JP2005068206A - Catalyst for olefin polymerization and method for producing olefin polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a catalyst for olefin polymerization, having a small amount of fine powder and high polymerization ability. <P>SOLUTION: The catalyst comprises (A) a solid catalytic component for olefin polymerization essentially composed of titanium, magnesium, a halogen and an electron donor, (B) an organoaluminum compound and (C) an electron donative compound. (A) The solid catalytic component is produced by a method comprising a first process for reducing a specific titanium compound with an organomagnesium compound in the presence of an organosilicon compound and/or an ester compound to give a solid product, a second process for slurrying the solid product with a diluent, controlling the slurry at a specific temperature, supplying an ester compound at a fixed rate and treating the solid product with the ester compound and a third process for treating the solid product treated with the ester compound with a mixture of an ether compound and titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

（Ｒ^１８〜Ｒ^２１は炭素数１〜２０の直鎖状または分岐状のアルキル、脂環式、アリール、アルキルアリール、アリールアルキル基であり、Ｒ^１８またはＲ^１９は水素であってもよい）で表されるようなジエーテル化合物を挙げることができる。具体例としては、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジアミルエーテル、ジイソアミルエーテル、ジネオペンチルエーテル、ジヘキシルエーテル、ジオクチルエーテル、メチルブチルエーテル、メチルイソアミルエーテル、エチルイソブチルエーテル、２，２−ジイソブチル−１，３−ジメトキシプロパン、２−イソプロピル−２−イソペンチル−１，３−ジメトキシプロパン、２，２−ビス（シクロヘキシルメチル）−１，３−ジメトキシプロパン、２−イソプロピル−２−３，７−ジメチルオクチル−１，３−ジメトキシプロパン、２，２−ジイソプロピル−１，３−ジメトキシプロパン、２−イソプロピル−２−シクロヘキシルメチル−１，３−ジメトキシプロパン、２，２−ジシクロヘキシル−１，３−ジメトキシプロパン、２−イソプロピル−２−イソブチル−１，３−ジメトキシプロパン、２，２−ジイソプロピル−１，３−ジメトキシプロパン、２，２−ジプロピル−１，３−ジメトキシプロパン、２−イソプロピル−２−シクロヘキシル−１，３−ジメトキシプロパン、２−イソプロピル−２−シクロペンチル−１，３−ジメトキシプロパン、２，２−ジシクロペンチル−１，３−ジメトキシプロパン、２−ヘプチル−２−ペンチル−１，３−ジメトキシプロパン等を挙げることができる。
【００４７】
これらの電子供与性化合物のうち一般式Ｒ^２２Ｒ^２３Ｓｉ（ＯＲ^２４）_２ で表される有機ケイ素化合物が特に好ましく用いられる。ここで式中、Ｒ^２２はＳｉに隣接する炭素が２級もしくは３級である炭素数３〜２０の炭化水素基であり、具体的には、イソプロピル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｔ−アミル基、等の分岐鎖状アルキル基、シクロペンンチル基、シクロヘキシル基等のシクロアルキル基、シクロペンテニル基等のシクロアルケニル基、フェニル基、トリル基等のアリール基等が挙げられる。また式中、Ｒ^２３は炭素数１〜２０の炭化水素基であり、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基等の直鎖状アルキル基、イソプロピル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｔ−アミル基、等の分岐鎖状アルキル基、シクロペンンチル基、シクロヘキシル基等のシクロアルキル基、シクロペンテニル基等のシクロアルケニル基、フェニル基、トリル基等のアリール基等が挙げられる。さらに式中、Ｒ^２４は炭素数１〜２０の炭化水素基であり、好ましくは炭素数１〜５の炭化水素基である。
【００４８】
このような電子供与性化合物として用いられる有機ケイ素化合物の具体例としては、ジイソプロピルジメトキシシラン、ジイソブチルジメトキシシラン、ジ−ｔ−ブチルジメトキシシラン、ｔ−ブチルメチルジメトキシシラン、ｔ−ブチルエチルジメトキシシラン、ｔ−ブチル−ｎ−プロピルジメトキシシラン、イソブチルイソプロピルジメトキシシラン、ｔ−ブチルイソプロピルジメトキシシラン、ｔ−ブチル−ｎ−ブチルジメトキシシラ、ｔ−ブチル−ｉｓｏ−ブチルジメトキシシラン、ｔ−ブチル−ｓｅｃ−ブチルジメトキシシラン、ジシクロペンチルジメトキシシラン、シクロペンチルイソプロピルジメトキシシラン、シクロペンチルイソブチルジメトキシシラン、シクロペンチル−ｔ−ブチルジメトキシシラン、ジシクロヘキシルジメトキシシラン、シクロヘキシルメチルジメトキシシラン、シクロヘキシルエチルジメトキシシラン、シクロヘキシルイソプロピルジメトキシシラン、シクロヘキシルイソブチルジメトキシシラン、シクロヘキシル−ｔ−ブチルジメトキシシラン、シクロヘキシルシクロペンチルジメトキシシラン、シクロヘキシルフェニルジメトキシシラン、ジフェニルジメトキシシラン、フェニルメチルジメトキシシラン、フェニルイソプロピルジメトキシシラン、フェニルイソブチルジメトキシシラン、フェニル−ｔ−ブチルジメトキシシラン、フェニルシクロペンチルジメトキシシラン、ジイソプロピルジエトキシシラン、ジイソブチルジエトキシシラン、ジ−ｔ−ブチルジエトキシシラン、ｔ−ブチルメチルジエトキシシラン、ジシクロペンチルジエトキシシラン、ジシクロヘキシルジエトキシシラン、シクロヘキシルメチルジエトキシシラン、シクロヘキシルエチルジエトキシシラン、ジフェニルジエトキシシラン、フェニルメチルジエトキシシラン、２−ノルボルナンメチルジメトキシシラン等を挙げることができる。
【００４９】
（ｉ）オレフィンの重合方法
本発明に適用できるオレフィンは、炭素数３以上のオレフィンであり、使用できるオレフィンの具体例としてはプロピレン、ブテン−１、ペンテン−１、ヘキセン−１、ヘプテン−１、オクテン−１、デセン−１などの直鎖状モノオレフィン類、３−メチルブテン−１、３−メチルペンテン−１、４−メチルペンテン−１、などの分岐モノオレフィン類、ビニルシクロヘキサンなどが挙げられる。これらのオレフィンは１種類を用いてもよいし、あるいは、２種類以上を組み合わせて用いてもよい。これらのオレフィンのうちでは、プロピレンまたはブテン−１を用いて単独重合を行うこと、あるいはプロピレンまたはブテン−１を主成分とする混合オレフィンを用いて共重合を行うことが好ましく、プロピレンを用いて単独重合を行うこと、あるいはプロピレンを主成分とする混合オレフィンを用いて共重合を行うことが特に好ましい。また、本発明における共重合に際しては、エチレン及び上記のオレフィンから選ばれる２種類または、それ以上の種類のオレフィンを混合して用いることができる。さらに、共役ジエンや非共役ジエンのような多不飽和結合を有する化合物を共重合に用いることも可能である。そして、重合を２段以上にして行うヘテロブロック共重合も容易に行うことができる。
【００５０】
各触媒成分を重合槽に供給する方法としては、窒素、アルゴン等の不活性ガス中で水分のない状態で供給する以外は、特に制限すべき条件はない。
【００５１】
固体触媒成分（Ａ）、有機アルミニウム化合物（Ｂ）、および電子供与性化合物（Ｃ）は、個別に供給しても良いし、いずれか２者を予め接触させて供給しても良い。
【００５２】
本発明においては、前記のオレフィン重合用触媒存在下にオレフィンの重合を行うことが可能であるが、このような重合（本重合）の実施前に以下に述べる予備重合を行ってもかまわない。
【００５３】
予備重合は、固体触媒成分（Ａ）および有機アルミニウム化合物（Ｂ）の存在下、少量のオレフィンを供給して実施され、スラリー状態で行うのが好ましい。スラリー化するのに用いる溶媒としては、プロパン、ブタン、イソブタン、ペンタン、イソペンタン、ヘキサン、ヘプタン、オクタン、シクロヘキサン、ベンゼン、トルエンのような不活性炭化水素を挙げることができる。また、スラリー化するに際し、不活性炭化水素溶媒の一部または全部に変えて液状のオレフィンを用いることができる。
