JP3832039B2 - α-Olefin Polymerization Catalyst and Method for Producing α-Olefin Polymer - Google Patents

Description

（式中、Ｒ¹⁸〜Ｒ²¹は炭素数１〜２０の線状または分岐状のアルキル基、脂環式炭化水素基、アリール基、またはアラルキル基であり、Ｒ¹⁸またはＲ¹⁹は水素原子であってもよい。）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。
【００６１】
これらの電子供与性化合物のうち一般式Ｒ²²Ｒ²³Ｓｉ（ＯＲ²⁴）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、Ｒ²²はＳｉに隣接する炭素原子が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、ｔｅｒｔ−ブチル基、ｔｅｒｔ−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、Ｒ²³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、ｔｅｒｔ−ブチル基、ｔｅｒｔ−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、Ｒ²⁴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。
【００６２】
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−ｔｅｒｔ−ブチルジメトキシシラン、ｔｅｒｔ−ブチルメチルジメトキシシラン、ｔｅｒｔ−ブチルエチルジメトキシシラン、ｔｅｒｔ−ブチル−ｎ−プロピルジメトキシシラン、ｔｅｒｔ−ブチル−ｎ−ブチルジメトキシシラン、ｔｅｒｔ−アミルメチルジメトキシシラン、ｔｅｒｔ−アミルエチルジメトキシシラン、ｔｅｒｔ−アミル−ｎ−プロピルジメトキシシラン、ｔｅｒｔ−アミル−ｎ−ブチ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、ｔｅｒｔ−ブチルイソプロピ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−ｔｅｒｔ−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−ｔｅｒｔ−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−ｔｅｒｔ−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−ｔｅｒｔ−ブチルジエトキシシラン、ｔｅｒｔ−ブチルメチルジエトキシシラン、ｔｅｒｔ−ブチルエチルジエトキシシラン、ｔｅｒｔ−ブチル−ｎ−プロピルジエトキシシラン、ｔｅｒｔ−ブチル−ｎ−ブチルジエトキシシラン、ｔｅｒｔ−アミルメチルジエトキシシラン、ｔｅｒｔ−アミルエチルジエトキシシラン、ｔｅｒｔ−アミル−ｎ−プロピルジエトキシシラン、ｔｅｒｔ−アミル−ｎ−ブ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。
【００６３】
（ｊ）オレフィンの重合方法
本発明に適用できるα−オレフィンは、炭素数３以上のα−オレフィンであり、好ましくは炭素数３〜１０のα−オレフィンである。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α−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α−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α−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。
