなかったこと以外は実施例１１と同様に実験を行った。重合終了後、余剰のガスを排出し、冷却して内容物を取り出し、白色ポリマ−３６ｇを得た。触媒効率は１３２Ｋｇ／ｇＺｒであった。この白色ポリマーのＭＦＲを測定したところ，０．９０ｇ／１０ｍｉｎであり、Ｍｎは７２３００であった。
実施例１２
（Ａ）固体触媒の調製
実施例６と同様に調製した。
（Ｂ）重合
気相重合装置に攪拌機のついたステンレス製オートクレーブを使用し、ブロワー、流量調節器および乾式サイクロンでループをつくり、オートクレーブはジャケットに温水を流すことによって温度を調節した。６０℃に調節したオートクレーブに（Ａ）で得られた固体触媒を１００ｍｇ／ｈおよびヘキサンを８０ｍｌ／ｈ（０．６ｍｏｌ／ｈ）の速度で供給し、またオートクレーブ気相中のブテン−１／エチレンモル比を０．２５になるように調節しながら各々のガスを供給し、全圧を８Ｋｇｆ／ｃｍ^２Ｇに保ちながらブロワーにより系内のガスを循環させ、 生成ポリマーを間欠的に抜き出しながら１０時間の連続重合を行った。触媒効率は７０ｋｇ／ｇＺｒで、ＭＦＲは６．２ｇ／１０ｍｉｎであり、Ｍｎは３８５００であった。
実施例１３
実施例１２において、重合中に供給するヘキサン量を８ｍｌ／ｈ（０．０６ｍｏｌ／ｈ）としたこと以外は実施例１２と同様な重合を行った。触媒効率は７２ｋｇ／ｇＺｒで、ＭＦＲは５．３ｇ／１０ｍｉｎであり、Ｍｎは３９８００であった。
比較例６
実施例１２において、重合中にヘキサンを供給しなかったこと以外は実施例１２と同様な重合を行った。触媒効率は７１ｋｇ／ｇＺｒで、ＭＦＲは３．３ｇ／１０ｍｉｎであり、Ｍｎは５０１００であった。
【図面の簡単な説明】
【図１】本発明の重合用触媒の調製工程を示すフローシートである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel method for producing a polyolefin. More specifically, the present invention relates to a method for producing a polyolefin, which makes it possible to control the molecular weight of a produced polymer by a completely different means in a gas phase polymerization method.
[0002]
Problems to be solved by the prior art and the invention
In producing a polyolefin, particularly an ethylene polymer or an ethylene / α-olefin copolymer, adjusting the molecular weight of the polymer is an important issue in widening the product grade range. As a method for adjusting the molecular weight of the polymer, a method of adjusting the concentration of hydrogen introduced into the polymerization reaction system, or a method of controlling the polymerization temperature or the polymerization pressure is generally known.
An object of the present invention is to provide a method for producing a polyolefin, which employs a completely different method for controlling the molecular weight of a polymer.
[0003]
[Means for Solving the Problems]
One of the polyolefin production methods according to the present invention,
(1) General formula Me¹R¹ _p(OR^Two)_qX¹ _4-pqA compound represented by
[Wherein, R¹, R^TwoIndependently represents a hydrocarbon group having 1 to 24 carbon atoms;¹Represents a halogen atom or a hydrogen atom;¹Represents Zr, Ti or Hf, and p and q are respectively 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, and 0 ≦ p + q ≦ 4.
(2) General formula Me^TwoR^Three _m(OR^Four)_nX^Two _zmnA compound represented by
[Wherein, R^Three, R^FourIndependently represents a hydrocarbon group having 1 to 24 carbon atoms;^TwoRepresents a halogen atom or a hydrogen atom;^TwoIs a group I-III element of the periodic table,
z is Me^TwoAnd m and n are respectively 0 <m ≦ z, 0 ≦ n ≦ z, and 0 <m + n ≦ z.]
(3) a cyclic organic compound having two or more conjugated double bonds, and
(4) Modified organoaluminum compound containing Al-O-Al bond
When polymerizing or copolymerizing olefins in a substantially gaseous phase in the presence of a catalyst obtained by contacting the olefins with each other, at least one liquid selected from a saturated hydrocarbon compound and an aromatic hydrocarbon compound and / or Or gaseous hydrocarbon compoundsIn an amount of 0.001 to 100 mol per 1 g of the catalyst.Coexist in the reaction systemLetThe molecular weight of the resulting polyolefinReduces compared to when no hydrocarbon compound is usedIt is characterized by the following.
Another one of the polyolefin production method according to the present invention,
(1) General formula Me¹R¹ _p(OR^Two)_qX¹ _4-pqA compound represented by
[Wherein, R¹, R^TwoIndependently represents a hydrocarbon group having 1 to 24 carbon atoms;¹Represents a halogen atom or a hydrogen atom;¹Represents Zr, Ti or Hf, and p and q are respectively 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, and 0 ≦ p + q ≦ 4.
(2) General formula Me^TwoR^Three _m(OR^Four)_nX^Two _zmnA compound represented by
[Wherein, R^Three, R^FourIndependently represents a hydrocarbon group having 1 to 24 carbon atoms;^TwoRepresents a halogen atom or a hydrogen atom;^TwoIs a group I-III element of the periodic table,
z is Me^TwoAnd m and n are respectively 0 <m ≦ z, 0 ≦ n ≦ z, and 0 <m + n ≦ z.]
(3) a cyclic organic compound having two or more conjugated double bonds,
(4) a modified organoaluminum compound containing an Al-O-Al bond, and
(5) Inorganic compound carrier and / or particulate polymer carrier
When polymerizing or copolymerizing olefins in a substantially gaseous phase in the presence of a catalyst obtained by contacting the olefins with each other, at least one liquid selected from a saturated hydrocarbon compound and an aromatic hydrocarbon compound and / or Or gaseous hydrocarbon compoundsIn an amount of 0.001 to 100 mol per 1 g of the catalyst.Coexist in the reaction systemLetThe molecular weight of the resulting polyolefinReduces compared to when no hydrocarbon compound is usedIt is characterized by the following.
According to the method of the present invention, when producing an olefin polymer, a polymer having a high molecular weight and a relatively wide molecular weight distribution can be produced in high yield, and when producing an olefin copolymer. Thus, a copolymer having a narrow composition distribution can be produced at a high yield. Further, according to the present invention, an olefin polymer and a copolymer having good particle properties can be obtained.
In the method of the present invention, the specific hydrocarbon compound coexisting in the polymerization reaction systemBy setting the amount in the range of 0.001 to 100 mol per 1 g of the catalyst, the molecular weight of the produced polyolefin can be reduced as compared with the case where no hydrocarbon compound is used.
[0004]
BEST MODE FOR CARRYING OUT THE INVENTION
First, the catalyst used in the present invention will be described.
The catalyst used in the present invention is
General formula Me¹R¹ _p(OR²)_qX¹ _4-pq(Component (1)) represented by the formula:²R³ _m(OR⁴)_nX² _zmn(Component (2)), an organic compound having two or more conjugated double bonds in a ring (component (3)), a modified organoaluminum compound containing an Al—O—Al bond (component (4)) ,
By contacting the four components with each other or by contacting the five components obtained by adding the inorganic compound carrier and / or the particulate polymer carrier (component (5)) to the above four components. .
[0005]
Component (1) is represented by the following general formula (1).
General formula Me¹R¹ _p(OR²)_qX¹ _4-pq              (1)
In the general formula (1), R¹And R²Represents a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. R¹And R²Examples of the hydrocarbon group which can be individually taken are methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, tert-butyl, cyclobutyl, pentyl, isopentyl, Alkyl groups such as neopentyl group, cyclopentyl group, hexyl group, isohexyl group, cyclohexyl group, heptyl group and octyl group; alkenyl groups such as vinyl group and allyl group; phenyl group, tolyl group, xylyl group, mesityl group, indenyl group, Aryl groups such as a naphthyl group; and aralkyl groups such as a benzyl group, a trityl group, a phenethyl group, a styryl group, a benzhydryl group, a phenylbutyl group, a phenylpropyl group, and a neophyl group. These hydrocarbon groups may have a branched chain.
X¹Is a halogen atom or a hydrogen atom of fluorine, iodine, chlorine and bromine.
Me¹Represents Zr, Ti or Hf, and is preferably Zr.
p and q are respectively 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, and 0 ≦ p + q ≦ 4, and are preferably integers satisfying the range of 0 <p + q ≦ 4.
[0006]
The compound represented by the general formula (1) can be used alone or as a mixture of two or more kinds as the component (1) of the present invention.