【００５４】
予備重合時の有機アルミニウム化合物の使用量は、固体触媒成分中のチタン原子１ｍｏｌ当たり、０．５〜７００ｍｏｌのごとく広範囲に選ぶことができるが、０．８〜５００ｍｏｌが好ましく、１〜２００ｍｏｌが特に好ましい。また、予備重合されるオレフィンの量は、固体触媒成分１ｇ当たり０．０１〜１０００ｇ、好ましくは０．０５〜５００ｇ、特に好ましくは０．１〜２００ｇである。
【００５５】
予備重合を行う際のスラリー濃度は、１〜５００（ｇ−固体触媒成分）／（Ｌ−溶媒）が好ましく、特に３〜３００（ｇ−固体触媒成分）／（Ｌ−溶媒）が好ましい。予備重合温度は、−２０〜１００℃が好ましく、特に０〜８０℃が好ましい。また、予備重合中の気相部でのオレフィンの分圧は、０．００１〜２ Ｍｐａが好ましく、特に０．０１〜１ Ｍｐａが好ましいが、予備重合の圧力、温度において液状であるオレフィンについては、この限りではない。さらに、予備重合時間に特に制限はないが、通常２分から１５時間が好適である。
【００５６】
予備重合を実施する際、固体触媒成分（Ａ）、有機アルミニウム化合物（Ｂ）、オレフィンを供給する方法としては、固体触媒成分（Ａ）と有機アルミニウム化合物（Ｂ）を接触させておいた後オレフィンを供給する方法、固体触媒成分（Ａ）とオレフィンを接触させておいた後有機アルミニウム化合物（Ｂ）を供給する方法のいずれの方法を用いても良い。また、オレフィンの供給方法としては、重合槽内が所定の圧力になるように保持しながら順次オレフィンを供給する方法、或いは所定のオレフィン量を最初にすべて供給する方法のいずれの方法を用いても良い。また、得られる重合体の分子量を調節するために水素等の連鎖移動剤を添加することも可能である。
【００５７】
さらに、有機アルミニウム化合物（Ｂ）の存在下、固体触媒成分（Ａ）を少量のオレフィンで予備重合するに際し、必要に応じて電子供与性化合物（Ｃ）を共存させても良い。使用される電子供与性化合物は、上記の電子供与性化合物（Ｃ）の一部または、全部である。その使用量は、固体触媒成分（Ａ）中に含まれるチタン原子１ｍｏｌに対し、０．０１〜４００ｍｏｌ、好ましくは０．０２〜２００ｍｏｌ、特に好ましくは、０．０３〜１００ｍｏｌであり、有機アルミニウム化合物（Ｂ）に対し、０．００３〜５ｍｏｌ、好ましくは０．００５〜３ｍｏｌ、特に好ましくは０．０１〜２ｍｏｌである。
【００５８】
予備重合の際の電子供与性化合物（Ｃ）の供給方法に特に制限なく、有機アルミニウム化合物（Ａ）と別個に供給しても良いし、予め接触させて供給しても良い。また、予備重合で使用されるオレフィンは、本重合で使用されるオレフィンと同一であっても異なっていても良い。
【００５９】
上記のように予備重合を行った後、あるいは、予備重合を行うことなく、前述の固体触媒成分（Ａ）、有機アルミニウム化合物（Ｂ）および電子供与性化合物（Ｃ）からなるオレフィン重合用触媒の存在下に、α−オレフィンの本重合を行うことができる。本重合時の有機アルミニウム化合物の使用量は、固体触媒成分（Ａ）中のチタン原子１ｍｏｌ当たり、１〜１０００ｍｏｌのごとく広範囲に選ぶことができるが、特に５〜６００ｍｏｌの範囲が好ましい。
【００６０】
また、本重合時に使用される電子供与性化合物（Ｃ）は、固体触媒成分（Ａ）中に含まれるチタン原子１ｍｏｌに対し、０．１〜２０００ｍｏｌ、好ましくは０．３〜１０００ｍｏｌ、特に好ましくは、０．５〜８００ｍｏｌであり、有機アルミニウム化合物に対し、０．００１〜５ｍｏｌ、好ましくは０．００５〜３ｍｏｌ、特に好ましくは０．０１〜１ｍｏｌである。
【００６１】
本重合は、−３０〜３００℃までにわたって実施することができるが、２０〜１８０℃が好ましい。重合圧力に関しては特に制限は無いが、工業的かつ経済的であるという点で、一般に、常圧〜１０ Ｍｐａ 、好ましくは０．２〜５ Ｍｐａ 程度の圧力が採用される。重合形式としては、バッチ式、連続式いずれでも可能である。また、プロパン、ブタン、イソブタン、ペンタン、ヘキサン、ヘプタン、オクタンの如き不活性炭化水素溶媒によるスラリー重合もしくは溶液重合、重合温度において液状のオレフィンを媒体としたバルク重合または気相重合も可能である。
【００６２】
本重合時には重合体の分子量を調節するために水素等の連鎖移動剤を添加することも可能である。
【００６３】
【実施例】
以下、実施例及び比較例によって本発明を更に詳細に説明するが、本発明は、以下の実施例によって特に限定をうけるものではない。
【００６４】
実施例における重合体の各種物性の評価方法を、以下に示す。
（１）２０℃キシレン可溶部（以下ＣＸＳと略す）：１ｇの重合パウダーを２００ｍｌの沸騰キシレンに溶解したのち、５０℃まで徐冷し、次いで氷水に浸し攪拌しながら２０℃まで冷却し、２０℃で３時間放置したのち、析出したポリマーを濾別する。濾液からキシレンを蒸発させ、６０℃で減圧乾燥して２０℃のキシレンに可溶なポリマーを回収する。
【００６５】
（２）オレフィン重合用固体触媒成分の活性測定
３Ｌのかき混ぜ式ステンレス製オートクレーブをアルゴン置換し、オレフィン重合用固体触媒成分１ｍｇあたりトリエチルアルミニウムを０．４６ ｍｍｏｌ、シクロヘキシルエチルジメトキシシランを０．０４６ｍｍｏｌの割合で仕込み、０．３３ｋｇ／ｃｍ^２ の分圧に相当する水素を加えた。次いで７８０ｇの液化プロピレンを仕込み、オートクレーブの温度を８０℃に昇温し、攪拌しながら８０℃で１時間重合を行う。オレフィン重合用固体触媒成分は、５ないし６ｍｇ程度とした。活性の表し方は、重合によって得られたポリプロピレンパウダー量を投入したオレフィン重合用固体触媒成分の量で除したものとした。
【００６６】
（３） 微粉重合体；（２）で重合して得られたパウダーを、ＦＵＪＩＷＡＲＡＳＣＩＥＮＴＩＦＩＣ ＣＡＭＰＡＮＹ社製 開口径２５０μｍ （線径１８７μｍ）の篩を用い、振動機として、ＣＭＴ Ｌｔｄ社製ＭＡＧＮＥＴＩＣ ＳＩＥＶＥ ＳＨＡＫＥＲ Ｍｏｄｅｌ ＭＶＳ ｓｅｒｉｅｓで、振幅１．６ｍｍ、振動数１８００回／分の条件で３０分間振動し、篩を通過した重合体を微粉重合体とし、その重量を篩分けを行った全パウダー重量で除し、重量％で示した。
【００６７】
（４）嵩密度；重合体粉体の嵩密度は、筒井理化学機器製 かさ比重測定器 Ｋ ６７２１を用いて測定した。
【００６８】
（５）流動性；固体触媒成分の流動性とは特に規定はないが、所謂粉落ちが良好で、粉体移送上の支障がない状況を良好とする。
【００６９】
実施例１
オレフィン重合用固体触媒成分の合成
▲１▼ 滴下設備を備えたジャケット付撹拌槽（以下単に攪拌槽と呼ぶ）を静電容量式露点計による測定で露点−６５℃の窒素で十分置換した後、ヘキサンを投入する。このとき投入するヘキサン重量を基準量とする。次いで、テトラブトキシチタン０．０８重量比、およびテトラエトキシシラン ０．７７重量比、フタル酸ジイソブチル ０．０３重量比を投入し、攪拌して均一溶液とした。攪拌層の内部温度を８ ℃に保ち、攪拌しながら、ｎ−ブチルマグネシウムクロライドのジ−ｎ−ブチルエーテル溶液（有機合成薬品社製、ｎ−ブチルマグネシウムクロライド濃度２．１ｍｍｏｌ／ｍｌ） １．６７重量比を、滴下設備から５時間かけて徐々に滴下し、微粒子粉体を生成した。滴下終了後、還元槽の内部温度を８℃に温度を保ったままさらに１時間撹拌した後、２０℃に昇温し、さらに１時間攪拌した。
▲２▼ 次いで、焼結金属フィルターを備えた濾過洗浄槽（以下単に濾過槽と呼ぶ）の内部を静電容量式露点計による測定で露点−６５℃の窒素で置換し、▲１▼のスラリーを濾過槽へ窒素圧によって移送（以下、圧送という）し、濾過操作によって固液分離し、さらにトルエン ２．１２重量比で濾過洗浄を３回行った。
▲３▼ 次いで、▲２▼のスラリーを攪拌槽へ圧送し、トルエンを希釈液として適量加え、スラリー濃度０．２（ｇ−固体）／（ｍｌ−希釈液）（以下、スラリー濃度は単にｇ／ｍｌと記す）になるように調整し、９５℃に昇温後、フタル酸ジイソブチル０．４９重量比を４０分間掛けて均等量で投入し、投入終了後さらに３０分間攪拌しながら処理した。このフタル酸ジイソブチルの投入速度は、０．９３ｍｏｌ／（Ｌ−希釈液・Ｈｒ）に相当する。
▲４▼ ▲３▼の処理終了後、▲３▼のスラリーを、濾過層へ圧送し、トルエン２．１２重量比で濾過洗浄を行った。
▲５▼ ▲４▼のスラリーを攪拌槽に圧送し、さらにトルエンを適量加えてスラリー濃度を０．４０ｇ／ｍｌとし、攪拌しながら、ジブチルエーテル ０．０４重量比、四塩化チタン１．６２重量比、フタル酸ジイソブチル０．０３重量比の混合液を供給し、攪拌槽を１１０℃まで昇温し、この温度で３時間反応を行った。
▲６▼ ▲５▼の反応終了後、▲５▼のスラリーを濾過槽に圧送し、濾過操作によって固液分離し、さらに固体分をトルエン ２．１２重量比で濾過洗浄を３回行った。
▲７▼ ▲６▼のスラリーを攪拌層へ圧送し、さらにトルエンを適量加えてスラリー濃度を０．４０ｇ／ｍｌとし、攪拌しながら、 ジブチルエーテル０．０４重量比 、四塩化チタン０．８１重量比の混合液を供給後、１１０℃まで昇温し、この温度で１時間反応を行った。
▲８▼ ▲７▼の反応終了後、▲７▼のスラリーを、濾過槽に圧送し、濾過操作によって固液分離し、さらに固体分をトルエン２．１２重量比で濾過洗浄を３回行い、次いでヘキサン１．４９重量比での濾過洗浄を３回行った。