【００６４】
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。
【００６５】
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。
【００６６】
本発明においては、前記の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。
【００６７】
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。
【００６８】
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１モル当たり、通常０．５〜７００モルのごとく広範囲に選ぶことができるが、０．８〜５００モルが好ましく、１〜２００モルが特に好ましい。
【００６９】
また、予備重合されるオレフィンの量は、固体触媒成分１ｇ当たり通常０．０１〜１０００ｇ、好ましくは０．０５〜５００ｇ、特に好ましくは０．１〜２００ｇである。
【００７０】
予備重合を行う際のスラリー濃度は、１〜５００ｇ−固体触媒成分／リットル−溶媒が好ましく、特に３〜３００ｇ−固体触媒成分／リットル−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、０．０１〜２０ｋｇ／ｃｍ² が好ましく、特に０．１〜１０ｋｇ／ｃｍ² 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。
【００７１】
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。
【００７２】
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１モルに対し、通常０．０１〜４００モル、好ましくは０．０２〜２００モル、特に好ましくは、０．０３〜１００モルであり、有機アルミニウム化合物（Ｂ）に対し、通常０．００３〜５モル、好ましくは０．００５〜３モル、特に好ましくは０．０１〜２モルである。
【００７３】
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（Ｂ）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。
【００７４】
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α−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。
【００７５】
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１モル当たり、通常１〜１０００モルのごとく広範囲に選ぶことができるが、特に５〜６００モルの範囲が好ましい。
【００７６】
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１モルに対し、通常０．１〜２０００モル、好ましくは０．３〜１０００モル、特に好ましくは、０．５〜８００モルであり、有機アルミニウム化合物に対し、通常０．００１〜５モル、好ましくは０．００５〜３モル、特に好ましくは０．０１〜１モルである。
【００７７】
本重合は、通常−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〜１００ｋｇ／ｃｍ² 、好ましくは２〜５０ｋｇ／ｃｍ² 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。
【００７８】
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。
【００７９】