Specific examples of the compound represented by the general formula (1) include tetramethyl zirconium, tetraethyl zirconium, tetrapropyl zirconium, tetra n-butyl zirconium, tetrapentyl zirconium, tetraphenyl zirconium, tetratolyl zirconium, tetrabenzyl zirconium, Tetraallyl zirconium, tetraneofilzirconium, tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetrabutoxyzirconium, tetrapentyloxyzirconium, tetraphenoxyzirconium, tetratolyloxyzirconium, tetrabenzyloxyzirconium, tetraallyloxyzirconium, tetra Neofiloxyzirconium, trimethylmonochlorodisiloxane , Triethylmonochlororhosiliconium, tripropylmonochlororhosiliconium, trin-butylmonochlororhosiliconium, tripentylmonochlororhosiliconium, triphenylmonochlororhosiliconium, tritolylmonochlororhoconiconium, tribenzylmonochlororhosiliconium, triallylmonochlororhosiliconium, trineofil monochlororhosiliconium, dimethyl Dichloro zirconium, diethyl dichloro zirconium, dipropyl dichloro zirconium, di-n-butyl dichloro zirconium, dipentyl dichloro zirconium, diphenyl dichloro zirconium, ditolyl dichloro zirconium, dibenzyl dichloro zirconium, diallyl dichloro zirconium, dineophil dichloro zirconium, monomethyl trichloro zirconium Conium, monoethyltrichlorozirconium, monopropyltrichlorozirconium, monon-butyltrichlorozirconium, monopentyltrichlorozirconium, monophenyltrichlorozirconium, monotolyltrichlorozirconium, monobenzyltrichlorozirconium, monoallyltrichlorozirconium, mononeophyltrichlorozirconium, Tetrachlorozirconium, trimethoxymonochlororodiconium, dimethoxydichlorozirconium, monomethoxytrichlorozirconium, triethoxymonochlorozirconium, diethoxydichlorozirconium, monoethoxytrichlorozirconium, tripropoxymonochlororsiliconium, dipropoxydichlorozirconium, monopropoxytrichlorozil Conium, tri-n-butoxymonochlororodiconium, di-n-butoxydichlorozirconium, mono-n-butoxytrichlorozirconium, tripentyloxymonochlororodiconium, dipentyloxydichlorozirconium, monopentyloxytrichlorozirconium, triphenoxymonochlororhodilconium, diphenoxydichlorozirconium, Monophenoxytrichlorozirconium, tolyloxydichlorozirconium, ditolyloxydichlorozirconium, monotolyloxytrichlorozirconium, tribenzyloxymonochlorodisilconium, dibenzyloxydichlorozirconium, monobenzyloxytrichlorozirconium, triallyloxymonochlororsiliconium, diallyloxydichloro Zirconi System, monoallyloxytrichlorozirconium, trineofiloxymonochlorodisilconium, dineofiloxydichlorozirconium, mononeofiloxytrichlorozirconium, tetrabromozirconium, trimethylmonobromozirconium, triethylmonobromozirconium, tripropylmonobromozirconium, tripropyl n-butyl monobromo zirconium, tripentyl monobromo zirconium, triphenyl monobromo zirconium, tolyl monobromo zirconium, tribenzyl monobromo zirconium, triallyl monobromo zirconium, trineofil monobromo zirconium, dimethyl dibromo zirconium, diethyl dibromo zirconium , Dipropyldibromozirconium, di-n-butyldibro Zirconium, dipentyl dibromo zirconium, diphenyl dibromo zirconium, ditolyl dibromo zirconium, dibenzyl dibromo zirconium, diallyl dibromo zirconium, dyneophil dibromo zirconium, monomethyl tribromo zirconium, monoethyl tribromo zirconium, monopropyl tribromo zirconium, mono n- Butyl tribromo zirconium, monopentyl tribromo zirconium, monophenyl tribromo zirconium, monotolyl tribromo zirconium, monobenzyl tribromo zirconium, monoallyl tribromo zirconium, mononeophyl tribromo zirconium, trimethoxy monobromo zirconium, dimethoxy dibromo Zirconium, monomethoxytribromozirconium, g Liethoxy monobromo zirconium, diethoxy dibromo zirconium, triethoxy tribromo zirconium, tripropoxy monobromo zirconium, dipropoxy dibromo zirconium, monopropoxy tribromo zirconium, tri n-butoxy monobromo zirconium, di n-butoxy dibromo zirconium, mono n-butoxytribromozirconium, tripentyloxymonobromozirconium, dipentyloxydibromozirconium, monopentyloxytribromozirconium, triphenoxymonobromozirconium, diphenoxydibromozirconium, monophenoxytribromozirconium, tolyloxymonobromozirconium, Ditolyloxydibromozirconium, monotolyloxytribromozil , Tribenzyloxymonobromozirconium, dibenzyloxydibromozirconium, monobenzyloxytribromozirconium, triallyloxymonobromozirconium, diallyloxydibromozirconium, monoallyloxytribromozirconium, trineofiloxymonobromozirconium, dine Neofiloxydibromozirconium, mononeophyloxytribromozirconium, tetraiodozirconium, trimethylmonoiodozirconium, triethylmonoiodozirconium, tripropylmonoiodozirconium, tri-n-butylmonoiodozirconium, tripentylmonoiodozirconium, triphenyl Zirconium monoiodo, zirconium tritolyl monoiodo, tribenzyl mono Zirconium chloride, triallyl monoiodo zirconium, trineofil monoiodo zirconium, dimethyl diiodo zirconium, diethyl diiodo zirconium, dipropyl diiodo zirconium, di-n-butyl diiodo zirconium, dipentyl diiodo zirconium, diphenyl diiodo zirconium, ditrizium Rudiiodozirconium, dibenzyldiiodozirconium, diallyldiiodozirconium, dineophilediiodozirconium, monomethyltriiodozirconium, monoethyltriiodozirconium, monopropyltriiodozirconium, mono-n-butyltriiodozirconium, monopentyltri Iodo zirconium, monophenyl triiodo zirconium, monotolyl triiodo zirconium, monobenzyl Triiodo zirconium, tetraiodo zirconium, trimethoxy monoiodo zirconium, dimethoxy diiodo zirconium, monomethoxy triiodo zirconium, triethoxy monoiodo zirconium, diethoxy diiodo zirconium, monoethoxy triiodo zirconium, tripropoxy monoiodo zirconium, dipropionate Propoxy diiodo zirconium, monopropoxy triiodo zirconium, tri n-butoxy monoiodo zirconium, di n-butoxy diiodo zirconium, mono n-butoxy triiodo zirconium, tripentyloxy monoiodo zirconium, dipentyloxy diiodo zirconium, monopentyl Zirconium oxytriiodo, zirconium triphenoxymonoiodo, diphenoxydiiododi Conium, monophenoxy triiodo zirconium, tolyloxy monoiodo zirconium, ditolyloxy diiodo zirconium, monotolyloxy triiodo zirconium, tribenzyloxy monoiodo zirconium, dibenzyloxy diiodo zirconium, monobenzyloxy triiodo zirconium, Triallyloxymonoiodozirconium, diallyloxydiiodozirconium, monoallyloxytriiodozirconium, trineofiloxymonoiodozirconium, dineophileoxydiiodozirconium, mononeofiloxytriiodozirconium, tribenzylmonomethoxyzirconium, Tribenzyl monoethoxy zirconium, tribenzyl monopropoxy zirconium, tribenzyl monobu Xyzirconium, tribenzylmonopentyloxyzirconium, tribenzylmonophenoxyzirconium, tribenzylmonotolyloxyzirconium, tribenzylmonobenzyloxyzirconium, tribenzylmonoallyloxyzirconium, tribenzylmononeophyloxyzirconium, dibenzyldimethoxyzirconium, Dibenzyldiethoxyzirconium, dibenzyldipropoxyzirconium, dibenzyldibutoxyzirconium, dibenzyldipentyloxyzirconium, dibenzyldiphenoxyzirconium, dibenzylditolyloxyzirconium, dibenzyldibenzyloxyzirconium, dibenzyldiallyloxyzirconium, Dibenzyldineophile oxyzirconium, monobenzyltrime Toxizirconium, monobenzyltriethoxyzirconium, monobenzyltripropoxyzirconium, monobenzyltributoxyzirconium, monobenzyltripentyloxyzirconium, monobenzyltriphenoxyzirconium, monobenzyltritolyloxyzirconium, monobenzyltribenzyloxyzirconium, monobenzyl Triallyloxyzirconium, monobenzyltrineophyloxyzirconium, trineofilmonomethoxyzirconium, trineofilmonoethoxyzirconium, trineofilmonopropoxyzirconium, trineofilmonobutoxyzirconium, trineofilmonophenoxyzirconium, dineo Fildimethoxyzirconium, Dineophilediethoxyzirconium , Dineophile dipropoxy zirconium, Dineophile dibutoxy zirconium, Dineophile diphenoxy zirconium, Mononeophile trimethoxy zirconium, Mononeophile triethoxy zirconium, Mononeophile tripropoxy zirconium, Mononeophile tributoxy zirconium, Mononeophyltriphenoxyzirconium, zirconium tetrahydride, zirconium monohydride trimethoxide, zirconium monohydride triethoxide, zirconium monohydride tripropoxide, zirconium monohydride tributoxide, zirconium dihydride dimethoxide, zirconium dihydride dioxide Toxide, zirconium dihydride dipropoxide, Ruconium dihydride dibutoxide, zirconium trihydride monomethoxide, zirconium trihydride monoethoxide, zirconium trihydride monopropoxide, zirconium trihydride monobutoxide, zirconium monohydride trichloride, zirconium monohydride tribromide, Zirconium monohydride triiodide, zirconium monohydride trifluoride, zirconium dihydride dichloride, zirconium dihydride dibromide, zirconium dihydride diiodide, zirconium dihydride difluoride, zirconium trihydride monochloride, zirconium trihydride monobromide, Zirconi Trihydride monoiodide, zirconium trihydride monofluoride, zirconium monohydride trimethyl, zirconium monohydride tribenzyl, zirconium monohydride triphenyl, zirconium dihydride dimethyl, zirconium dihydride dibenzyl, zirconium dihydride diphenyl, zirconium trihydride Monomethyl, zirconium trihydride monobenzyl, zirconium trihydride monophenyl, zirconium monohydride dimethoxide monochloride, zirconium monohydride diethoxide monochloride, zirconium monohydride dipropoxide monochloride, zirconium monohydride dibutoxide mono Chloride, zirconium dihydride monomethoxide monochloride, zirconium dihydride monoethoxide monochloride, zirconium dihydride monopropoxide monochloride, zirconium dihydride monobutoxide monochloride, zirconium monohydride dimethoxide monomethyl, zirconium mono Hydride diethoxide monobenzyl, zirconium monohydride dipropoxide monophenyl, zirconium dihydride monomethoxide monomethyl, zirconium dihydride monoethoxide monobenzyl, zirconium dihydride monopropoxide monophenyl, zirconium monohydride monomethoxide monochrome Ride monobenzyl, zirconium Roh hydride mono methoxide monochloride monophenyl, zirconium monohydride mono methoxide monochloride monomethyl,
[0007]