▲９▼ ▲１▼から▲８▼の手順で得られたオレフィン重合用固体触媒成分のスラリーを、静電容量式露点計による測定で露点−６５℃の窒素を７０℃に加温し流通させた粉体乾燥機に圧送し、有機溶媒分を蒸発・乾燥させて粉体化した後、さらに真空乾燥機にて、１ないし３ＫｐａＡ（絶対圧表示）、７０℃の条件で、１６時間乾燥し、粉体状のオレフィン重合用固体触媒成分を得た。
【００７０】
得られた固体触媒成分の分析、流動性の評価および活性評価等を行った。固体触媒成分には、チタン原子が１．９重量％、エトキシ基が０．２重量％、ブトキシ基が０．５重量％、フタル酸エステル類が１０．８重量％含有されていた。また、固体触媒成分の流動性は特に問題なく良好であり、高活性を示した。これらの評価結果を結果を表１にまとめて示す。
【００７１】
実施例２
実施例１に示す手順のうち、▲３▼でフタル酸ジイソブチル０．４９重量比を５０分間掛けて均等量で投入した以外は、全て同様に行った。このフタル酸ジイソブチルの投入速度は、０．７４ｍｏｌ／（Ｌ−希釈液・Ｈｒ）に相当する。得られた固体触媒成分の分析、流動性の評価および活性評価等の結果を表１に示す。
【００７２】
実施例３
実施例１に示す手順のうち、▲３▼でフタル酸ジイソブチル０．４９重量比を３０分間掛けて均等量で投入した以外は、全て同様に行った。このフタル酸ジイソブチルの投入速度は、１．２３ｍｏｌ／（Ｌ−希釈液・Ｈｒ）に相当する。得られた固体触媒成分の分析、流動性の評価および活性評価等の結果を表１に示す。
【００７３】
比較例１
実施例１に示す手順のうち、▲３▼でフタル酸ジイソブチル０．４９重量比を２０分間掛けて均等量で投入した以外は、全て同様に行った。このフタル酸ジイソブチルの投入速度は、１．８５ｍｏｌ／（Ｌ−希釈液・Ｈｒ）に相当する。得られた固体触媒成分の分析、流動性の評価および活性評価等の結果を表１に示す。
【００７４】
比較例２
実施例１に示す手順のうち、▲３▼でフタル酸ジイソブチル０．４９重量比を６０分間掛けて均等量で投入した以外は、全て同様に行った。このフタル酸ジイソブチルの投入速度は、０．６２ｍｏｌ／（Ｌ−希釈液・Ｈｒ）に相当する。乾燥した固体触媒成分の流動性は悪く、容器排出部でブリッジングを起こし、ハンドリング上支障をきたした。得られた固体触媒成分の分析、流動性の評価および活性評価等の結果を表１に示す。
【００７５】
【表１】

【００７６】
【発明の効果】
本発明により、微粉が少なく、かつ、オレフィン重合能力が高いオレフィン重合用固体触媒成分を用いたオレフィン重合用触媒と、当該触媒を用いた高立体規則性で、微粉重合体の発生が少ないオレフィン重合体の製造方法の提供が可能になった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer. More specifically, the present invention relates to an olefin polymerization catalyst having a small amount of fine powder and a very high catalytic activity per unit weight, and a method for producing a highly stereoregular olefin polymer having a small content of fine powder polymer using the catalyst.
[0002]
[Prior art]
As a method for producing an olefin polymer such as ethylene, propylene, and butene-1, a so-called Ziegler-Natta catalyst comprising a group IV-VI transition metal compound and a group I-III organometallic compound in the periodic table is used. Is well known. For example, Japanese Patent Publication Nos. 6-60216, 2950168, 3-43283, 1-319508, 9-3118, 10-212312, 10 No. 251324, No. 11-228616, No. 2000-309606, No. 2001-294610, No. 2001-204611, and No. 2003-105020.
[0003]
The solid catalyst component for olefin polymerization (hereinafter sometimes simply referred to as solid catalyst component) provided by these methods is very olefinic when used in combination with an organoaluminum compound and an organosilicon compound as a polymerization third component. It is known that production of an olefin polymer having high polymerization ability and high stereoregularity can be realized.
[0004]
In many cases, the solid catalyst component obtained by the above-described method is dried to a normal fluidized state for convenience of handling and is subjected to polymerization. Various dryers have been proposed for use in drying powders. For example, as a material stationary and material transport type dryer, vacuum box dryer, freeze dryer, box dryer, atmospheric drum dryer, vacuum drum dryer, vertical dryer, cylindrical dryer, band dryer As a material agitation dryer, there are aeration rotary dryer, aeration agitation dryer, fluidized bed dryer, cylindrical agitation dryer, multistage disk dryer, grooved agitation dryer, etc. There are spray dryers, air flow dryers and the like. Various dryers combining these methods are also used.
[0005]
In the drying of solid catalysts for olefin polymerization that must be handled in an inert gas and remove organic solvents, aeration rotary dryer, aeration agitation dryer, aeration dryer, fluidization from the viewpoint of safety, convenience, and cost Often, a dryer combining aeration and agitation such as a layer dryer is used. However, the solid catalyst obtained by the above-described method has a problem that fine powder is generated due to friction between particles generated during the drying step accompanied by the flow of these powders. The solid catalyst component in which the fine powder is produced produces a fine powder polymer that deteriorates the particle size distribution of the olefin polymer. Further, the fine powder polymer causes clogging of the line of the olefin polymerization production equipment, and the olefin polymerization production equipment. It causes inconvenience in stable operation.