【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。なお実施例中、重合体の各種物性の評価方法は、次のとおりである。
【００８０】
（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、次いで氷水に浸し撹拌しながら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・秤量し、全ポリマーに対する重量％を求める。
ＣＸＳは値が小さいほど、無定形重合体が少なく、高立体規則性であることを示す。
【００８１】
（２）極限粘度（以下［η］と略す）：ウベローデ型粘度計を用いて、テトラリン溶媒、１３５℃で測定した。
【００８２】
（３）ロジン・ラムラーの式におけるＮ：堀場製作所（株）製超遠心式自動粒度分布測定装置ＣＡＰＡ−７００を用いて頻度分布を測定した後、得られたデータを下記のロジン・ラムラーの式（Rosin,P.and E.Rammler :J.Inst.Fuel,7,P29(1933). 及び化学工学便覧 改訂３版 ３６１〜３６２ページ）に適用することにより求めた。
Ｒ（Ｄp ）＝１００ｅｘｐ｛−（Ｄp ／Ｄe ）^N ｝
ここで、Ｒ（Ｄp ）は残留率分布であり、ある粒子径Ｄp よりも大きい粒子群の積算量と全体量との比を粒子径に対して残留率曲線として示したものである。またＤe はＲ（Ｄp ）＝３６．８％における粒子径を表わす。
Ｎの値が大きいほど分布は狭くなる傾向を示し、この値が大きい固体触媒成分は、粒径分布が狭く、得られた重合体は嵩密度が高く工業的にも好ましい。
【００８３】
実施例１
（ａ） 還元固体生成物の合成
撹拌機、滴下ロートを備えた５００ｍｌのフラスコを窒素で置換した後、ヘキサン２９０ｍｌ、テトラブトキシチタン８．９ｍｌ（８．９ｇ、２６．１ミリモル）、フタル酸ジイソブチル３．１ｍｌ（３．３ｇ、１１．８ミリモル）およびテトラエトキシシラン８７．４ｍｌ（８１．６ｇ、３９２ミリモル）を投入し、均一溶液とした。次に、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）１９９ｍｌを、フラスコ内の温度を６℃に保ちながら、滴下ロートから５時間かけて徐々に滴下した。滴下終了後、６℃でさらに１時間撹拌した後、室温でさらに１時間攪拌した。その後、固液分離し、トルエン２６０ｍｌで３回洗浄を繰り返した後、トルエンを適量加え、スラリー濃度０．１７６ｇ／ｍｌとした。
固体生成物スラリーの一部をサンプリングし、組成分析を行ったところ固体生成物中にはチタン原子が１．９６重量％、フタル酸エステルが０．１２重量％、エトキシ基が３７．２重量％、ブトキシ基が２．８重量％含有されていた。
【００８４】
（ｂ） 固体触媒成分の合成
撹拌機、滴下ロート、温度計を備えた１００ｍｌのフラスコを窒素で置換したのち、上記（ａ）で得られた固体生成物を含むスラリーを５２ｍｌ投入し、上澄み液を２５．５ｍｌ抜き出しブチルエーテル０．８０ｍｌ（６．４５ミリモル）と四塩化チタン１６．０ｍｌ（０．１４６モル）の混合物を加え、ついで、フタル酸クロライド１．６ｍｌ（１１．１ミリモル：０．２０ｍｌ／１ｇ固体生成物）を加え、１１５℃まで昇温しそのまま３時間攪拌した。反応終了後、同温度で固液分離した後、同温度でトルエン４０ｍｌで２回洗浄を行った。次いで、トルエン１０．０ｍｌ、フタル酸ジイソブチル０．４５ｍｌ（１．６８ミリモル）、ブチルエーテル０．８０ｍｌ（６．４５ミリモル）、及び四塩化チタン８．０ｍｌ（０．０７３モル）の混合物を加え、１１５℃で１時間処理を行った。反応終了後、同温度で固液分離し、同温度でトルエン４０ｍｌで３回洗浄を行ったのち、ヘキサン４０ｍｌで３回洗浄し、さらに減圧乾燥して固体触媒成分７．３６ｇを得た。
固体触媒成分中には、チタン原子が２．１８重量％、フタル酸エステルが１１．３７重量％、エトキシ基が０．３重量％、ブトキシ基が０．１重量％含まれていた。また、固体触媒成分を実体顕微鏡で観察したところ、微粉の無い良好な粒子性状を有していた。