Tetramethyl titanium, tetraethyl titanium, tetrapropyl titanium, tetra n-butyl titanium, tetrapentyl titanium, tetraphenyl titanium, tetratolyl titanium, tetrabenzyl titanium, tetraallyl titanium, tetraneofil titanium, tetramethoxy titanium, tetraethoxy titanium, Tetrapropoxytitanium, tetrabutoxytitanium, tetrapentyloxytitanium, tetraphenoxytitanium, tetratolyloxytitanium, tetrabenzyloxytitanium, tetraallyloxytitanium, tetraneophyloxytitanium, trimethylmonochlorotitanium, triethylmonochlorotitanium, tripropylmonochlorotitanium , Tri-n-butyl monoc Rotitanium, tribenzylmonochlorotitanium, dimethyldichlorotitanium, diethyldichlorotitanium, di-n-butyldichlorotitanium, dibenzyldichlorotitanium, monomethyltrichlorotitanium, monoethyltrichlorotitanium, monon-butyltrichlorotitanium, monobenzyltrichlorotitanium, tetrabenzyl Chlorotitanium, trimethoxymonochlorotitanium, dimethoxydichlorotitanium, monomethoxytrichlorotitanium, triethoxymonochlorotitanium, ethoxydichlorotitanium, monoethoxytrichlorotitanium, tripropoxymonochlorotitanium, dipropoxydichlorotitanium, monopropoxytrichlorotitanium, trin-butoxy Monochlorotitanium, di-n Butoxydichlorotitanium, mono-n-butoxytrichlorotitanium, tripentyloxymonochlorotitanium, dipentyloxydichlorotitanium, monopentyloxytrichlorotitanium, triphenoxymonochlorotitanium, diphenoxydichlorotitanium, monophenoxytrichlorotitanium, tritolyloxymonochlorotitanium, ditolyloxymonochlorotitanium Tolyloxydichlorotitanium, monotolyloxytrichlorotitanium, tribenzyloxymonochlorotitanium, dibenzyloxydichlorotitanium, monobenzyloxytrichlorotitanium, tetrabromotitanium, trimethylmonobromotitanium, triethylmonobromotitanium, tripropylmonobromotitanium, tripropyl n-butyl monobromo titani , Tribenzylmonobromotitanium, dimethyldibromotitanium, diethyldibromotitanium, di-n-butyldibromotitanium, dibenzyldibromotitanium, monomethyltribromotitanium, monoethyltribromotitanium, monon-butyltribromotitanium, monobenzyltrimo Bromotitanium, tetrabromotitanium, trimethoxymonobromotitanium, dimethoxydibromotitanium, trimethoxytribromotitanium, triethoxymonobromotitanium, diethoxydibromotitanium, monoethoxytribromotitanium, tripropoxymonobromotitanium, dipropoxydibromotitanium , Monopropoxytribromotitanium, tri-n-butoxymonobromotitanium, di-n-butoxy Dibromotitanium, mono-n-butoxytribromotitanium, tripentyloxymonobromotitanium, dipentyloxydibromotitanium, monopentyloxytribromotitanium, triphenoxymonobromotitanium, diphenoxydibromotitanium, monophenoxytribromotitanium, tolyloxy Monobromotitanium, ditolyloxydibromotitanium, monotolyloxytribromotitanium, tribenzyloxymonobromotitanium, dibenzyloxydibromotitanium, monobenzyloxytribromotitanium, tetraiodotitanium, trimethylmonoiodotitanium, triethylmonoiodotitanium , Tripropyl monoiodo titanium, tri n-butyl monoiodo titanium, tri Benzyl monoiodo titanium, dimethyl diiodo titanium, diethyl diiodo titanium, di-n-butyl diiodo titanium, dibenzyl diiodo titanium, monomethyl triiodo titanium, monoethyl triiodo titanium, mono n-butyl triiodo titanium, monobenzyl Triiodo titanium, tetraiodo titanium, trimethoxy monoiodo titanium, dimethoxy diiodo titanium, monomethoxy triiodo titanium, triethoxy monoiodo titanium, diethoxy diiodo titanium, monoethoxy triiodo titanium, tripropoxy monoiodo titanium, dipropitanium Propoxydiioditanium, monopropoxytriiodotitanium, tri-n-butoxymonoiodotitanium, di-n-butoxydiiodide Titanium, mono-n-butoxytriiodotitanium, tripentyloxymonoiodotitanium, dipentyloxydiiodotitanium, monopentyloxytriiodotitanium, triphenoxymonoiodotitanium, diphenoxydiiodotitanium, monophenoxytriiodotitanium, tritolyl Oxymonoiodo titanium, ditolyloxy diiodo titanium, monotolyloxy triiodo titanium, tribenzyloxy monoiodo titanium, dibenzyloxy diiodo titanium, monobenzyloxy triiodo titanium, tribenzyl monomethoxy titanium, tribenzyl monoethoxy Titanium, tribenzylmonopropoxytitanium, tribenzylmonobutoxytitanium, tribenzylmonophenoki Titanium, dibenzyldimethoxytitanium, dibenzyldiethoxytitanium, dibenzyldipropoxytitanium, dibenzyldibutoxytitanium, dibenzyldiphenoxytitanium, monobenzyltrimethoxytitanium, monobenzyltriethoxytitanium, monobenzyltripropoxytitanium, monobenzyl Benzyltributoxytitanium, Monobenzyltriphenoxytitanium, Trineophile monomethoxytitanium, Trineophile monoethoxytitanium, Trineophile monopropoxytitanium, Trineophile monobutoxytitanium, Trineophile monophenoxytitanium, Dineofil dimethoxy Titanium, Dineophile Diethoxy Titanium, Dineophile Dipropoxy Titanium, Dineoff Yldibutoxytitanium, dineophile diphenoxytitanium, mononeophyltrimethoxytitanium, mononeophyltriethoxytitanium, mononeophile tripropoxytitanium, mononeophile tributoxytitanium, mononeophile tributoxytitanium, mononeophile triphenoxytitanium,
[0008]
Tetramethyl hafnium, tetraethyl hafnium, tetrapropyl hafnium, tetra n-butyl hafnium, tetrapentyl hafnium, tetraphenyl hafnium, tetratolyl hafnium, tetrabenzyl hafnium, tetraallyl hafnium, tetraneophyl hafnium, tetramethoxy hafnium, tetraethoxy hafnium, Tetrapropoxyhafnium, tetrabutoxyhafnium, tetrapentyloxyhafnium, tetraphenoxyhafnium, tetratolyloxyhafnium, tetrabenzyloxyhafnium, tetraallyloxyhafnium, tetraneophyloxyhafnium, trimethylmonochlorohafnium, triethylmonochlorohafnium, tripropylmonochlorohafnium , Tri-n-butyl monoc Rohafnium, tribenzylmonochlorohafnium, dimethyldichlorohafnium, diethyldichlorohafnium, di-n-butyldichlorohafnium, dibenzyldichlorohafnium, monomethyltrichlorohafnium, monoethyltrichlorohafnium, monon-butyltrichlorohafnium, monobenzyltrichlorohafnium, tetrachloro Hafnium, trimethoxymonochlorohafnium, dimethoxydichlorohafnium, monomethoxytrichlorohafnium, triethoxymonochlorohafnium, diethoxydichlorohafnium, monoethoxytrichlorohafnium, tripropoxymonochlorohafnium, dipropoxydichlorohafnium, monopropoxytrichlorohafnium, trin-butoxy Monochlorohafnium, di -Butoxydichlorohafnium, mono-n-butoxytrichlorohafnium, tripentyloxymonochlorohafnium, dipentyloxydichlorohafnium, monopentyloxytrichlorohafnium, triphenoxymonochlorohafnium, diphenoxydichlorohafnium, monophenoxytrichlorohafnium, tolyloxymonochlorohafnium, Ditolyloxydichlorohafnium, monotolyloxytrichlorohafnium, tribenzyloxymonochlorohafnium, dibenzyloxydichlorohafnium, monobenzyloxytrichlorohafnium, tetrabromohafnium, trimethylmonobromohafnium, triethylmonobromohafnium, tripropylmonobromohafnium, Tri-n-butyl monobromohafni , Tribenzylmonobromohafnium, dimethyldibromohafnium, diethyldibromohafnium, di-n-butyldibromohafnium, dibenzyldibromohafnium, monomethyltribromohafnium, monoethyltribromohafnium, monon-butyltribromohafnium, monobenzyltrif Bromohafnium, tetrabromohafnium, trimethoxymonobromohafnium, dimethoxydibromohafnium, monomethoxytribromohafnium, triethoxymonobromohafnium, diethoxydibromohafnium, monoethoxytribromohafnium, tripropoxymonobromohafnium, dipropoxydibromohafnium , Monopropoxytribromohafnium, tri-n-butoxymonobromohafnium, di-n-butoxy Dibromohafnium, mono-n-butoxytribromohafnium, tripentyloxymonobromohafnium, dipentyloxydibromohafnium, monopentyloxytribromohafnium, triphenoxymonobromohafnium, diethoxydibromohafnium, monophenoxytribromohafnium, tolyloxy Monobromohafnium, ditolyloxydibromohafnium, monotolyloxytribromohafnium, tribenzyloxymonobromohafnium, dibenzyloxydibromohafnium, monobenzyloxytribromohafnium, tetraiodohafnium, trimethylmonoiodohafnium, triethylmonoiodohafnium , Tripropyl monoiodohafnium, tri-n-butyl monoiodohafnium, tri Benzyl monoiodohafnium, dimethyldiiodohafnium, diethyldiiodohafnium, di-n-butyldiiodohafnium, dibenzyldiiodohafnium, monomethyltriiodohafnium, monoethyltriiodohafnium, monon-butyltriiodohafnium, monobenzyl Triiodohafnium, Tetraiodohafnium, Trimethoxymonoiodohafnium, Dimethoxydiiodohafnium, Monomethoxytriiodohafnium, Triethoxymonoiodohafnium, Diethoxydiiodohafnium, Monoethoxytriiodohafnium, Tripropoxymonoiodohafnium, Dipropoxymonoiodohafnium Propoxydiiodohafnium, monopropoxytriiodohafnium, tri-n-butoxymonoiodohafnium, di-n-butoxydiiodohafnium Funium, mono-n-butoxytriiodohafnium, tripentyloxymonoiodohafnium, dipentyloxydiiodohafnium, monopentyloxytriiodohafnium, triphenoxymonoiodohafnium, diphenoxydiiodohafnium, monophenoxytriiodohafnium, tritolyl Oxymonoiodohafnium, ditolyloxydiiodohafnium, monotolyloxytriiodohafnium, tribenzyloxymonoiodohafnium, dibenzyloxydiiodohafnium, monobenzyloxytriiodohafnium, tribenzylmonomethoxyhafnium, tribenzylmonoethoxy Hafnium, tribenzyl monopropoxy hafnium, tribenzyl monobutoxy hafnium, tribenzyl monophenoxy Funium, dibenzyl dimethoxy hafnium, dibenzyl diethoxy hafnium, dibenzyl dipropoxy hafnium, dibenzyl dibutoxy hafnium, dibenzyl diphenoxy hafnium, monobenzyl trimethoxy hafnium, monobenzyl triethoxy hafnium, monobenzyl tripropoxy hafnium, mono Benzyl tributoxy hafnium, monobenzyl triphenoxy hafnium, trineofil monomethoxy hafnium, trineofil monoethoxy hafnium, trineofil monopropoxy hafnium, trineofil monobutoxy hafnium, trineofil monophenoxy hafnium, dineophile dimethoxy Hafnium, Dineophile Diethoxy Hafnium, Dineophile Dipropoxy Hafnium, Zineoff Distearate butoxy hafnium, di neophyl diphenoxy hafnium, mono neophyl trimethoxy hafnium, mono neophyl triethoxy hafnium, mono neophyl tripropoxy hafnium, mono neophyl tributoxy hafnium, and the like mono- neophyl triphenoxy hafnium.
Each of the compounds exemplified above is a compound represented by the general formula (1)¹And R²Is a linear (normal), but structural isomers in which these are iso-, sec-, tert-, and neo- can of course be used as the component (1).
[0009]
Among the compounds exemplified above as specific examples, tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetrabutoxyzirconium, tetrabutoxytitanium, and tetrabutoxyhafnium are preferred. Particularly preferably, a general formula Zr (OR) such as tetraethoxyzirconium, tetrapropoxyzirconium or tetrabutoxyzirconium is preferable.₄It is a compound represented by [R = alkyl group].
[0010]
Component (2) is represented by the following general formula (2).
Me²R³ _m(OR⁴)_nX² _zmn                    (2)
In the general formula (2), Me²Represents any of Group I to III elements of the periodic table, including lithium, sodium, potassium, magnesium, calcium, zinc, boron, aluminum, and the like. In particular, Group III is particularly desirable.
R³And R⁴Represents a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. R³And R⁴Can be taken individually as methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, cyclopentyl Alkyl group such as group, hexyl group, isohexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, dodecyl group; alkenyl group such as vinyl group, allyl group, phenyl group, tolyl group, xylyl group, mesityl group, indenyl And aralkyl groups such as benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, phenylbutyl group, phenylpropyl group and neophyl group. These hydrocarbon groups may have a branched chain.
X²Represents a halogen atom or a hydrogen atom such as fluorine, iodine, chlorine, or bromine;²Is a hydrogen atom, Me²Is a Group III element of the periodic table exemplified by boron, aluminum and the like.
z is Me²And m and n are numbers having a relationship of 0 ≦ m ≦ z, 0 ≦ n ≦ z, and 0 <m + n ≦ z.
[0011]
The compound represented by the general formula (2) can be used alone or as a mixture of two or more kinds as the component (2) of the present invention.