[0006]
As a method for suppressing the formation of such a fine powder polymer, the following techniques are disclosed. For example, a method in which water and / or oxygen and a transition metal compound are contacted with a solid component obtained by supporting aluminoxane by contact reaction with an inorganic oxide (see Patent Document 1), a dried solid catalyst for olefin polymerization From the components, a fine powder is removed and a nonionic surfactant is added (see Patent Document 2). From the dried solid catalyst component for olefin polymerization, a fine powder of 11 μm or less is removed, and a nonionic surfactant is added. A method of adding (see Patent Document 3), a method of pre-polymerizing a solid catalyst component and then removing fine particles of 5 μm or less under an antistatic agent (see Patent Document 4), a method of adding melted polystyrene ( Patent Document 5), a method of producing a solid product using a magnesium compound, a titanium compound and a specific aromatic dicarboxylic acid ester (refer to Patent Document 6), mug A method for purifying a solid product using a nesium compound, a titanium compound, a halogen compound and a diol compound (see Patent Document 7), a suspension slurry of a magnesium compound and a titanium compound is maintained at a specific temperature or lower, and a specific phthalic acid A method of raising the temperature while controlling the rate of temperature rise and stirring after the diester contact reaction (see Patent Document 8), a solid component obtained by reacting a magnesium compound, a titanium compound, a silicon compound, and an alcohol with titanium When contacting with a compound, the solid product obtained by contacting the compound with a method of raising the temperature while controlling the temperature rise rate while controlling the temperature rise rate (see Patent Document 9), a magnesium compound, and a titanium compound is polyvalent. A method for controlling the temperature during the solid-liquid separation process of the solid substance slurry carrying the carboxylic acid ester in a temperature range of 70 to 130 ° C. Reference 10), a method of obtaining a solid product by spraying a mixture of a magnesium compound and an alcohol in a molten state without substantially evaporating (see Patent Document 11), and a method of prepolymerizing a solid catalyst component for olefin polymerization (See Patent Document 12). However, there has been a demand for a catalyst for olefin polymerization having a smaller amount of fine powder and having a very high catalytic activity per unit weight, and a method for producing a highly stereoregular olefin polymer having a small content of fine powder polymer using the catalyst.
[0007]
[Patent Document 1]
Japanese Patent Laid-Open No. 6-93030 (first page to second page)
[Patent Document 2]
JP-A-6-287217 (first page to second page)
[Patent Document 3]
JP-A-6-287225 (first page to second page)
[Patent Document 4]
JP-A-7-247308 (pages 1 and 2)
[Patent Document 5]
JP-A-6-184230 (first page to second page)
[Patent Document 6]
Japanese Patent Laid-Open No. 11-29611 (first page to second page)
[Patent Document 7]
JP-A-8-269122 (first page to second page)
[Patent Document 8]
JP-A-11-147908 (first page to second page)
[Patent Document 9]
JP-A-8-176226 (pages 1 and 2)
[Patent Document 10]
JP-A-9-165414 (first page to second page)
[Patent Document 11]
JP-A-9-12424 (first page to second page)
[Patent Document 12]
Japanese Patent Publication No. 7-98842 (pages 1 and 2)
[0008]
[Problems to be solved by the invention]
A problem to be solved by the present invention, that is, an object of the present invention is to provide an olefin polymerization catalyst using a solid catalyst component for olefin polymerization that has a small amount of fine powder and has a high olefin polymerization ability (hereinafter sometimes referred to simply as activity). Another object of the present invention is to provide a method for producing an olefin polymer having high stereoregularity using the catalyst and generating less fine powder polymer.
[0009]
[Means for Solving the Problems]
The present invention is characterized in that it comprises the following (A), (B) and (C), and the olefin polymerization solid catalyst component (A) is produced by a method comprising the following first to third steps. This relates to an olefin polymerization catalyst.
(A) Solid catalyst component for olefin polymerization comprising titanium, magnesium, halogen and electron donor as essential components
(B) Organoaluminum compound
(C) electron donating compound
First step: In the presence of an organosilicon compound and / or ester compound having a Si—O bond, the general formula Ti (OR¹  )_a  X_4-a  (R¹  Represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and a represents a number of 0 <a ≦ 4. The step of obtaining a solid product by reducing the titanium compound represented by
Second step: The solid product is slurried with a diluent and controlled at a temperature of 50 to 100 ° C., and then a speed of 0.7 to 1.2 (mol-ester compound) / (L-diluent / Hr) is obtained. Supplying the ester compound in step and treating the solid product with the ester compound
Third step: A step of treating the solid product treated with the ester compound with a mixture of an ether compound and titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound.
Moreover, the olefin polymerization obtained by controlling the slurry concentration when slurrying a solid product with a diluent to a condition of 0.1 to 0.2 (g-solid product) / (ml-diluent). The catalyst for olefin polymerization containing the solid catalyst component for use is a preferred embodiment in the present invention. Furthermore, the second invention is a method for producing an olefin polymer, wherein the olefin is homopolymerized or copolymerized using the solid catalyst component for olefin polymerization.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
(A) Titanium compound
The titanium compound used for the synthesis of the solid catalyst component (A) of the present invention has the general formula Ti (OR¹  )_a  X_4-a  (R¹  Is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and a is a number of 0 ≦ a ≦ 4). R¹  Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, decyl, dodecyl, etc. alkyl groups, phenyl, cresyl, xylyl And cycloalkyl groups such as naphthyl, allyl groups such as propenyl, and aralkyl groups such as benzyl. Among these, an alkyl group having 2 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms are preferable. A linear alkyl group having 2 to 18 carbon atoms is particularly preferable. Also two or more different OR¹  It is also possible to use a titanium compound having a group. Examples of the halogen atom represented by X include chlorine, bromine and iodine. Of these, chlorine gives particularly favorable results.
[0011]
General formula Ti (OR¹  )_a  X_4-a  The value of a of the titanium compound represented by the formula is 0 <a ≦ 4, preferably 2 ≦ a ≦ 4, particularly preferably a = 4. General formula Ti (OR¹  )_a  X_4-a  As a method for synthesizing the titanium compound represented by the formula, a known method can be used. For example, Ti (OR¹  )₄  And TiX₄  In a predetermined ratio, or TiX₄  And a corresponding amount of the corresponding alcohols can be used. These titanium compounds may be used after diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.
[0012]
Specifically, tetrahalogenated titanium compounds such as titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxy titanium trichloride, ethoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, ethoxy titanium tribromide Dihalogenated dialkoxytitanium compounds such as trihalogenated alkoxytitanium compounds, dimethoxytitanium dichloride, diethoxytitanium dichloride, dibutoxytitanium dichloride, diphenoxytitanium dichloride, diethoxytitanium dibromide, trimethoxytitanium chloride, triethoxytitanium Monohalogenated trialkoxytitanium compounds such as chloride, tributoxytitanium chloride, triphenoxytitanium chloride, triethoxytitanium bromide, Tiger methoxy titanium, may be mentioned tetraethoxy titanium, tetra butoxy titanium, tetra-alkoxy titanium compounds such as tetra-phenoxy titanium.
[0013]
(B) Organosilicon compound having Si-O bond
As the organosilicon compound having a Si—O bond used in the synthesis of the solid catalyst component of the present invention, those represented by the following general formula can be used.
Si (OR²  )_m  R³ _4-m,
R⁴(R⁵ ₂SiO)_pSiR⁶ ₃,
Or (R⁷ ₂SiO)_q
Where R²  Is a hydrocarbon group having 1 to 20 carbon atoms, R³  , R⁴  , R⁵  , R⁶  And R⁷  Is a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, m is a number of 0 <m ≦ 4, p is an integer of 1 to 1000, and q is an integer of 2 to 1000.
[0014]
Specific examples of such organosilicon compounds include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetraisopropoxysilane, diisopropoxydiisopropylsilane, tetra Propoxysilane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane, tetraphenoxysilane, triethoxyphenylsilane, hexamethyl Disiloxane, hexaethyldisiloxane, hexapropyldisiloxane, octaethyltrisiloxane, dimethylpolysiloxane Diphenyl polysiloxane, may be exemplified methylhydropolysiloxane, phenyl hydropolysiloxane like. Among these organosilicon compounds, preferred are those represented by the general formula Si (OR²  )_m  R³ _4-mEmbedded image, preferably 1 ≦ m ≦ 4, and particularly preferably a tetraalkoxysilane compound of m = 4.
[0015]
(C) Ester compound
As the ester compound used in the present invention, mono- and polyvalent carboxylic acid esters are used, and examples thereof include aliphatic carboxylic acid esters, olefin carboxylic acid esters, alicyclic carboxylic acid esters, and aromatic carboxylic acid esters. Can be mentioned. Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, toluyl Methyl acid, ethyl toluate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate And methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, di-n-octyl phthalate, and diphenyl phthalate. Of these ester compounds, olefinic carboxylic acid esters such as methacrylic acid esters and maleic acid esters and phthalic acid esters are preferred, and diesters of phthalic acid are particularly preferred.