【００８５】
（ｃ） プロピレンの重合
３リットル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、トリエチルアルミニウム２．６ミリモル、シクロヘキシルエチルジメトキシシラン０．２６ミリモル及び（ｂ）で合成した固体触媒成分５．７ｍｇを仕込み、０．３３ｋｇ／ｃｍ² 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、８０℃で１時間重合を行った。重合終了後未反応モノマーをパージした。生成した重合体を６０℃で２時間減圧乾燥し、２３１ｇのポリプロピレンパウダーを得た。
従って、固体触媒成分１ｇ当たりのポリプロピレンの収量（以下、ＰＰ／Ｃａｔと略す）は、ＰＰ／Ｃａｔ＝４０，６００（ｇ／ｇ）であった。また、全重合体収量に占める２０℃キシレンに可溶な成分の割合はＣＸＳ＝０．４９（ｗｔ％）、重合体の極限粘度は［η］＝１．９６、嵩密度＝０．３８５g/mlであった。重合条件及び重合結果を表１に示す。
【００８６】
比較例１
（ａ） 還元固体生成物の合成
使用する試薬の量をテトラブトキシチタン７．５ｍｌ（７．５ｇ、２２ミリモル）、フタル酸ジイソブチル２．５ｍｌ（２．６ｇ、９．３ミリモル）およびテトラエトキシシラン７４．８ｍｌ（７０．３ｇ、３３８ミリモル）、有機マグネシウム化合物溶液１７３ｍｌとした以外は、実施例１の（ａ）と同様にして反応を行った。固液分離して得た固体生成物は、ヘキサン３００ｍｌで３回、トルエン３００ｍｌで３回洗浄を繰り返した後トルエン２７０ｍｌを加えた。
固体生成物スラリーの一部をサンプリングし、組成分析を行ったところ固体生成物中にはチタン原子が１．８０重量％、フタル酸エステルが０．１重量％、エトキシ基が３５．０重量％、ブトキシ基が３．２重量％含有されていた。
【００８７】
（ｂ） 固体触媒成分の合成
攪拌機、滴下ロート、温度計を備えた２００ｍｌのフラスコをアルゴンで置換したのち、上記（ａ）で得られた固体生成物を含むスラリーを８４ｍｌ投入し、更に上澄み液を１２．１ｍｌを抜き取り、フタル酸ジイソブチル７．８ｍｌ（２９ミリモル）を加え、９５℃で３０分反応を行った。反応後、固液分離し、トルエン５９ｍｌで２回洗浄を行った。
次いで、フラスコにトルエン１５．３ｍｌ、フタル酸ジイソブチル０．６６ｍｌ（２．５ミリモル）、ブチルエーテル１．２ｍｌ（６．９ミリモル）、および四塩化チタン２３．４ｍｌ（０．２１３モル）の混合物を加え、１０５℃で３時間処理を行った。処理終了後、同温度で固液分離した後、同温度でトルエン５９ｍｌで２回洗浄を行った。次いで、トルエン１２．０ｍｌ、ブチルエーテル１．２ｍｌ（６．９ミリモル）、および四塩化チタン１１．７ｍｌ（０．１０６モル）の混合物を加え、１０５℃で１時間処理を行った。処理終了後、同温度で固液分離した。同温度でトルエン５９ｍｌで３回洗浄を行ったのち、ヘキサン５９ｍｌで３回洗浄し、さらに減圧乾燥して固体触媒成分８．１ｇを得た。
固体触媒成分中には、チタン原子が１．５重量％、フタル酸エステルが８．９重量％、エトキシ基が０．４重量％、ブトキシ基が０．１重量％含まれていた。
【００８８】
（ｃ） プロピレンの重合
実施例１（ｃ）のプロピレンの重合において、上記（ｃ）で得た固体触媒成分を４．０ｍｇ用いた以外は同様にしてプロピレンの重合を行った。
重合結果は、ＰＰ／Ｃａｔ＝３０，０００（ｇ／ｇ）と重合活性は低く、ＣＸＳ＝０．７４（ｗｔ％）と立体規則性が低かった。また、嵩密度＝０．３６０g/ml、［η］＝２．０１であった。重合条件及び重合結果を表１に示す。
【００８９】
実施例２
（ｃ） プロピレンの重合
実施例１（ｂ）で調製した固体触媒成分を用い、シクロヘキシルエチルジメトキシシランの代わりにｔｅｒｔ−ブチル−ｎ−プロピルジメトキシシランを用いた以外は実施例１（ｃ）のプロピレンの重合と同様にして重合を行った。