Specific examples of the compound represented by the general formula (2) include methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, butyl lithium, t-butyl lithium, pentyl lithium, octyl lithium, phenyl lithium, benzyl lithium, and dimethyl lithium. Magnesium, diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dibutyl magnesium, di-t-butyl magnesium, dipentyl magnesium, dioctyl magnesium, diphenyl magnesium, dibenzyl magnesium, methyl magnesium chloride, ethyl magnesium chloride, propyl magnesium chloride, isopropyl magnesium Chloride, butylmagnesium chloride, t-butylmagnesium chloride, Methyl magnesium chloride, octyl magnesium chloride, phenyl magnesium chloride, benzyl magnesium chloride, methyl magnesium bromide, methyl magnesium iodide, ethyl magnesium bromide, ethyl magnesium iodide, propyl magnesium bromide, propyl magnesium iodide, isopropyl magnesium bromide, isopropyl magnesium Iodide, butyl magnesium bromide, butyl magnesium iodide, t-butyl magnesium bromide, t-butyl magnesium iodide, pentyl magnesium bromide, pentyl magnesium iodide, octyl magnesium bromide, octyl magnesium iodide, phenylma Nesium bromide, phenyl magnesium iodide, benzyl magnesium bromide, benzyl magnesium iodide, dimethyl zinc, diethyl zinc, dipropyl zinc, diisopropyl zinc, di n-butyl zinc, di-t-butyl zinc, dipentyl zinc, dioctyl zinc, diphenyl zinc, Dibenzyl zinc, trimethyl boron, triethyl boron, tripropyl boron, triisopropyl boron, tributyl boron, tri-t-butyl boron, tripentyl boron, trioctyl boron, triphenyl boron, tribenzyl boron, trimethyl aluminum, triethyl aluminum, diethyl aluminum chloride , Diethylaluminum bromide, diethylaluminum fluoride, diethylaluminum iodide, Chill aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum difluoride, ethyl aluminum diiodide, tripropyl aluminum, dipropyl aluminum chloride, dipropyl aluminum bromide, dipropyl aluminum fluoride, dipropyl aluminum iodide, propyl aluminum dichloride , Propyl aluminum dibromide, propyl aluminum difluoride, propyl aluminum diiodide, triisopropyl aluminum, diisopropyl aluminum chloride, diisopropyl aluminum bromide, diisopropyl aluminum fluoride, diisopropyl aluminum iodide, ethyl aluminum sesquichloride, ethyl alcohol Minium sesquibromide, propyl aluminum sesquichloride, propyl aluminum sesquibromide, butyl aluminum sesquichloride, butyl aluminum sesquibromide, isopropyl aluminum dichloride, isopropyl aluminum dibromide, isopropyl aluminum difluoride, isopropyl aluminum diiodide, tributyl aluminum, dibutyl aluminum Chloride, dibutylaluminum bromide, dibutylaluminum fluoride, dibutylaluminum iodide, butylaluminum dichloride, butylaluminum dibromide, butylaluminum difluoride, butylaluminum diiodide, trisec-butylaluminum, disec-butyl Aluminum chloride, disec-butylaluminum bromide, disec-butylaluminum fluoride, disec-butylaluminum iodide, sec-butylaluminum dichloride, sec-butylaluminum dibromide, sec-butylaluminum difluoride, sec-butyl Aluminum diiodide, tri-tert-butyl aluminum, di-tert-butyl aluminum chloride, di-tert-butyl aluminum bromide, di-tert-butyl aluminum fluoride, di-tert-butyl aluminum iodide, tert-butyl aluminum dichloride, tert-butyl Aluminum dibromide, tert-butyl aluminum difluoride, tert-butyl aluminum Minium diiodide, triisobutylaluminum, diisobutylaluminum chloride, diisobutylaluminum bromide, diisobutylaluminum fluoride, diisobutylaluminum iodide, isobutylaluminum dichloride, isobutylaluminum dibromide, isobutylaluminum difluoride, isobutylaluminum diiodide, trihexyl Aluminum, dihexyl aluminum chloride, dihexyl aluminum bromide, dihexyl aluminum fluoride, dihexyl aluminum iodide, hexyl aluminum dichloride, hexyl aluminum dibromide, hexyl aluminum difluoride, hexyl aluminum diiodide, tripentyl Luminium, dipentyl aluminum chloride, dipentyl aluminum bromide, dipentyl aluminum fluoride, dipentyl aluminum iodide, pentyl aluminum dichloride, pentyl aluminum dibromide, pentyl aluminum difluoride and pentyl aluminum diiodide, methyl aluminum methoxide, methyl aluminum ethoxide , Methyl aluminum propoxide, methyl aluminum butoxide, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, dimethyl aluminum propoxide, dimethyl aluminum butoxide, ethyl aluminum methoxide, ethyl aluminum ethoxide, ethyl aluminum propoxide, ethyl aluminum butoxide , Diethyl aluminum methoxide, diethyl aluminum ethoxide, diethyl aluminum propoxide, diethyl aluminum butoxide, propyl aluminum methoxide, propyl aluminum ethoxide, propyl aluminum propoxide, propyl aluminum butoxide, dipropyl aluminum methoxide, dipropyl aluminum methoxide , Dipropyl aluminum propoxide, dipropyl aluminum butoxide, butyl aluminum methoxide, butyl aluminum ethoxide, butyl aluminum propoxide, butyl aluminum butoxide, dibutyl aluminum methoxide, dibutyl aluminum ethoxide, dibutyl aluminum propoxide, dibutyl aluminum butoxide , Dimethylal Minium hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisopropyl aluminum hydride, dibutyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride, methyl aluminum dihydride, ethyl aluminum dihydride, propyl aluminum dihydride, isopropyl aluminum hydride Hydride, butyl aluminum dihydride, isobutyl aluminum dihydride, hexyl aluminum dihydride, cyclohexyl aluminum dihydride, dimethyl boron hydride, diethyl boron hydride, methyl boron dihydride, ethyl Such as longitudinals hydride and the like.
[0012]
Among the above compounds, preferred compounds as component (2) include trimethylaluminum, triethylaluminum, diethylaluminum chloride, tripropylaluminum, triisopropylaluminum, tributylaluminum, tri-sec-butylaluminum, tri-tert. -Butyl aluminum, triisobutyl aluminum, trihexyl aluminum, tripentyl aluminum, diisobutyl aluminum hydride, tridecyl aluminum and the like.
[0013]
The component (3) of the present invention is a compound having two or more conjugated double bonds in a cyclic form, and one or more of the compounds can be used as the component (3).
As an example of a compound that can be used as the component (3),
{Circle around (1)} One or more carbon rings having two or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds, and having a total carbon number of 4 to 24, preferably 4 A cyclic hydrocarbon compound,
(2) A cyclic hydrocarbon compound in which the cyclic hydrocarbon compound of (1) is partially substituted with 1 to 6 hydrocarbon groups (typically, an alkyl group or an aralkyl group having 1 to 12 carbon atoms). ,
{Circle around (3)} One or two or more carbon rings having two or more, preferably 2 to 4, more preferably 2 to 3, conjugated double bonds, and having a total carbon number of 4 to 24, preferably 4 An organosilicon compound having a cyclic hydrocarbon group of from 1 to 12,
(4) an organosilicon compound comprising a cyclic hydrocarbon group in which hydrogen of the cyclic hydrocarbon group of (3) is partially substituted with 1 to 6 hydrocarbon groups,
(5) alkali metal salts (sodium salts or lithium salts) of the compounds shown in (1) to (4) above,
Can be mentioned. Among these compounds, those having a cyclopentadiene structure in the molecule are preferable.
[0014]
One of the cyclic hydrocarbon compounds suitable as the component (3) is represented by the following general formula (3).
Embedded image

[Wherein, R⁵, R⁶, R⁷, R⁸, R⁹Each independently represents hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and any two of the hydrocarbon groups can form a cyclic hydrocarbon group together. ]
Examples of the hydrocarbon group represented by the general formula (3) include an alkyl group such as methyl, ethyl, propyl, butyl, t-butyl, hexyl, and octyl; an aryl group such as phenyl; an alkoxy group such as methoxy, ethoxy, and propoxy; And an aralkyl group such as benzyl. When any two of the hydrocarbon groups of the general formula (3) together form a cyclic hydrocarbon group, the skeleton includes cycloheptatriene, aryl and a condensed ring thereof.
Among the cyclic hydrocarbon compounds represented by the general formula (3), preferred are cyclopentadiene, indene, azulene and the like, as well as alkyl, aryl, aralkyl, alkoxy or aryloxy having 1 to 10 carbon atoms. And the like.
A compound in which the cyclic hydrocarbon compound of the general formula (3) is bonded (cross-linked) via an alkylene group (the number of carbon atoms is usually 2 to 8, preferably 2 to 3) is also suitable as the component (3) of the present invention. Used for
[0015]
The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula (4).
(Cp)_rSiR¹⁰ _sX³ _4-rs
Here, Cp represents the above-mentioned cyclic hydrocarbon group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group;¹⁰Is an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group and an octyl group; an alkenyl group such as a vinyl group and an allyl group; a methoxy group and an ethoxy group; Alkoxy groups such as propoxy group and butoxy group; aryl groups such as phenyl group, tolyl group and xylyl group; aryloxy groups such as phenoxy group; aralkyl groups such as benzyl group, phenethyl group, styryl group and neophyl group. Such a hydrocarbon residue having 1 to 24, preferably 1 to 12 carbon atoms or hydrogen is shown. This hydrocarbon residue does not necessarily have to be linear (normal), but may be branched (iso-, sec-, tert-, neo-, etc.). X³Represents a halogen atom such as fluorine, iodine, chlorine or bromine, and r and s are in the range of 0 <r ≦ 4, 0 ≦ s ≦ 3, and preferably 1 ≦ r + s ≦ 4.
[0016]
The following compounds are included in the organic cyclic hydrocarbon compound usable as the component (3) of the present invention.
Cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, t-butylcyclopentadiene, hexylcyclopentadiene, octylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene , 1,2,3,4-tetramethylcyclopentadiene, substituted cyclopentadiene such as pentamethylcyclopentadiene, indene, 4-methylindene, 4,7-dimethylindene, 4,5,6,7-tetrahydroindene and the like Substituted cycloheptatrienes such as indene, cycloheptatriene and methylcycloheptatriene; cyclooctatetraenes such as cyclooctatetraene and methylcyclooctatetraene; azure , Methyl azulene, ethyl azulene, fluorene, cyclopolyenes or substituted cyclopolyenes having 7 to 24 carbon atoms such as a substituted fluorene such as methyl fluorene,
[0017]
Monocyclopentadienyl silane, dicyclopentadienyl silane, tricyclopentadienyl silane, tetracyclopentadienyl silane, monocyclopentadienyl monomethyl silane, monocyclopentadienyl monoethyl silane, monocyclopentadienyl Dimethylsilane, monocyclopentadienyldiethylsilane, monocyclopentadienyltrimethylsilane, monocyclopentadienyltriethylsilane, monocyclopentadienylmonomethoxysilane, monocyclopentadienylmonoethoxysilane, monocyclopentadienyl Monophenoxysilane, monocyclopentadienyl monomethyl monochlorosilane, monocyclopentadienyl monoethyl monochlorosilane, monocyclopentadienyl monomethyl dichlorosilane, Cyclopentadienyl monoethyldichlorosilane, monocyclopentadienyltrichlorosilane, dicyclopentadienylmonomethylsilane, dicyclopentadienylmonoethylsilane, dicyclopentadienyldimethylsilane, dicyclopentadienyldiethylsilane, Dicyclopentadienylmethylethylsilane, dicyclopentadienyldipropylsilane, dicyclopentadienylethylpropylsilane, dicyclopentadienyldiphenylsilane, dicyclopentadienylphenylmethylsilane, dicyclopentadienylmethyl Chlorosilane, dicyclopentadienylethylchlorosilane, dicyclopentadienyldichlorosilane, dicyclopentadienylmonomethoxysilane, dicyclopentadienylmonoethoxysilane, disilicone Lopentadienyl monomethoxy monochlorosilane, dicyclopentadienyl monoethoxy monochlorosilane, tricyclopentadienyl monomethyl silane, tricyclopentadienyl monoethyl silane, tricyclopentadienyl monomethoxy silane, tricyclopentadienyl Monoethoxysilane, tricyclopentadienylmonochlorosilane, 3-methylcyclopentadienylsilane, bis3-methylcyclopentadienylsilane, 3-methylcyclopentadienylmethylsilane, 1,2-dimethylcyclopentadienyl Silane, 1,3-dimethylcyclopentadienylsilane, 1,2,4-trimethylcyclopentadienylsilane, 1,2,3,4-tetramethylcyclopentadienylsilane, pentamethylcyclopentadienylsila ,
[0018]
Monoindenyl silane, diindenyl silane, triindenyl silane, tetraindenyl silane, monoindenyl monomethyl silane, monoindenyl monoethyl silane, monoindenyl dimethyl silane, monoindenyl diethyl silane, monoindenyl trimethyl silane , Monoindenyltriethylsilane, monoindenylmonomethoxysilane, monoindenylmonoethoxysilane, monoindenylmonophenoxysilane, monoindenylmonomethylmonochlorosilane, monoindenylmonoethylmonochlorosilane, monoindenylmonomethyldichlorosilane, Monoindenylmonoethyldichlorosilane, monoindenyltrichlorosilane, diindenylmonomethylsilane, diindenylmonoethylsilane, diindenyldimethylsilane, Ndenyldiethylsilane, diindenylmethylethylsilane, diindenyldipropylsilane, diindenylethylpropylsilane, diindenyldiephenylsilane, diindenylphenylmethylsilane, diindenylmethylchlorosilane, diindenyl Ethylchlorosilane, diindenyldichlorosilane, diindenylmonomethoxysilane, diindenylmonoethoxysilane, diindenylmonomethoxymonochlorosilane, diindenylmonoethoxymonochlorosilane, triindenylmonomethylsilane, triindenylmonoethyl Silane, triindenylmonomethoxysilane, triindenylmonoethoxysilane, triindenylmonochlorosilane, 3-methylindenylsilane, bis-3-methylindenylsilane, 3-methylin Nylmethylsilane, 1,2-dimethylindenylsilane, 1,3-dimethylindenylsilane, 1,2,4-trimethylindenylsilane, 1,2,3,4-tetramethylindenylsilane, pentamethylindene Nylsilane and the like. Preferably, cyclopentadiene, substituted cyclopentadiene, indene, substituted indene and the like.