[0016]
(D) Organomagnesium compound
Next, as the organic magnesium used in the present invention, any type of organic magnesium compound containing an Mg-carbon bond can be used. In particular the general formula R⁸  MgX (wherein R⁸  Represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen. And Grignard compounds represented by general formula R⁹  R¹⁰Mg (wherein R⁹  And R¹⁰Represents a hydrocarbon group having 1 to 20 carbon atoms. A dialkylmagnesium compound or a diarylmagnesium compound represented by Where R⁸, R⁹, R¹⁰May be the same or different, and alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, amyl, isoamyl, hexyl, octyl, 2-ethylhexyl, phenyl, benzyl, aryl Examples include groups, aralkyl groups, and alkenyl groups.
[0017]
Specifically, as the Grignard compound, methyl magnesium chloride, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium iodide, propyl magnesium chloride, propyl magnesium bromide, butyl magnesium chloride, butyl magnesium bromide, sec-butyl magnesium chloride, sec- Butylmagnesium bromide, tert-butylmagnesium chloride, tert-butylmagnesium bromide, amylmagnesium chloride, isoamylmagnesium chloride, hexylmagnesium chloride, phenylmagnesium chloride, phenylmagnesium bromide and the like are represented by the general formula R⁹R¹⁰Examples of the compound represented by Mg include dimethyl magnesium, diethyl magnesium, dipropyl magnesium, diisopropyl magnesium, dibutyl magnesium, di-sec-butyl magnesium, di-tert-butyl magnesium, butyl-sec-butyl magnesium, diamyl magnesium, Examples include dihexyl magnesium, diphenyl magnesium, and butyl ethyl magnesium.
[0018]
Synthetic solvents for the above organomagnesium compounds include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diamyl ether, diisoamyl ether, dihexyl ether, dioctyl ether, diphenyl ether, dibenzyl ether, phenetole, anisole , Ether solvents such as tetrahydrofuran and tetrahydropyran can be used. Further, a hydrocarbon solvent such as hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, or a mixed solvent of an ether solvent and a hydrocarbon solvent may be used.
[0019]
The organic magnesium compound is preferably used in the form of an ether solution. In this case, as the ether compound, an ether compound containing 6 or more carbon atoms in the molecule or an ether compound having a cyclic structure is used. And in particular the general formula R⁸  The Grignard compound represented by MgX is preferably used in the form of an ether solution from the viewpoint of catalyst performance. Moreover, the hydrocarbon soluble complex of said organomagnesium compound and organometallic compound can also be used. Examples of such an organometallic compound include organic compounds of Li, Be, B, Al, or Zn.
[0020]
(E) Ether compound
Next, the ether compound used in the present invention includes diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diamyl ether, diisoamyl ether, dineopentyl ether, dihexyl ether, dioctyl ether, methyl butyl ether, Examples thereof include dialkyl ethers such as methyl isoamyl ether and ethyl isobutyl ether. Of these, dibutyl ether and diisoamyl ether are particularly preferably used.
[0021]
(F) Synthesis of solid catalyst component
The solid catalyst of the present invention is obtained by treating a solid product obtained by reducing a titanium compound with an organomagnesium compound in the presence of an organosilicon compound and / or an ester compound, and then treating the ether compound and titanium tetrachloride. It is synthesized by treating with a mixture or a mixture of an ether compound, titanium tetrachloride and an ester compound. These synthesis reactions are all carried out in an inert gas atmosphere such as nitrogen or argon.
[0022]
As a method for the reduction reaction of the titanium compound by the organomagnesium compound, a method of adding the organomagnesium compound to a mixture of the titanium compound, organosilicon compound and ester compound, or conversely, a titanium compound or organosilicon compound in a solution of the organomagnesium compound And a method of adding a mixture of ester compounds. Among these, the method of adding an organomagnesium compound to a mixture of a titanium compound, an organosilicon compound and an ester compound is preferable from the viewpoint of activity.
[0023]
The titanium compound, organosilicon compound and ester compound are preferably used after being dissolved or diluted in a suitable solvent. Such solvents include aliphatic hydrocarbons such as hexane, heptane, octane and decane, aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin, diethyl ether and dibutyl ether. , Ether compounds such as diisoamyl ether and tetrahydrofuran.
[0024]
The reduction reaction temperature is −50 to 70 ° C., preferably −30 to 50 ° C., and particularly preferably −25 to 35 ° C. If the reduction reaction temperature is too high, the activity decreases. In addition, when a solid product is synthesized by a reduction reaction, a porous material such as an inorganic oxide or an organic polymer can coexist, and the solid product can be impregnated with the porous material. As such a porous substance, those having a pore volume of 0.3 ml / g or more at a pore radius of 20 to 200 nm are preferable.
[0025]
As the porous inorganic oxide, SiO₂, Al₂  O₃  , MgO, TiO₂  , ZrO₂  , SiO₂  ・ Al₂O₃  Composite oxide, MgO / Al₂  O₃  Composite oxide, MgO / SiO₂  ・ Al₂  O₃  Examples include composite oxides. In addition, as the porous polymer, polystyrene, styrene-divinylbenzene copolymer, styrene-n, n′-alkylene dimethacrylamide copolymer, styrene-ethylene glycol dimethyl methacrylate copolymer, polyethyl acrylate, Methyl acrylate-divinylbenzene copolymer, ethyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyethylene glycol dimethyl methacrylate, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer Representative examples include polymers, polyvinyl chloride, polyvinyl pyrrolidine, polyvinyl pyridine, ethyl vinyl benzene-divinyl benzene copolymer, polyethylene, ethylene-methyl acrylate copolymer, polypropylene, etc. That polystyrene, polyacrylate, polyacrylonitrile, polyvinyl chloride, mention may be made of the polymers of the polyolefin. Of these porous materials, SiO₂  , Al₂O₃A styrene-divinylbenzene copolymer is preferably used.
[0026]
Although there is no restriction | limiting in particular in dripping time, Usually, it is about 30 minutes-12 hours. After the reduction reaction, a post-reaction may be performed at a temperature of 20 to 120 ° C.
[0027]
The amount of the organosilicon compound used is the atomic ratio of silicon atoms to titanium atoms in the titanium compound, and Si / Ti = 1 to 50, preferably 3 to 30, particularly preferably 5 to 25. The amount of the ester compound used is the molar ratio of the ester compound to the titanium atom of the titanium compound, and the ester compound / Ti = 0.05 to 10, preferably 0.1 to 6, particularly preferably 0.2 to 3. It is a range. Furthermore, the amount of the organic magnesium compound used is the atomic ratio of the sum of titanium atoms and silicon atoms and magnesium atoms, (Ti + Si) /Mg=0.1 to 10, preferably 0.2 to 5.0, particularly preferably Is in the range of 0.5 to 2.0.
[0028]
The solid product obtained by the reduction reaction is solid-liquid separated and washed several times with an inert hydrocarbon solvent such as hexane or heptane. The solid product thus obtained contains trivalent titanium, magnesium and hydrocarbyloxy groups and generally exhibits amorphous or very weak crystallinity. From the viewpoint of catalyst performance, an amorphous structure is particularly preferable.
[0029]
Next, the solid product obtained by the above method is treated with an ester compound. The amount of the ester compound used is 0.1 to 50 mol, more preferably 0.3 to 20 mol, and particularly preferably 0.5 to 10 mol per mol of titanium atom in the solid product. Moreover, the usage-amount of the ester compound per 1 mol of magnesium atoms in a solid product is 0.01-1.0 mol, Preferably it is 0.03-0.5 mol. When the amount of the ester compound used is excessively large, the particles collapse.
[0030]
The treatment of the solid product with the ester compound can be performed by any known method such as a slurry method or a mechanical pulverization means such as a ball mill. However, when the mechanical pulverization is performed, fine particles are formed in the solid catalyst component. It is generated in a large amount and has a wide particle size distribution, which is not preferable from an industrial viewpoint, and it is preferable to contact both in the presence of a diluent.
[0031]
Diluents include aliphatic hydrocarbons such as pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane and cyclopentane, 1,2-dichloroethane, and monochloro. Halogenated hydrocarbons such as benzene can be used. Among these, aromatic hydrocarbons and halogenated hydrocarbons are particularly preferable.