重合結果は、ＰＰ／Ｃａｔ＝５５，７００（ｇ／ｇ）、ＣＸＳ＝０．３３（ｗｔ％）、嵩密度＝０．４０５g/ml、［η］＝２．６９であった。重合条件及び重合結果を表１に示す。
【００９０】
実施例３
（ｂ） 固体触媒成分の合成
実施例１の（ａ）で調製した固体生成物を含むスラリーの量を４６ｍｌ投入し、上澄み液を２２．５ｍｌ抜き出しブチルエーテル０．７１ｍｌ（５．７３ミリモル）、および四塩化チタン１１．４ｍｌ（０．１０４モル）の混合物を加え、ついで、フタル酸クロライド１．４２ｍｌ（９．８６ミリモル：０．２０ｍｌ／１ｇ固体生成物）を加え、１１５℃まで昇温しそのまま３時間攪拌した。処理終了後、同温度で固液分離した後、同温度でトルエン３６ｍｌで２回洗浄を行った。次いで、トルエン９．０ｍｌ、フタル酸ジイソブチル０．４０ｍｌ（１．４９ミリモル）、ブチルエーテル０．７１ｍｌ（５．７３ミリモル）、および四塩化チタン５．７ｍｌ（０．０５２モル）の混合物を加え、１１５℃で１時間反応を行った。反応終了後、同温度で固液分離し、同温度でトルエン３６ｍｌで３回洗浄を行ったのち、ヘキサン３６ｍｌで３回洗浄し、さらに減圧乾燥して固体触媒成分６．５３ｇを得た。
固体触媒成分中には、チタン原子が２．３４重量％、フタル酸エステルが１０．５７重量％、エトキシ基が０．４重量％、ブトキシ基が０．１重量％含まれていた。また、固体触媒成分を実体顕微鏡で観察したところ、微粉の無い良好な粒子性状を有していた。
【００９１】
（ｃ） プロピレンの重合
上記（ｂ）で得た固体触媒成分を用いた以外は、実施例１（ｃ）のプロピレンの重合と同様にしてプロピレンの重合を行った。
重合結果は、ＰＰ／Ｃａｔ＝４６，７００（ｇ／ｇ）、ＣＸＳ＝０．４６（ｗｔ％）、嵩密度＝０．３９６g/ml、［η］＝１．９５であった。重合条件及び重合結果を表１に示す。
【００９２】
実施例４
（ｂ） 固体触媒成分の合成
フタル酸ジイソブチルを０．２２ｍｌ用いた以外は、全て実施例１（ｂ）と同様に固体触媒成分の合成を行った。
固体触媒成分中には、チタン原子が２．２２重量％、フタル酸エステルが１０．２０重量％、エトキシ基が０．３７重量％、ブトキシ基が０．１４重量％含まれていた。また、固体触媒成分を実体顕微鏡で観察したところ、微粉の無い良好な粒子性状を有していた。
【００９３】
（ｃ） プロピレンの重合
上記（ｂ）で得た固体触媒成分を用いた以外は，実施例１（ｃ）のプロピレンの重合と同様にしてプロピレンの重合を行った。
重合結果は、ＰＰ／Ｃａｔ＝４９，１００（ｇ／ｇ）、ＣＸＳ＝０．５０（ｗｔ％）、嵩密度＝０．３９９g/ml、［η］＝１．９０であった。重合条件及び重合結果を表１に示す。
【００９４】
実施例５
（ｃ） プロピレンの重合
シクロヘキシルエチルジメトキシシランの代わりにｔｅｒｔ−ブチル−ｎ−プロピルジメトキシシランを用いた以外は、実施例４（ｃ）のプロピレンの重合と同様にして重合を行った。
重合結果は、ＰＰ／Ｃａｔ＝５７，５００（ｇ／ｇ）、ＣＸＳ＝０．４７（ｗｔ％）、嵩密度＝０．４０６g/ml、［η］＝２．６７であった。重合条件及び重合結果を表１に示す。
【００９５】
実施例６
（ａ） 還元固体生成物の合成
実施例１（ａ）と同様の方法で固体生成物の合成を行った。得られた固体生成物のスラリー濃度は０．１８４ｇ／ｍｌであった。
固体生成物スラリーの一部をサンプリングし、組成分析を行ったところ固体生成物中にはチタン原子が１．９４重量％、フタル酸エステルが０．１８重量％、エトキシ基が３４．６重量％、ブトキシ基が３．２重量％含有されていた。
【００９６】
（ｂ） 固体触媒成分の合成