[0019]
Further, a compound in which any of the above-mentioned compounds is bonded via an alkylene group (the number of carbon atoms of which is usually 2 to 8, preferably 2 to 3) can also be used as the component (3) of the present invention. Examples of such compounds include bisindenylethane, bis (4,5,6,7-tetrahydro-1-indenyl) ethane, 1,3-propanedienylbisindene, and 1,3-propanedienylbis ( 4,5,6,7-tetrahydro) indene, propylylenebis (1-indene), isopropylene (1-indenyl) cyclopentadiene, diphenylmethylene (9-fluorenyl) cyclopentadiene, isopropylylenecyclopentadienyl-1-fluorene and so on.
[0020]
The component (4) of the present invention is a modified organoaluminum compound having 1 to 100, preferably 1 to 50 Al-O-Al bonds in the molecule. Such a modified organoaluminum compound is usually a reaction product obtained by reacting an organoaluminum compound with water in an inert hydrocarbon solvent. Examples of the inert hydrocarbon solvent include aliphatic hydrocarbons (eg, pentane, hexane, heptane, etc.), alicyclic hydrocarbons (eg, cyclohexane, methylcyclohexane, etc.) and aromatic hydrocarbons (eg, benzene, toluene, xylene) Etc.) can be used, but it is preferable to use an aliphatic hydrocarbon or an aromatic hydrocarbon.
The organoaluminum compound used for preparing the modified organoaluminum compound can be represented by the following general formula (5).
R¹¹ _tAlX⁴ _3-t                                      (5)
[Wherein, R¹¹Represents a hydrocarbon group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, such as an alkyl group, an alkenyl group, an aryl group, and an aralkyl group;⁴Represents a hydrogen atom or a halogen atom, and t represents an integer of 1 ≦ t ≦ 3]
Among them, trialkylaluminum is preferred. The alkyl group of the trialkylaluminum may be any of a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group. Is particularly preferred.
The reaction ratio (water / Al molar ratio) between water and the organic aluminum compound is preferably from 0.25 / 1 to 1.2 / 1, particularly preferably from 0.5 / 1 to 1/1, and the reaction temperature is It is usually in the range of -70 to 100 ° C, preferably -20 to 20 ° C. The reaction time is selected in the range of usually 5 minutes to 24 hours, preferably 10 minutes to 5 hours. As the water required for the reaction, so-called water can be used, and water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate and the like can also be used.
Among the above-mentioned modified organoaluminum compounds, those obtained by reacting alkylaluminum with water are usually called aluminoxanes, and in particular, methylaluminoxane (or one substantially consisting of methylaluminoxane) is a compound of the present invention. Suitable as component (4).
Of course, as the component (4) of the present invention, two or more of the above-mentioned modified organoaluminum compounds may be used in combination, and the modified organoaluminum compound may be dissolved or dispersed in the above-mentioned inert hydrocarbon solvent. May be used.
[0021]
As the component (5) of the present invention, an inorganic carrier and / or a particulate polymer carrier is used. The inorganic carrier may be in any shape such as powder, granule, flake, foil, and fiber, as long as the inorganic carrier retains its original shape at the stage of preparing the catalyst of the present invention. Is suitable, the maximum diameter is usually in the range of 5 to 200 μm, preferably 10 to 150 μm. Further, the inorganic carrier is preferably porous, and usually has a surface area of 30 to 1000 m.²/ G, pore volume is 0.1-3cm³/ G.
As the inorganic carrier of the present invention, metals, metal oxides, metal chlorides, metal carbonates, carbon materials, or mixtures thereof can be used. These are usually in the air at 200 to 900 ° C. or in nitrogen or argon. It is used after firing in an inert gas.
Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminum, nickel and the like.
Examples of the metal oxide include a single oxide or a double oxide of an element selected from Groups I to VIII of the periodic table.₂, Al₂O₃, MgO, CaO, B₂O₃, TiO₂, ZrO₂, Fe₂O₃, Al₂O₃・ MgO, Al₂O₃・ CaO, Al₂O₃・ SiO₂, Al₂O₃・ MgO ・ CaO 、 Al₂O₃・ MgO ・ SiO₂, Al₂O₃・ CuO, Al₂O₃・ Fe₂O₃, Al₂O₃・ NiO, SiO₂-Various natural or synthetic double oxides such as MgO can be exemplified. Here, the above formula is not a molecular formula but a composition only, and the structure and component ratio of the double oxide used in the present invention are not particularly limited. In addition, the metal oxide used in the present invention may absorb a small amount of moisture or may contain a small amount of impurities.
As the metal chloride, for example, alkali metal and alkaline earth metal chlorides are preferable.₂, CaCl₂Etc. are particularly preferred. The metal carbonate is preferably an alkali metal or alkaline earth metal carbonate, and specific examples include magnesium carbonate, calcium carbonate, barium carbonate and the like.
Examples of the carbonaceous material include carbon black and activated carbon.
Although any of the above inorganic carriers can be suitably used in the present invention, it is particularly preferable to use metal oxides, silica, alumina and the like.
[0022]
As the particle polymer carrier, any of a thermoplastic resin and a thermosetting resin can be used as long as they maintain a solid state without melting or the like at the time of catalyst preparation and polymerization reaction. It is desirable that the thickness be in the range of ２０００2000 μm, preferably 10-100 μm. The molecular weight of these polymer carriers is not particularly limited as long as the polymer can exist as a solid substance at the time of catalyst preparation and polymerization reaction, and is arbitrarily selected from low molecular weight to ultrahigh molecular weight. Can be used.
Specific examples of the particulate polymer carrier include various polyolefins represented by particulate ethylene polymer, ethylene / α-olefin copolymer, propylene polymer or copolymer, poly 1-butene (preferably carbon In addition to polyesters, polyamides, polyvinyl chloride, polymethyl methacrylate, polymethyl acrylate, polystyrene, and polynorbornene, various natural polymers and mixtures thereof can be exemplified.
[0023]
The above-mentioned inorganic carrier and particulate polymer carrier can be used as they are as the component (5) of the present invention. Before use, these carriers are treated with trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum. Organic aluminum compounds such as dimethylaluminum chloride, diethylaluminum chloride, and diethylmonoethoxyaluminum; and modified organoaluminum compounds containing an Al—O—Al bond (this compound is the same as the compound exemplified in the aforementioned component (4)). Or a preliminary treatment comprising contacting with a silane compound or the like.
Speaking of the inorganic carrier, this is an alcohol, an active hydrogen-containing compound such as an aldehyde, an ester, an electron-donating compound such as an ether, a tetraalkoxysilicate, a trialkoxyaluminum, an alkoxide machine-containing compound such as a transition metal tetraalkoxide, and the like, A method of contacting in advance and then using it as the component (5) is also preferably used.
As the contact treatment method, an aromatic hydrocarbon (generally having 6 to 12 carbon atoms) such as benzene, toluene, xylene and ethylbenzene, heptane, hexane, decane, dodecane and cyclohexane are generally used in an inert atmosphere such as nitrogen or argon. And a method in which a carrier is contacted with a compound for pretreatment in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (usually 5 to 12). This contact is carried out at a temperature of usually -100 ° C to 200 ° C, preferably -50 ° C to 100 ° C for 30 minutes to 50 hours, preferably 1 hour to 24 hours.
This contact reaction is preferably carried out in a solvent in which the above-mentioned compound for pretreatment is soluble, that is, in an aromatic hydrocarbon such as benzene, toluene, xylene and ethylbenzene (normally having 6 to 12 carbon atoms). In this case, after the contact reaction, the solvent can be directly used for preparing the contact component of the present invention without removing the solvent. Further, a liquid inert hydrocarbon in which the pretreatment compound is insoluble or hardly soluble in the contact reaction product (for example, when the pretreatment compound is a modified organoaluminum compound, pentane, hexane, decane, dodecane, cyclohexane Such as an aliphatic or alicyclic hydrocarbon), and the component (5) is precipitated as a solid component and dried, or a part or all of the aromatic hydrocarbon which is a solvent solution at the time of the pretreatment is added. After removal by means such as drying, the component (5) can be taken out as a solid component.
The ratio of the inorganic carrier and / or the particulate polymer carrier to be subjected to the pretreatment and the pretreatment compound is not particularly limited as long as the object of the present invention is not impaired, but is usually 1 to 10000 mmol per 100 g of the carrier, Preferably, it is selected within the range of 5 to 1500 mmol (however, in a modified aluminum compound, the Al atom concentration).
[0024]
As described above, the olefin polymerization catalyst of the present invention can be obtained by bringing component (1), component (2), component (3), component (4) and, if desired, component (5) into contact with each other. However, the order of contact of these components is not particularly limited. For example, when the catalyst of the present invention is obtained by contacting the components (1) to (4),
<1> A method of simultaneously adding the components (1), (2), (3), and (4).
<2> A method in which the components (1), (2) and (3) are brought into contact simultaneously, and then the component (4) is brought into contact.