[0032]
The amount of the diluent used is such that the slurry concentration is 0.05 to 0.7 (g-solid product) / (ml-diluent), particularly 0.1 to 0.2 (g-solid product) / The amount is (ml-diluent). Moreover, the speed | rate which supplies an ester compound to the slurry of a solid product is 0.7-1.2 (mol-ester compound) / (L-diluent * Hr). When the feeding rate is high, the content of the fine powder polymer in the olefin polymer increases, and when it is slow, the content of the fine powder polymer in the olefin polymer decreases, but the fluidity of the solid catalyst component deteriorates.
[0033]
The temperature at which the ester compound is charged and the temperature at which the solid product is treated with the ester compound is −50 to 150 ° C., preferably 0 to 120 ° C., more preferably 50 to 100 ° C. The treatment time is 5 minutes or more, preferably 15 minutes to 3 hours. After completion of the treatment, solid-liquid separation is performed, followed by washing with an inert hydrocarbon solvent several times to obtain an ester-treated solid.
[0034]
Next, the ester-treated solid is treated with a mixture of an ether compound and titanium tetrachloride. This treatment is preferably performed in a slurry state. Solvents used for slurrying include aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin, Halogens or hydrocarbons such as dichloroethane, trichloroethylene, monochlorobenzene, dichlorobenzene, trichlorobenzene and the like can be mentioned. Among them, halogenated hydrocarbons and aromatic hydrocarbons are preferable.
[0035]
The slurry concentration is preferably 0.05 to 0.7 (g-solid) / (ml-solvent), particularly 0.1 to 0.5 (g-solid) / (ml-solvent). The reaction temperature is 30 to 150 ° C, preferably 45 to 135 ° C, particularly preferably 60 to 120 ° C. Although there is no restriction | limiting in particular in reaction time, Usually, about 30 minutes to about 6 hours are suitable.
[0036]
The method of supplying the ester-treated solid, the ether compound and titanium tetrachloride includes the method of adding the ether compound and titanium tetrachloride to the ester-treated solid, and the method of adding the ester-treated solid in the solution of the ether compound and titanium tetrachloride. Either method is acceptable. In the method of adding the ether compound and titanium tetrachloride to the ester-treated solid, a method of adding the ether compound and then adding titanium tetrachloride, or a method of simultaneously adding the ether compound and titanium tetrachloride is preferable. A method of adding a mixture of a previously prepared ether compound and titanium tetrachloride is preferred.
[0037]
The reaction of the ester-treated solid ether compound and titanium tetrachloride may be repeated twice or more. From the viewpoint of activity and stereoregularity, it is preferable to repeat the reaction with a mixture of an ether compound and titanium tetrachloride at least twice.
[0038]
The usage-amount of an ether compound is 0.1-100 mol with respect to 1 mol of titanium atoms contained in a solid product, Preferably it is 0.5-50 mol, Most preferably, it is 1-20 mol. The amount of titanium tetrachloride added is 1-1000 mol, preferably 3-500 mol, particularly preferably 10-300 mol, with respect to 1 mol of titanium atoms contained in the solid product. Moreover, the addition amount of titanium tetrachloride with respect to 1 mol of ether compounds is 1-100 mol, Preferably it is 1.5-75 mol, Most preferably, it is 2-50 mol.
[0039]
Further, an ester compound may be allowed to coexist when the ester-treated solid is treated with a mixture of an ether compound and titanium tetrachloride. In this case, the amount of the ester compound used is 30 mol or less, preferably 15 mol or less, particularly preferably 5 mol or less, with respect to 1 mol of titanium atoms contained in the solid product.
[0040]
The trivalent titanium compound-containing solid catalyst component obtained by the above method is used for the polymerization after solid-liquid separation, washing several times with an inert hydrocarbon solvent such as hexane and heptane. After solid-liquid separation, wash with a large amount of halogenated hydrocarbon solvent such as monochlorobenzene or aromatic hydrocarbon solvent such as toluene at least once at a temperature of 50 to 120 ° C. and then with an aliphatic hydrocarbon solvent such as hexane. It is preferable from the viewpoint of activity and stereoregularity to be used for polymerization after repeated washing.
[0041]
(G) Organoaluminum compound
The organoaluminum compound used in the present invention has at least one Al-carbon bond in the molecule. A typical one is shown in the following general formula.
R¹¹γAlY_{3 − γ}
R¹²R¹³Al-O-AlR¹⁴R¹⁵
(R¹¹~ R¹⁵Is a hydrocarbon group having 1 to 20 carbon atoms, Y is a halogen, hydrogen or alkoxy group, and γ is a number represented by 2 ≦ γ ≦ 3. Trialkylaluminum such as trialkylaluminum, trihexylaluminum, etc., diethylaluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride, dialkylaluminum halide such as diethylaluminum chloride, and a mixture of triethylaluminum and diethylaluminum chloride And alkyl alumoxane such as tetraethyl dialumoxane, tetrabutyl dialumoxane, and the like.
[0042]
Among these organoaluminum compounds, trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, and alkylalumoxane are preferable, and triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride and tetraethyldialumoxane are particularly preferable. preferable.
[0043]
The amount of the organoaluminum compound used can be selected in a wide range such as 0.5 to 1000 mol per 1 mol of titanium atom in the solid catalyst component, and the range of 1 to 600 mol is particularly preferable.
[0044]
(H) electron donating compound
Examples of the electron donating compound used in the polymerization in the present invention include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides and the like. Examples thereof include oxygen-containing electron donors, nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates. Of these electron donors, inorganic acid esters and ethers are preferably used.
[0045]
Preferably, the inorganic acid esters are represented by the general formula R¹⁶nSi (OR¹⁷)_4-n(R¹⁶Is a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, R¹⁷Is a hydrocarbon group having 1 to 20 carbon atoms, R¹⁶, R¹⁷May have different substituents in the same molecule, and n may be a silicon compound represented by 0 ≦ n <4. Specific examples include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, t-butyltrimethoxysilane, isopropyltri Methoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, propylmethyldimethoxysilane, diisopropyldimethoxysilane, dibutyldimethoxysilane, diisobutyldimethoxysilane, di- t-butyldimethoxysilane, butylmethyldimethoxysilane, butylethyldimethoxysilane, t-butyl Tildimethoxysilane, t-butylethyldimethoxysilane, t-butyl-n-propyldimethoxysilane, isobutylisopropyldimethoxysilane, t-butylisopropyldimethoxysilane, t-butyl-n-butyldimethoxysilane, t-butyl-iso-butyl Dimethoxysilane, t-butyl-sec-butyldimethoxysilane, hexylmethyldimethoxysilane, hexylethyldimethoxysilane, dodecylmethyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyl Dimethoxysilane, cyclopentyl-t-butyldimethoxysilane, dicyclohexyldimeth Sisilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenyl Isopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-t-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, vinylmethyldimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, t-butyltri Ethoxysilane, isopropyltriethoxysilane, cyclohexyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, dipropyldiethoxysilane, propylmethyldiethoxysilane, diisopropyldiethoxysilane, Dibutyldiethoxysilane, diisobutyldiethoxysilane, di-t-butyldiethoxysilane, butylmethyldiethoxysilane, butylethyldiethoxysilane, t-butylmethyldiethoxysilane, hexylmethyldiethoxysilane, hexylethyldiethoxysilane , Dodecylmethyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane, Rohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, vinylmethyldiethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, phenyltri-t-butoxysilane, 2-norbornanetrimethoxysilane, Examples include 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, trimethylphenoxysilane, and methyltriallyloxysilane.
[0046]
Further, the ethers are preferably dialkyl ethers, general formula

(R¹⁸~ R²¹Is a linear or branched alkyl, alicyclic, aryl, alkylaryl, arylalkyl group having 1 to 20 carbon atoms, and R¹⁸Or R¹⁹May be hydrogen). Specific examples include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diisoamyl ether, dineopentyl ether, dihexyl ether, dioctyl ether, methyl butyl ether, methyl isoamyl ether, ethyl isobutyl ether, 2, 2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-isopropyl-2-3 , 7-dimethyloctyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,2-disi Rohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-heptyl-2- Examples thereof include pentyl-1,3-dimethoxypropane.
[0047]
Of these electron donating compounds, the general formula R²²R²³Si (OR²⁴)₂  An organosilicon compound represented by the formula is particularly preferably used. Where R²²Is a hydrocarbon group having 3 to 20 carbon atoms in which the carbon adjacent to Si is secondary or tertiary, specifically, isopropyl group, sec-butyl group, t-butyl group, t-amyl group, etc. A branched alkyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a cycloalkenyl group such as a cyclopentenyl group, an aryl group such as a phenyl group and a tolyl group. In the formula, R²³Is a hydrocarbon group having 1 to 20 carbon atoms, specifically, a linear alkyl group such as methyl group, ethyl group, propyl group, butyl group and pentyl group, isopropyl group, sec-butyl group, t- Examples thereof include branched alkyl groups such as butyl group and t-amyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, cycloalkenyl groups such as cyclopentenyl group, and aryl groups such as phenyl group and tolyl group. In the formula, R²⁴Is a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms.