(Hereinafter, the case of simultaneous contact is represented by 、, and the case of sequential contact is represented by →. For example, in the case of <2>, it is represented by {(1) (2) (3)} → (4). )
<3> {(1) (2) (4)} → (3)
<4> {(1) (3) (4)} → (2)
<5> {(2) (3) (4)} → (1)
<6> {(1) (2)} → {(3) (4)}
<7> {(1) (3)} → {(2) (4)}
<8> {(1) (4)} → {(2) (3)}
<9> {(1) (2)} → (3) → (4)
<10> {(1) (2)} → (4) → (3)
<11> {(1) (3)} → (2) → (4)
<12> {(1) (3)} → (4) → (2)
<13> {(1) (4)} → (2) → (3)
<14> {(1) (4)} → (3) → (2)
<15> ｛(2) (3)｝ → (1) → (4)
<16> ｛(2) (3)｝ → (4) → (1)
<17> ｛(2) (4)｝ → (1) → (3)
<18> {(2) (4)} → (3) → (1)
<19> {(3) (4)} → (1) → (2)
<20> {(3) (4)} → (2) → (1)
<21> (3) → ((1) (2)｝ → (4)
<22> (4) → ((1) (2)｝ → (3)
<23> (2) → ((1) (3)｝ → (4)
<24> (4) → ((1) (3)｝ → (2)
<25> (2) → {(1) (4)} → (3)
<26> (3) → {(1) (4)} → (2)
<27> (1) → {(2) (3)} → (4)
<28> (4) → {(2) (3)} → (1)
<29> (1) → {(2) (4)} → (3)
<30> (3) → {(2) (4)} → (1)
<31> (1) → {(3) (4)} → (2)
<32> (2) → {(3) (4)} → (1)
And the like. Of these contact sequences, <1>, <2>, <5>, <7>, <11>, <15>, <23>, and <27> are preferably used.
The method of contacting the four components is also optional, but usually in an inert atmosphere such as nitrogen or argon, in the presence of an inert hydrocarbon solvent such as heptane, hexane, benzene, toluene or xylene, usually at -100 ° C to 200 ° C. The components (1), (2), (3) and (4) are contacted at a temperature of preferably -50C to 150C for 5 minutes to 250 hours, preferably 30 minutes to 24 hours. The method is adopted. When each component is contacted in an inert hydrocarbon solvent, the formed catalyst may be subjected to polymerization as it is in a solution state after completion of all contact reactions, or, if possible, precipitation, drying, etc. The solid catalyst component may be once taken out by the means described above and then used for polymerization. Of course, the contact reaction of each component may be performed a plurality of times.
[0025]
When the catalyst of the present invention is obtained by contacting the components (1) to (5), for example,
<33> A method of preparing a reaction product of the components (1) to (4) in the contact sequence of the above <1> to <32> and contacting it with the component (5). (｛(1) (2) (3) (4)｝ → (5))
<34> (5) → (4) → {(1) (2) (3)}
<35> (5) → (4) → {(1) (2)} → (3)
<36> (5) → (4) → {(1) (3)} → (2)
<37> (5) → (4) → {(2) (3)} → (1)
<38> (5) → (4) → (3) → {(1) (2)}
<39> (5) → (4) → (2) → {(1) (3)}
<40> (5) → (4) → (1) → {(2) (3)}
<41> (5) → (4) → (1) → (2) → (3)
<42> (5) → (4) → (1) → (3) → (2)
<43> (5) → (4) → (2) → (3) → (1)
<44> (5) → (4) → (2) → (1) → (3)
<45> (5) → (4) → (3) → (1) → (2)
<46> (5) → (4) → (3) → (2) → (1)
<47> (5) → (1) → {(2) (3) (4)}
<48> (5) → (1) → {(2) (3)} → (4)
<49> (5) → (1) → {(2) (4)} → (3)
<50> (5) → (1) → {(3) (4)} → (2)
<51> (5) → (1) → (4) → {(2) (3)}
<52> (5) → (1) → (3) → {(2) (4)}
<53> (5) → (1) → (2) → {(3) (4)}
<54> (5) → (1) → (2) → (3) → (4)
<55> (5) → (1) → (2) → (4) → (3)
<56> (5) → (1) → (3) → (2) → (4)
<57> (5) → (1) → (3) → (4) → (2)
<58> (5) → (1) → (4) → (2) → (3)
<59> (5) → (1) → (4) → (3) → (2)
<60> (5) → (2) → {(1) (3) (4)}
<61> (5) → (3) → {(1) (2) (4)}
Etc. can be adopted.
Of these contact sequences, <33> <34> <47> are preferably used.
The contact of the components (1) to (5) is usually carried out in an inert atmosphere such as nitrogen or argon, generally with an aromatic hydrocarbon such as benzene, toluene, xylene and ethylbenzene, heptane, hexane, decane, dodecane, cyclohexane and the like. The reaction is carried out with or without stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon. In particular, the reaction is preferably performed in a solvent in which the components (1) to (4) are soluble, that is, an aromatic hydrocarbon such as benzene, toluene, xylene, and ethylbenzene. This contact is usually performed at a temperature of -100 to 200C, preferably -50 to 150C, for 5 minutes to 250 hours, preferably 30 minutes to 24 hours.
When the components (1) to (5) are contacted, as described above, an aromatic hydrocarbon solvent in which a certain component is soluble and an aliphatic or alicyclic hydrocarbon in which a certain component is insoluble or hardly soluble, as described above. Although any solvent can be used, it is particularly preferable to use an aromatic hydrocarbon in which the components (1) to (4) are soluble as the solvent. And, when the contact reaction between the components is performed stepwise, without removing the soluble aromatic hydrocarbon solvent used in the previous step at all, it may be used as it is in the solvent for the subsequent contact reaction. Good. In addition, after the previous contact reaction using a soluble solvent, a liquid inert hydrocarbon in which certain components are insoluble or hardly soluble (for example, aliphatic or alicyclic hydrocarbons such as pentane, hexane, decane, dodecane, and cyclohexane) ) To remove the desired product as a solid, followed by a subsequent catalytic reaction of the desired product using any of the inert hydrocarbon solvents described above. The present invention does not prevent the contact reaction of each component from being performed a plurality of times.
[0026]
In preparing the catalyst of the present invention, the proportion of the components (1) to (4) or the components (1) to (5) is usually 0.01 to 1 mol of the component (1). Component (3) is generally used in an amount of 0.01 to 1000 mol, preferably 0.1 to 100 mol, and more preferably 0.1 to 1000 mol, preferably 0.1 to 100 mol, more preferably 0.5 to 50 mol. Is used in the range of 0.5 to 50 mol, and the component (4) is used usually in the range of 1 to 10,000 mol, preferably 5 to 1000 mol, more preferably 10 to 500 mol. When the component (5) is used in combination, the proportion of the component (1) is usually 5 mmol or less, preferably 0.0001 to 5 mmol, and more preferably 0.001 to 0. It is desirable that the ratio be 5 mmol, more preferably 0.01 to 0.1 mmol.
The catalyst of the present invention obtained by bringing the components (1) to (4) or the components (1) to (5) into contact with each other may optionally have a halogen having a CX bond (X: halogen such as fluorine). It may be used in combination with a fluorinated hydrocarbon compound, a halogenated oxygen-containing hydrocarbon compound, a halogen / carbon compound or a sulfide, and borane or borate not falling under the component (2).
[0027]
In the polymerization method of the present invention, olefins are polymerized or copolymerized in the presence of one or more hydrocarbon compounds selected from a saturated hydrocarbon compound and an aromatic hydrocarbon compound in the presence of the catalyst. As the hydrocarbon compound coexisting in the polymerization reaction system, a compound which is liquid or gaseous at ordinary temperature (usually about 25 ° C.) and ordinary pressure is used. The present invention relates to this hydrocarbon compoundTo have a certain amountTherefore, the molecular weight of the produced polymer isDecreaseThe feature is that it can be made to work.
Molecular weightDecreaseThe saturated hydrocarbon compound which is involved in the reaction is usually a linear hydrocarbon having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms (regardless of whether it is linear or branched) and a cyclic hydrocarbon. It may be any of hydrocarbons, and the aromatic compound usually has 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms.
Specifically, methane, ethane, propane, n-butane, isobutane, 2,2-dimethylpropane, n-pentane, isopentane, cyclopentane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2- Dimethylbutane, 2,3-dimethylbutane, cyclohexane, methylcyclopentane, n-heptane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane , 3,3-dimethylpentane, 2,2,3-trimethylbutane, cycloheptane, methylcyclohexane, ethylcyclopentane, n-octane, 2-methylheptane, 3-methylheptane, 2,2-dimethylhexane, 2, 4-dimethylhexane, 2,5-dimethylhexane, 3,4-dimethyl Xane, 2,2,4-trimethylpentane, 2,3,4-limethylpentane, cyclooctane, ethylcyclohexane, n-nonane, n-decane, cyclodecane, n-undecane, n-dodecane, n-tridecane, n Aliphatic or alicyclic saturated hydrocarbons such as tetradecane and n-pentadecane, and aromatic hydrocarbons such as ethylbenzene, toluene, xylene and mesitylene have a molecular weight ofDecreaseUsed for the purpose of. Among them, it is preferable to use methane, ethane, propane, 2,2-dimethylpropane, n-pentane, n-hexane, cyclohexane, n-heptane, n-octane, cyclooctane, n-decane, toluene, xylene and the like. . These compounds can be used as a mixture of two or more kinds.
Molecular weightDecreaseHydrocarbons involved inCompoundIs used in the range of 0.001 to 100 mol, preferably 0.005 to 50 mol, more preferably 0.01 to 10 mol, per 1 g of the catalyst.
[0028]
In the process of the present invention, olefins are homopolymerized or copolymerized. The olefins in the present invention include α-olefins, cyclic olefins, dienes, and trienes.
The α-olefins include those having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and specifically include ethylene, propylene, butene-1, hexene-1, 4-methylpentene-1 and the like. Is done. The α-olefins can be homopolymerized, and two or more α-olefins can be copolymerized. The copolymerization may be any of alternating copolymerization, random copolymerization, and block copolymerization. Absent. For the copolymerization of α-olefins, ethylene and propylene have 3 to 12 carbon atoms, preferably 3 to 12 carbon atoms, such as ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, and ethylene and 4-methylpentene-1. When copolymerizing the α-olefin of No. 8, propylene and butene-1, propylene and 4-methylpentene-1, propylene and 4-methylbutene-1, propylene and hexene-1, propylene and octene-1, The case where propylene is copolymerized with an α-olefin having 3 to 12, preferably 3 to 8 carbon atoms is included. When ethylene or propylene is copolymerized with another α-olefin, the amount of the other α-olefin can be arbitrarily selected within a range of 90 mol% or less of all monomers. In a copolymer, it is 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, and in a propylene copolymer, it is 1 to 90 mol%, preferably 5 to 90 mol%. %, More preferably in the range of 10 to 70 mol%.
As the cyclic olefin, those having 3 to 24, preferably 3 to 18 carbon atoms can be used in the present invention, and include, for example, cyclopentene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene, cyclodecene , Cyclododecene, tetracyclodecene, octacyclodecene, dicyclopentadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene , 5,5,6-trimethyl-2-norbornene, ethylidene norbornene and the like. Usually, the cyclic olefin is copolymerized with the above-mentioned α-olefin. In this case, the amount of the cyclic olefin is 50 mol% or less of the copolymer, usually 1 to 50 mol%, preferably 2 to 50 mol. % Range.
Dienes and trienes that can be used as a raw material monomer are polyenes having 4 to 26 carbon atoms, preferably 6 to 26 carbon atoms. Specifically, butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene , 1,9-decadiene, 1,13-tetradecadiene, 2,6-dimethyl-1,5-heptadiene, 2-methyl-2,7-octadiene, 2,7-dimethyl-2,6-octadiene, , 3 dimethylbutadiene, ethylidene norbornene, dicyclopentadiene, isoprene, 1,3,7-octatriene, 1,5,9-decatriene and the like. When a chain diene or triene is used as a monomer in the present invention, it is customary to copolymerize with the above-mentioned α-olefin, but the content of the chain diene and / or triene in the copolymer is as follows. , Generally in the range of 0.1 to 50 mol%, preferably 0.2 to 10 mol%.