[0048]
Specific examples of the organosilicon compound used as such an electron donating compound include diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t -Butyl-n-propyldimethoxysilane, isobutylisopropyldimethoxysilane, t-butylisopropyldimethoxysilane, t-butyl-n-butyldimethoxysila, t-butyl-iso-butyldimethoxysilane, t-butyl-sec-butyldimethoxysilane , Dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-t-butyldimethoxysilane, dicyclohexyl Methoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl-t-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, Phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-t-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, di-t-butyldiethoxysilane, t-butylmethyldiethoxysilane, Dicyclopentyl Silane, dicyclohexyl diethoxysilane, cyclohexyl methyl diethoxy silane, cyclohexylethyl diethoxy silane, diphenyl diethoxy silane, phenyl methyl diethoxy silane, and 2-norbornane methyl dimethoxy silane.
[0049]
(I) Olefin polymerization method
The olefin applicable to the present invention is an olefin having 3 or more carbon atoms. Specific examples of olefins that can be used include propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, and decene-1. Linear monoolefins such as, branched monoolefins such as 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, and vinylcyclohexane. One type of these olefins may be used, or two or more types may be used in combination. Among these olefins, it is preferable to carry out homopolymerization using propylene or butene-1, or to carry out copolymerization using a mixed olefin mainly composed of propylene or butene-1, and use propylene alone. It is particularly preferable to perform polymerization or to perform copolymerization using a mixed olefin mainly composed of propylene. In the copolymerization in the present invention, two or more kinds of olefins selected from ethylene and the above-mentioned olefins can be mixed and used. Furthermore, a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene can be used for the copolymerization. And hetero block copolymerization which superposes | polymerizes in 2 steps or more can also be performed easily.
[0050]
The method for supplying each catalyst component to the polymerization tank is not particularly limited except that the catalyst component is supplied in an inert gas such as nitrogen or argon in the absence of moisture.
[0051]
The solid catalyst component (A), the organoaluminum compound (B), and the electron donating compound (C) may be supplied individually, or may be supplied in contact with any two of them.
[0052]
In the present invention, it is possible to carry out olefin polymerization in the presence of the above-mentioned catalyst for olefin polymerization. However, preliminary polymerization described below may be carried out before such polymerization (main polymerization).
[0053]
The prepolymerization is preferably carried out in a slurry state by supplying a small amount of olefin in the presence of the solid catalyst component (A) and the organoaluminum compound (B). Examples of the solvent used for the slurry include inert hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. Further, when slurrying, a liquid olefin can be used instead of a part or all of the inert hydrocarbon solvent.
[0054]
The amount of the organoaluminum compound used in the prepolymerization can be selected in a wide range such as 0.5 to 700 mol per 1 mol of titanium atom in the solid catalyst component, preferably 0.8 to 500 mol, particularly 1 to 200 mol. preferable. The amount of olefin to be prepolymerized is 0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 200 g, per 1 g of the solid catalyst component.
[0055]
The slurry concentration during the prepolymerization is preferably 1 to 500 (g-solid catalyst component) / (L-solvent), particularly preferably 3 to 300 (g-solid catalyst component) / (L-solvent). The prepolymerization temperature is preferably -20 to 100 ° C, particularly preferably 0 to 80 ° C. Further, the partial pressure of the olefin in the gas phase part during the prepolymerization is preferably 0.001 to 2 Mpa, and particularly preferably 0.01 to 1 Mpa, but for the olefin that is liquid at the prepolymerization pressure and temperature, This is not the case. Further, the prepolymerization time is not particularly limited, but usually 2 minutes to 15 hours is preferable.
[0056]
As a method of supplying the solid catalyst component (A), the organoaluminum compound (B), and the olefin when carrying out the prepolymerization, the olefin after the solid catalyst component (A) and the organoaluminum compound (B) are brought into contact with each other is used. Any of the method of supplying the organic aluminum compound (B) after the solid catalyst component (A) and the olefin are contacted may be used. In addition, as a method for supplying olefin, either a method of sequentially supplying olefin while maintaining the inside of the polymerization tank at a predetermined pressure, or a method of supplying all the predetermined amount of olefin first is used. good. It is also possible to add a chain transfer agent such as hydrogen in order to adjust the molecular weight of the resulting polymer.
[0057]
Further, when the solid catalyst component (A) is prepolymerized with a small amount of olefin in the presence of the organoaluminum compound (B), an electron donating compound (C) may coexist as necessary. The electron donating compound used is a part or all of the electron donating compound (C). The amount of use is 0.01 to 400 mol, preferably 0.02 to 200 mol, particularly preferably 0.03 to 100 mol, based on 1 mol of titanium atom contained in the solid catalyst component (A), and an organoaluminum compound It is 0.003-5 mol with respect to (B), Preferably it is 0.005-3 mol, Most preferably, it is 0.01-2 mol.
[0058]
The method for supplying the electron donating compound (C) during the preliminary polymerization is not particularly limited, and may be supplied separately from the organoaluminum compound (A) or may be supplied in contact with the organic aluminum compound (A). Further, the olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization.
[0059]
An olefin polymerization catalyst comprising the above-mentioned solid catalyst component (A), organoaluminum compound (B) and electron donating compound (C) after performing prepolymerization as described above or without performing prepolymerization. In the presence, the main polymerization of the α-olefin can be carried out. The amount of the organoaluminum compound used in the main polymerization can be selected in a wide range of 1 to 1000 mol per 1 mol of titanium atom in the solid catalyst component (A), but a range of 5 to 600 mol is particularly preferable.
[0060]
Further, the electron donating compound (C) used in the main polymerization is 0.1 to 2000 mol, preferably 0.3 to 1000 mol, particularly preferably, with respect to 1 mol of titanium atoms contained in the solid catalyst component (A). 0.5 to 800 mol, and 0.001 to 5 mol, preferably 0.005 to 3 mol, and particularly preferably 0.01 to 1 mol with respect to the organoaluminum compound.
[0061]
The main polymerization can be carried out over -30 to 300 ° C, preferably 20 to 180 ° C. Although there is no restriction | limiting in particular about the polymerization pressure, Generally the pressure of a normal pressure-10 Mpa, Preferably about 0.2-5 Mpa is employ | adopted from the point of being industrial and economical. As the polymerization method, either batch type or continuous type is possible. Further, slurry polymerization or solution polymerization using an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, and octane, and bulk polymerization or gas phase polymerization using a liquid olefin as a medium at the polymerization temperature are also possible.
[0062]
During the main polymerization, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer.
[0063]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not specifically limited by the following Examples.
[0064]
The evaluation methods for various physical properties of the polymers in the examples are shown below.
(1) 20 ° C. xylene soluble part (hereinafter abbreviated as CXS): 1 g of polymer powder is dissolved in 200 ml of boiling xylene, then slowly cooled to 50 ° C., then immersed in ice water and cooled to 20 ° C. with stirring, After standing at 20 ° C. for 3 hours, the precipitated polymer is filtered off. Xylene is evaporated from the filtrate and dried under reduced pressure at 60 ° C. to recover a polymer soluble in xylene at 20 ° C.
[0065]
(2) Activity measurement of solid catalyst component for olefin polymerization
A 3 L stirring type autoclave made of stainless steel was replaced with argon, and 0.46 mmol of triethylaluminum and 0.046 mmol of cyclohexylethyldimethoxysilane were charged at a rate of 0.33 kg / cm per 1 mg of the solid catalyst component for olefin polymerization.²  Hydrogen corresponding to the partial pressure of was added. Next, 780 g of liquefied propylene is charged, the temperature of the autoclave is raised to 80 ° C., and polymerization is carried out at 80 ° C. for 1 hour while stirring. The solid catalyst component for olefin polymerization was about 5 to 6 mg. The activity was expressed by dividing the amount of polypropylene powder obtained by polymerization by the amount of the solid catalyst component for olefin polymerization charged.