[0029]
The polymerization reaction of the present invention can be carried out in a substantially gaseous state and substantially without oxygen, water and the like. The polymerization conditions are a temperature of 20 to 200 ° C, preferably 50 to 120 ° C, and a pressure of normal pressure to 70 kg / cm.^TwoG, preferably normal pressure to 20 kg / cm^TwoG, and the polymerization time is usually from 5 minutes to 20 hours, preferably from 30 minutes to 10 hours. Also, the molecular weightDecreaseThe saturated hydrocarbon and / or aromatic hydrocarbon added in the reaction system for the purpose of the present invention may be gaseous or liquid under the polymerization reaction conditions, but when this is a liquid, Desirably, it is dispersed in the reactants.
Molecular weight of polymer producedTo reduceBefore and / or after the initiation of the polymerization reaction, an appropriate amount of a saturated hydrocarbon compound and / or an aromatic hydrocarbon compound is supplied to the reactor. Prior to the supply of the catalyst, the method of supplying to the reactor may be any of a method involving entrainment with a scavenger supplied to remove impurities in the reactor, a method involving entrainment with a raw material monomer, or a method supplying alone. Alternatively, both the scavenger and the raw material monomer may be entrained and charged into the reactor. In addition, even after the polymerization is substantially started, it is possible to supply the mixture to the reactor together with the inert gas and / or olefins.
As the scavenger, organic aluminum such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, the above-mentioned modified organic aluminum compound, and modified organic aluminum containing a branched alkyl can be used. One of the features of the present invention is that a saturated hydrocarbon and / or an aromatic hydrocarbon coexist in the reaction system so that the molecular weight of the produced polymer can be adjusted. This means that by adjusting the polymerization conditions (temperature, pressure, amount of catalyst used, hydrogen partial pressure, etc.), the molecular weight of the produced polymer is reduced.ReduceThe present invention excludes the use of means.WhenDoes not mean Furthermore, the present invention can be applied to a multi-stage polymerization system using two or more reaction stages having different polymerization conditions without any trouble.
[0030]
【Example】
Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
The physical properties of the polymers obtained in Examples and Comparative Examples were measured by the following methods.
Melt flow rate (MFR)
ASTM D 1238-57T Measured at 190 ° C. under a load of 2.16 kg.
Number average molecular weight (Mn)
The gel permeation chromatography (manufactured by Waters, model type 150-C) was used with orthodichlorobenzene as the solvent and the measurement temperature was calculated at 135 ° C.
Example 1
(A) Preparation of catalyst
Under a nitrogen atmosphere, 10 ml of purified toluene was added to a 100 ml three-necked flask equipped with an electromagnetic induction stirrer and a condenser, then 0.1 g of tetrapropoxyzirconium, 0.1 g of 1,2-bisindenylethane and 0.7 g of triisobutylaluminum. Was added thereto, and the mixture was stirred and reacted under a reflux condition for 2 hours. Next, 11 ml of a toluene solution of methylaluminoxane (manufactured by Schering, concentration: 3.1 mmol Al / ml) was added, and the mixture was stirred and reacted at room temperature for 1 hour.
(B) polymerization
A 3 L stainless steel autoclave equipped with a stirrer was purged with nitrogen, and 200 g of sea sand subjected to acid washing and heat treatment at 300 ° C. was introduced into the autoclave, and dried sufficiently at 80 ° C. under reduced pressure. Next, 2 ml of the above-mentioned catalyst solution was added, and then 3.9 ml (30 mmol) of hexane was added. While continuously supplying a mixed gas of ethylene and 1-butene (butene / ethylene = 0.2), the total pressure was increased. 9kgf / cm²G was maintained at 80 ° C. for 2 hours to carry out polymerization. The catalyst efficiency was 134 kg / gZr, the MFR was 4.5 g / 10 min, and the Mn was 39,800.
Example 2
Polymerization was carried out in the same manner as in Example 1 except that the amount of hexane supplied during the polymerization was changed to 1.3 ml (10 mmol). The catalyst efficiency was 130 kg / gZr, the MFR was 3.5 g / 10 min, and the Mn was 47,200.
Comparative Example 1
Example 1 was repeated in the same manner as in Example 1 except that the polymerization was carried out without supplying hexane during the polymerization. The catalyst efficiency was 132 kg / gZr, the MFR was 3.0 g / 10 min, and the Mn was 52,300.
Example 3
(A) Preparation of solid catalyst
Under a nitrogen atmosphere, 100 ml of purified toluene was added to a 500 ml three-necked flask equipped with an electromagnetic induction stirrer and a condenser, 2.0 g of tetrapropoxyzirconium, 1.9 g of methylcyclopentadiene and 2.1 g of triethylaluminum were added, and the mixture was heated under reflux. For 2 hours with stirring.
Next, 195 ml of a toluene solution of methylaluminoxane (manufactured by Schering, concentration: 3.1 mmol Al / ml) was added, and the mixture was stirred and reacted at room temperature for 1 hour.
Under a nitrogen atmosphere, 150 g of silica (Fuji Devison # 952), which had been calcined at 500 ° C. for 7 hours, was placed in a 1 L three-necked flask equipped with an electromagnetic induction stirrer and a condenser, and the flask was heated to 150 ° C. for 1 hour. Drying under reduced pressure was performed. After the drying was completed, the flask was cooled to room temperature, and the catalyst component solution obtained above was added thereto, and reacted at room temperature for 1 hour. Next, the temperature of the flask was raised to 40 ° C., and the obtained slurry solution was dried under reduced pressure for 60 minutes to remove the solvent, thereby obtaining 201 g of a solid catalyst having good fluidity.
(B) polymerization
After replacing a 3 L stainless steel autoclave equipped with a stirrer with nitrogen, the inside of the autoclave was heated to 75 ° C. Subsequently, to perform scavenging in the polymerization system, 0.3 ml of a toluene-diluted solution of triethylaluminum (1 mmol / ml) was added, and then 3.9 ml (30 mmol) of hexane was added, and a mixed gas of ethylene and butene-1 ( 8 kgf / cm of butene-1 / ethylene molar ratio 0.15)²G, and 100 mg (Zr = 0.27 mg) of the solid catalyst obtained above was supplied to start polymerization, and a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.05). While the total pressure is 9 kgf / cm.²G was maintained for 2 hours to carry out polymerization. After completion of the polymerization, excess gas was discharged, and the content was taken out by cooling, to obtain 45 g of a white polymer. The catalyst efficiency at this time was 166 kg / gZr. When the MFR of this white polymer was measured, it was 1.2 g / 10 min and Mn was 67,300.
Example 4
The experiment was performed in the same manner as in Example 3 except that the amount of the solid catalyst used in Example 3 was changed to 107 mg (Zr = 0.29 mg), and the amount of hexane to be added was changed to 1.3 ml (10 mmol).
After completion of the polymerization, excess gas was discharged, and the contents were taken out by cooling, to obtain 48 g of a white polymer. The catalyst efficiency was 166 Kg / gZr. When the MFR of this white polymer was measured, it was 0.97 g / 10 min, and Mn was 70,800.
Example 5
The experiment was performed in the same manner as in Example 3 except that the amount of the solid catalyst used was 98 mg (Zr = 0.27 mg) and the amount of hexane to be added was 0.26 ml (2 mmol).
After completion of the polymerization, excess gas was discharged, and the content was taken out by cooling, to obtain 46 g of a white polymer. The catalyst efficiency was 170 Kg / gZr. When the MFR of this white polymer was measured, it was 0.90 g / 10 min, and Mn was 72,300.
Comparative Example 2
An experiment was performed in the same manner as in Example 3 except that the amount of the solid catalyst used in Example 3 was 111 mg (Zr = 0.30 mg) and no hydrocarbon component was added.
After completion of the polymerization, excess gas was discharged, and the contents were taken out by cooling, thereby obtaining 50 g of a white polymer. The catalyst efficiency was 167 Kg / gZr. When the MFR of this white polymer was measured, it was 0.85 g / 10 min and Mn was 75,300.
Example 6
(A) Preparation of solid catalyst
Under a nitrogen atmosphere, 100 ml of purified toluene was added to a 500 ml three-necked flask equipped with an electromagnetic induction stirrer and a condenser, then 2.0 g of tetrapropoxyzirconium, 5.6 g of indene and 9.2 g of triisobutylaluminum were added, and the mixture was heated under reflux. The mixture was stirred and reacted for 2 hours to prepare a transition metal catalyst component. Next, 195 ml of a toluene solution of methylaluminoxane (manufactured by Schering, concentration: 3.1 mmol Al / ml) was added, and the mixture was stirred and reacted at room temperature for 1 hour.
Under a nitrogen atmosphere, 150 g of silica (Fuji Devison # 952), which had been calcined at 500 ° C. for 7 hours, was placed in a 1 L three-necked flask equipped with an electromagnetic induction stirrer and a condenser, and the flask was heated to 150 ° C. for 1 hour. Drying under reduced pressure was performed.
After drying was completed, the flask was cooled to room temperature, the catalyst component solution obtained above was added, and the reaction was carried out at room temperature for 1 hour. Next, the temperature of the flask was raised to 40 ° C., and the obtained slurry solution was dried under reduced pressure for 60 minutes to remove the solvent, thereby obtaining 199 g of a solid catalyst having good fluidity.
(B) polymerization
After replacing a 3 L stainless steel autoclave equipped with a stirrer with nitrogen, the inside of the autoclave was heated to 75 ° C. Subsequently, in order to perform scavenging in the polymerization system, 0.3 ml of a toluene diluted solution (1 mmol / ml) of triethylaluminum was added, and then 106 mg (Zr = 0.29 mg) of the solid catalyst was supplied. Next, 5.4 ml (50 mmol) of cyclohexane was mixed with 9 kgf / cm of a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.15).²G and the polymerization were started together with G. After the start of the polymerization, the total pressure was 9 kgf / cm while continuously supplying a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.05).²G was maintained for 2 hours to carry out polymerization. After completion of the polymerization, excess gas was discharged, the content was taken out by cooling, and 43 g of a white polymer was obtained. At this time, the catalyst efficiency was 148 Kg / gZr. When the MFR of this white polymer was measured, it was 8.5 g / 10 min, and Mn was 36,500.
Example 7
The experiment was performed in the same manner as in Example 6, except that the amount of the solid catalyst used was changed to 111 mg (Zr = 0.30 mg), and 5.6 ml (50 mmol) of methylcyclopentane was added.
After completion of the polymerization, excess gas was discharged, and the content was taken out by cooling, to obtain 45 g of a white polymer. The catalyst efficiency was 150 Kg / gZr. When the MFR of this white polymer was measured, it was 8.3 g / 10 min, and Mn was 36,900.
Example 8
An experiment was performed in the same manner as in Example 6, except that the amount of the solid catalyst used was changed to 95 mg (Zr = 0.26 mg), and 2.9 g (50 mmol) of isobutane was added.
After completion of the polymerization, excess gas was discharged, and the content was taken out by cooling, to obtain 40 g of a white polymer. The catalyst efficiency was 155 Kg / gZr. When the MFR of this white polymer was measured, it was 8.6 g / 10 min, and Mn was 36,200.
Example 9
An experiment was performed in the same manner as in Example 6 except that the amount of the solid catalyst used was changed to 110 mg (Zr = 0.30 mg), and 1.2 g (20 mmol) of isobutane was added.
After completion of the polymerization, excess gas was discharged, and the contents were taken out by cooling, to obtain 48 g of a white polymer. The catalyst efficiency was 160 Kg / gZr. When the MFR of this white polymer was measured, it was 7.2 g / 10 min and Mn was 37,700.
Comparative Example 3
The experiment was performed in the same manner as in Example 6, except that the amount of the solid catalyst used in Example 6 was 111 mg (Zr = 0.30 mg) and no hydrocarbon component was added.
After completion of the polymerization, excess gas was discharged, and the contents were taken out by cooling, to obtain 47 g of a white polymer. The catalyst efficiency was 156 Kg / gZr. When the MFR of this white polymer was measured, it was 6.5 g / 10 min, and Mn was 38,300.
Example 10
(A) Preparation of solid catalyst
Under a nitrogen atmosphere, 100 ml of purified toluene was added to a 500 ml three-necked flask equipped with an electromagnetic induction stirrer and a condenser, then 2.3 g of tetrabutosidylconium, 3.2 g of cyclopentadiene and 13.1 g of triethylaluminum were added, and the mixture was heated under reflux. For 2 hours with stirring. Next, 195 ml of a toluene solution of methylaluminoxane (manufactured by Schering, concentration: 3.1 mmol Al / ml) was added, and the mixture was stirred and reacted at room temperature for 1 hour.
Under a nitrogen atmosphere, 150 g of alumina previously calcined at 500 ° C. for 7 hours was placed in a 1-L three-necked flask equipped with an electromagnetic induction stirrer and a condenser, and the flask was heated to 150 ° C. and dried under reduced pressure for 1 hour. After drying was completed, the flask was cooled to room temperature, the above-mentioned catalyst component solution was added, and the reaction was carried out at room temperature for 1 hour. Next, the temperature of the flask was raised to 40 ° C., and the obtained slurry solution was dried under reduced pressure for 60 minutes to remove the solvent, thereby obtaining 190 g of a solid catalyst having good fluidity.
(B) polymerization
After replacing a 3 L stainless steel autoclave equipped with a stirrer with nitrogen, the inside of the autoclave was heated to 75 ° C. Subsequently, in order to perform scavenging in the polymerization system, 0.3 ml of a toluene diluted solution (1 mmol / ml) of triethylaluminum was added, and then 106 mg (Zr = 0.29 mg) of the solid catalyst was supplied. Next, 3.9 ml (30 mmol) of n-hexane was mixed with 9 kgf / cm of a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.15).²The penetration polymerization was started together with G. After the start of the polymerization, the total pressure was 9 kgf / cm while continuously supplying a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.05).²G was maintained for 2 hours to carry out polymerization. After completion of the polymerization, excess gas was discharged, and the contents were taken out by cooling, to obtain 41 g of a white polymer. At this time, the catalyst efficiency was 141 Kg / gZr. When the MFR of this white polymer was measured, it was 4.3 g / 10 min, and Mn was 4,1200.
Comparative Example 4
The experiment was performed in the same manner as in Example 10 except that the amount of the solid catalyst used in Example 10 was 111 mg (Zr = 0.30 mg) and no hydrocarbon component was added. After completion of the polymerization, excess gas was discharged, and the content was taken out by cooling, to obtain 41 g of a white polymer. The catalyst efficiency was 138 Kg / gZr. When the MFR of this white polymer was measured, it was 3.1 g / 10 min, and Mn was 5,1200.
Example 11
(A) Preparation of solid catalyst
Under a nitrogen atmosphere, 100 ml of purified toluene was added to a 500 ml three-necked flask equipped with an electromagnetic induction stirrer and a condenser, then 2.0 g of tetrapropoxyzirconium, 1.9 g of methylcyclopentadiene and 2.1 g of triethylaluminum were added, and the mixture was heated under reflux. For 2 hours with stirring.
Next, 195 ml of a toluene solution of methylaluminoxane (manufactured by Schering, concentration: 3.1 mmol Al / ml) was added, and the mixture was stirred and reacted at room temperature for 1 hour.
Under a nitrogen atmosphere, 150 g of styrene-divinylbenzene copolymer beads (manufactured by Organo Co., Ltd.) that had been sufficiently dried in advance were placed in a 1-L three-necked flask equipped with an electromagnetic induction stirrer and a condenser, and the flask was heated to 90 ° C. Drying under reduced pressure was performed for a time. After the drying was completed, the flask was cooled to room temperature, and the catalyst component solution obtained above was added thereto, and reacted at room temperature for 1 hour. Next, the temperature of the flask was raised to 40 ° C., and the obtained slurry solution was dried under reduced pressure for 60 minutes to remove the solvent, thereby obtaining 201 g of a solid catalyst having good fluidity.
(B) polymerization
After replacing a 3 L stainless steel autoclave equipped with a stirrer with nitrogen, the inside of the autoclave was heated to 75 ° C. Subsequently, in order to perform scavenging in the polymerization system, 0.3 ml of a toluene diluted solution (1 mmol / ml) of triethylaluminum was added, and then 106 mg (Zr = 0.29 mg) of the solid catalyst was supplied. Then, 0.5 L (22 mmol) of ethane was added to 9 kgf / cm of a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.15).²G and the polymerization started. After the start of the polymerization, the total pressure was 9 kgf / cm while continuously supplying a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.05).²G was maintained for 2 hours to carry out polymerization. After completion of the polymerization, excess gas was discharged, and the content was taken out by cooling, to obtain 38 g of a white polymer. The catalyst efficiency at this time was 130 Kg / gZr. When the MFR of this white polymer was measured, it was 1.03 g / 10 min and Mn was 69,500.
Comparative Example 5
The experiment was carried out in the same manner as in Example 11 except that the amount of the solid catalyst used in Example 11 was 98 mg (Zr = 0.27 mg), and ethane was not added. After completion of the polymerization, excess gas was discharged, and the contents were taken out by cooling, to obtain 36 g of a white polymer. The catalyst efficiency was 132 Kg / gZr. When the MFR of this white polymer was measured, it was 0.90 g / 10 min, and Mn was 72,300.
Example 12
(A) Preparation of solid catalyst
Prepared in a similar manner to Example 6.
(B) polymerization
Using a stainless steel autoclave with a stirrer in the gas phase polymerization apparatus, a loop was formed with a blower, a flow controller and a dry cyclone, and the temperature of the autoclave was controlled by flowing hot water through the jacket. 100 mg / h of the solid catalyst obtained in (A) and hexane at a rate of 80 ml / h (0.6 mol / h) were supplied to an autoclave adjusted to 60 ° C., and butene-1 / ethylene mole in an autoclave gas phase was supplied. Each gas was supplied while adjusting the ratio to be 0.25, and the total pressure was 8 kgf / cm.²The gas in the system was circulated by a blower while maintaining at G, and continuous polymerization was performed for 10 hours while intermittently extracting the produced polymer. The catalyst efficiency was 70 kg / gZr, the MFR was 6.2 g / 10 min, and the Mn was 38,500.
Example 13
Polymerization was carried out in the same manner as in Example 12, except that the amount of hexane supplied during the polymerization was 8 ml / h (0.06 mol / h). The catalyst efficiency was 72 kg / gZr, the MFR was 5.3 g / 10 min, and the Mn was 39,800.
Comparative Example 6
Polymerization was performed in the same manner as in Example 12, except that hexane was not supplied during the polymerization. The catalyst efficiency was 71 kg / gZr, the MFR was 3.3 g / 10 min, and the Mn was 50100.
[Brief description of the drawings]
FIG. 1 is a flow sheet showing a process for preparing a polymerization catalyst of the present invention.

Claims (5)

(1) a compound represented by the general formula Me ¹ R ¹ _p (OR ² ) _q X ¹⁴ _-pq ,
[Wherein, R ¹ and R ^{2 each} independently represent a hydrocarbon group having 1 to 24 carbon atoms, X ¹ represents a halogen atom or a hydrogen atom, Me ¹ represents Zr, Ti or Hf, and p and q each represent 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ p + q ≦ 4]
(2) a compound represented by the general formula Me ² R ³ _m (OR ⁴ ) _n X ² _zmn ;
[Wherein, R ³ and R ^{4 each} independently represent a hydrocarbon group having 1 to 24 carbon atoms, X ² represents a halogen atom or a hydrogen atom, Me ² represents an element belonging to Groups I to III of the periodic table,
z represents the valence of Me ² , and m and n are respectively 0 <m ≦ z, 0 ≦ n ≦ z, and 0 <m + n ≦ z.
In the presence of a catalyst obtained by mutually contacting (3) an organic compound having two or more conjugated double bonds in a ring and (4) a modified organoaluminum compound containing an Al—O—Al bond, the compound is substantially vaporized in the presence of a catalyst. When polymerizing or copolymerizing olefins in a phase state, at least one liquid and / or gaseous hydrocarbon compound selected from a saturated hydrocarbon compound and an aromatic hydrocarbon compound is added in an amount of 0.001 to 1 g of the catalyst. A method for producing a polyolefin, comprising reducing the molecular weight of a produced polyolefin by coexisting in a reaction system in an amount of from 100 to 100 mol as compared with a case where a hydrocarbon compound is not used . (1) a compound represented by the general formula Me ¹ R ¹ _p (OR ² ) _q X ¹⁴ _-pq ,
[Wherein, R ¹ and R ^{2 each} independently represent a hydrocarbon group having 1 to 24 carbon atoms, X ¹ represents a halogen atom or a hydrogen atom, Me ¹ represents Zr, Ti or Hf, and p and q each represent 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ p + q ≦ 4]
(2) a compound represented by the general formula Me ² R ³ _m (OR ⁴ ) _n X ² _zmn ;
[Wherein, R ³ and R ^{4 each} independently represent a hydrocarbon group having 1 to 24 carbon atoms, X ² represents a halogen atom or a hydrogen atom, Me ² represents an element belonging to Groups I to III of the periodic table,
z represents the valence of Me ² , and m and n are respectively 0 <m ≦ z, 0 ≦ n ≦ z, and 0 <m + n ≦ z.
(3) a cyclic organic compound having two or more conjugated double bonds,
In the presence of (4) a modified organoaluminum compound containing an Al-O-Al bond, and (5) a catalyst obtained by bringing an inorganic compound carrier and / or a particulate polymer carrier into contact with each other, in a substantially gas phase state. When polymerizing or copolymerizing an olefin, at least one liquid and / or gaseous hydrocarbon compound selected from a saturated hydrocarbon compound and an aromatic hydrocarbon compound is added in an amount of 0.001 to 100 mol per 1 g of the catalyst. method for producing a polyolefin, wherein the reducing than the molecular weight of the polyolefin by coexist in the reaction system in the amount ranging from when not using a hydrocarbon compound. When the hydrocarbon compound is methane, ethane, propane, 2,2-dimethylpropane, isobutane, n-pentane, methylcyclopentane, n-hexane, cyclohexane, n-heptane, n-octane, cyclooctane, n-decane, toluene 3. The method for producing a polyolefin according to claim 1, wherein the compound is at least one compound selected from the group consisting of and xylene. The method for producing a polyolefin according to any one of claims 1 to 3, wherein the amount of the hydrocarbon compound used is in the range of 0.005 to 50 mol per 1 g of the catalyst. The method for producing a polyolefin according to any one of claims 1 to 4, wherein the amount of the hydrocarbon compound used is in the range of 0.01 to 10 mol per 1 g of the catalyst.

Images