[0066]
(3) Fine powder polymer; the powder obtained by polymerizing in (2) was screened with a sieve having an opening diameter of 250 μm (wire diameter: 187 μm) manufactured by FUJI WARASCIENTIFIC CAMPANY, and MAGNETIC SIEVE SHAKER Model MVS manufactured by CMT Ltd. In series, the polymer vibrates for 30 minutes under conditions of an amplitude of 1.6 mm and a frequency of 1800 times / minute, and the polymer passing through the sieve is defined as a fine powder polymer, and the weight is divided by the total powder weight after sieving. %.
[0067]
(4) Bulk density; The bulk density of the polymer powder was measured using a bulk specific gravity meter K 6721 manufactured by Tsutsui Rikagakuki.
[0068]
(5) Fluidity: The fluidity of the solid catalyst component is not particularly specified, but the so-called powder falling off is good, and there is no problem in powder transfer.
[0069]
Example 1
Synthesis of solid catalyst components for olefin polymerization
(1) A jacketed stirring tank equipped with a dropping device (hereinafter simply referred to as a stirring tank) is sufficiently substituted with nitrogen having a dew point of -65 ° C. as measured by a capacitance type dew point meter, and then hexane is added thereto. The weight of hexane added at this time is used as a reference amount. Next, 0.08 weight ratio of tetrabutoxy titanium, 0.77 weight ratio of tetraethoxysilane and 0.03 weight ratio of diisobutyl phthalate were added and stirred to obtain a uniform solution. While maintaining the internal temperature of the stirring layer at 8 ° C, while stirring, a di-n-butyl ether solution of n-butylmagnesium chloride (Organic Synthetic Chemicals Co., Ltd., n-butylmagnesium chloride concentration 2.1 mmol / ml) 1.67 weight The ratio was gradually dropped over 5 hours from the dropping equipment to produce fine particle powder. After completion of the dropwise addition, the mixture was further stirred for 1 hour while maintaining the internal temperature of the reducing tank at 8 ° C., then heated to 20 ° C. and further stirred for 1 hour.
(2) Next, the inside of a filtration washing tank (hereinafter simply referred to as a filtration tank) equipped with a sintered metal filter was replaced with nitrogen having a dew point of −65 ° C. as measured by a capacitance type dew point meter, and the slurry of (1) Was transferred to a filtration tank by nitrogen pressure (hereinafter referred to as “pressure feeding”), solid-liquid separation was performed by filtration, and filtration and washing were performed three times at a toluene 2.12 weight ratio.
(3) Next, the slurry of (2) is pressure-fed to a stirring vessel, an appropriate amount of toluene is added as a diluent, and a slurry concentration of 0.2 (g-solid) / (ml-diluent) (hereinafter, the slurry concentration is simply g The temperature was raised to 95 ° C., and a 0.49 weight ratio of diisobutyl phthalate was added in an equal amount over 40 minutes. After completion of the addition, the mixture was further stirred for 30 minutes. The charging rate of diisobutyl phthalate corresponds to 0.93 mol / (L-diluent / Hr).
(4) After completion of the treatment of (3), the slurry of (3) was pumped to the filtration layer and subjected to filtration washing at a toluene ratio of 2.12.
(5) The slurry of (4) was pumped into a stirring tank, and an appropriate amount of toluene was added to make the slurry concentration 0.40 g / ml. While stirring, dibutyl ether 0.04 weight ratio, titanium tetrachloride 1.62 weight Ratio, diisobutyl phthalate 0.03 weight ratio was supplied, and the temperature of the stirring tank was raised to 110 ° C., and the reaction was carried out at this temperature for 3 hours.
(6) After completion of the reaction of (5), the slurry of (5) was pumped to a filtration tank and subjected to solid-liquid separation by filtration, and the solid content was filtered and washed three times with a toluene 2.12 weight ratio.
(7) The slurry of (6) is pumped to the stirring layer, and further, an appropriate amount of toluene is added to make the slurry concentration 0.40 g / ml. With stirring, dibutyl ether 0.04 weight ratio, titanium tetrachloride 0.81 weight After supplying the mixed solution of the ratio, the temperature was raised to 110 ° C., and the reaction was performed at this temperature for 1 hour.
After completion of the reaction of (8) and (7), the slurry of (7) is pumped to a filtration tank and separated into solid and liquid by filtration operation, and the solid content is filtered and washed three times with a weight ratio of toluene of 2.12. Subsequently, the filter was washed three times at a weight ratio of 1.49 by weight of hexane.
(9) Slurry of the solid catalyst component for olefin polymerization obtained by the procedures of (1) to (8) was heated by circulating nitrogen at a dew point of −65 ° C. to 70 ° C. as measured by a capacitance dew point meter. The mixture was pumped to a powder dryer and the organic solvent was evaporated and dried to form a powder, which was further dried in a vacuum dryer at 1 to 3 KpaA (absolute pressure display) at 70 ° C. for 16 hours. A powdery solid catalyst component for olefin polymerization was obtained.
[0070]
The obtained solid catalyst component was analyzed, evaluated for fluidity, evaluated for activity, and the like. The solid catalyst component contained 1.9% by weight of titanium atoms, 0.2% by weight of ethoxy groups, 0.5% by weight of butoxy groups, and 10.8% by weight of phthalates. Further, the fluidity of the solid catalyst component was good without any particular problem, and showed high activity. The evaluation results are summarized in Table 1.
[0071]
Example 2
Of the procedure shown in Example 1, all were performed in the same manner except that in (3), 0.49 weight ratio of diisobutyl phthalate was added in an equal amount over 50 minutes. The input rate of diisobutyl phthalate corresponds to 0.74 mol / (L-diluent / Hr). Table 1 shows the results of analysis of the obtained solid catalyst component, evaluation of fluidity and activity evaluation.
[0072]
Example 3
Of the procedures shown in Example 1, all were performed in the same manner except that in (3), 0.49 weight ratio of diisobutyl phthalate was added in an equal amount over 30 minutes. The charging rate of diisobutyl phthalate corresponds to 1.23 mol / (L-diluent / Hr). Table 1 shows the results of analysis of the obtained solid catalyst component, evaluation of fluidity and activity evaluation.
[0073]
Comparative Example 1
Of the procedures shown in Example 1, all were performed in the same manner except that in (3), 0.49 weight ratio of diisobutyl phthalate was added in an equal amount over 20 minutes. The charging rate of diisobutyl phthalate corresponds to 1.85 mol / (L-diluted solution · Hr). Table 1 shows the results of analysis of the obtained solid catalyst component, evaluation of fluidity and activity evaluation.
[0074]
Comparative Example 2
Of the procedures shown in Example 1, all were performed in the same manner except that in (3), 0.49 weight ratio of diisobutyl phthalate was added in an equal amount over 60 minutes. The input rate of diisobutyl phthalate corresponds to 0.62 mol / (L-diluent · Hr). The fluidity of the dried solid catalyst component was poor, causing bridging at the container discharge and hindering handling. Table 1 shows the results of analysis of the obtained solid catalyst component, evaluation of fluidity and activity evaluation.
[0075]
[Table 1]

[0076]
【The invention's effect】
According to the present invention, an olefin polymerization catalyst using a solid catalyst component for olefin polymerization having a small amount of fine powder and a high olefin polymerization ability, and an olefin weight having a high stereoregularity using the catalyst and generating a fine powder polymer are small. It has become possible to provide a manufacturing method for coalescence.

Claims (3)

For olefin polymerization, comprising the following (A), (B) and (C), wherein the solid catalyst component for olefin polymerization (A) is produced by a method comprising the following first to third steps: catalyst.
(A) Solid catalyst component for olefin polymerization comprising titanium, magnesium, halogen and electron donor as essential components (B) Organoaluminum compound (C) Electron donating compound First step: Organosilicon compound having Si-O bond and / or Alternatively, in the presence of an ester compound, the general formula Ti (OR ¹ ) _a X _4-a (R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and a represents a number of 0 <a ≦ 4. Step 2 in which a solid product is obtained by reducing the titanium compound represented by organomagnesium compound, the solid product is slurried with a diluent and controlled at a temperature of 50 to 100 ° C. Step of supplying an ester compound at a rate of 7 to 1.2 (mol-ester compound) / (L-diluent / Hr) and treating the solid product with the ester compound Third step: The ester compound Treating the solid product treated in step with a mixture of ether compound and titanium tetrachloride or a mixture of ether compound, titanium tetrachloride and ester compound The slurry concentration when slurrying the solid product with a diluent in the second step is 0.1 to 0.2 (g-solid product) / (ml-diluent). Olefin polymerization catalyst. A method for producing an olefin polymer, wherein the olefin is homopolymerized or copolymerized using the olefin polymerization catalyst according to claim 1.