上記（ａ）で調製した固体生成物を含むスラリーの量を５０ｍｌ投入し、上澄み液を２３．５ｍｌ抜き出しブチルエーテル０．８０ｍｌ（６．４５ミリモル）と四塩化チタン１６．０ｍｌ（０．１４６モル）との混合物を加え、ついで、フタル酸クロライド１．６０ｍｌ（１１．１ミリモル：０．２０ｍｌ／１ｇ固体生成物）を加え、１１５℃まで昇温しそのまま３時間攪拌した。処理終了後、同温度で固液分離した後、同温度でトルエン４０ｍｌで２回洗浄を行った。次いで、トルエン１０ｍｌ、フタル酸ジイソブチル０．４５ｍｌ（１．６８ミリモル）、ブチルエーテル０．８０ｍｌ（６．４５ミリモル）、および四塩化チタン８．０ｍｌ（０．０７３モル）の混合物を加え、１１５℃で１時間処理を行った。処理終了後、同温度で固液分離した後、同温度でトルエン４０ｍｌで２回洗浄を行った。次いで、トルエン１０ｍｌ、フタル酸ジイソブチル０．４５ｍｌ（１．６８ミリモル）、ブチルエーテル０．８０ｍｌ（６．４５ミリモル）、および四塩化チタン８．０ｍｌ（０．０７３モル）の混合物を加え、１１５℃で１時間処理を行った。処理終了後、同温度で固液分離し、同温度でトルエン４０ｍｌで３回洗浄を行ったのち、ヘキサン４０ｍｌで３回洗浄し、さらに減圧乾燥して固体触媒成分７．０７ｇを得た。
固体触媒成分中には、チタン原子が２．１３重量％、フタル酸エステルが１２．３７重量％、エトキシ基が０．１重量％、ブトキシ基が０．１重量％含まれていた。また、固体触媒成分を実体顕微鏡で観察したところ、微粉の無い良好な粒子性状を有していた。
【００９７】
（ｃ） プロピレンの重合
上記（ｂ）で得た固体触媒成分を用いた以外は、実施例１（ｃ）のプロピレンの重合と同様にしてプロピレンの重合を行った。
重合結果は、ＰＰ／Ｃａｔ＝４１，３００（ｇ／ｇ）、ＣＸＳ＝０．４１（ｗｔ％）、嵩密度＝０．４００g/ml、［η］＝１．９３であった。重合条件及び重合結果を表１に示す。
【００９８】
実施例７
（ｂ） 固体触媒成分の合成
実施例６（ａ）で調製した固体生成物を含むスラリーの量を５０ｍｌ投入し、上澄み液を２３．５ｍｌ抜き出しブチルエーテル０．８０ｍｌ（６．４５ミリモル）と四塩化チタン１６．０ｍｌ（０．１４６モル）の混合物を加え、ついで、フタル酸クロライド１．６０ｍｌ（１１．１ミリモル：０．２０ｍｌ／１ｇ固体生成物）を加え、１１５℃まで昇温しそのまま３時間攪拌した。処理終了後、同温度で固液分離した後、同温度でトルエン４０ｍｌで２回洗浄を行った。次いで、トルエン１０ｍｌ、フタル酸ジイソブチル０．４５ｍｌ（１．６８ミリモル）、ブチルエーテル０．８０ｍｌ（６．４５ミリモル）、および四塩化チタン８．０ｍｌ（０．０７３モル）の混合物を加え、１１５℃で１時間処理を行った。処理終了後、同温度で固液分離した後、同温度でトルエン４０ｍｌで２回洗浄を行った。次いで、トルエン１０ｍｌ、ブチルエーテル０．８０ｍｌ（６．４５ミリモル）、および四塩化チタン６．４ｍｌ（０．０５８モル）の混合物を加え、１１５℃で１時間処理を行った。処理終了後、同温度で固液分離した後、同温度でトルエン４０ｍｌで２回洗浄を行った。次いで、トルエン１０ｍｌ、ブチルエーテル０．８０ｍｌ（６．４５ミリモル）、および四塩化チタン６．４ｍｌ（０．０５８モル）の混合物を加え、１１５℃で１時間処理を行った。処理終了後、同温度で固液分離し、同温度でトルエン４０ｍｌで３回洗浄を行ったのち、ヘキサン４０ｍｌで３回洗浄し、さらに減圧乾燥して固体触媒成分６．５８ｇを得た。固体触媒成分中には、チタン原子が１．７８重量％、フタル酸エステルが８．６６重量％、エトキシ基が０．１重量％、ブトキシ基が０．２重量％含まれていた。また、固体触媒成分を実体顕微鏡で観察したところ、微粉の無い良好な粒子性状を有していた。
【００９９】
（ｃ） プロピレンの重合
上記（ｂ）で得た固体触媒成分を用いた以外は、実施例１（ｃ）のプロピレンの重合と同様にしてプロピレンの重合を行った。
重合結果は、ＰＰ／Ｃａｔ＝５１，２００（ｇ／ｇ）、ＣＸＳ＝０．４４（ｗｔ％）、嵩密度＝０．４０７g/ml、［η］＝１．９５であった。重合条件及び重合結果を表１に示す。
【０１００】
比較例２
（ｂ） 固体触媒成分の合成
攪拌機、滴下ロート、温度計を備えた１００ｍｌのフラスコをアルゴンで置換したのち、実施例６（ａ）で調製した固体生成物を含むスラリーの量を５０ｍｌ投入し、更に上澄み液を２３．５ｍｌ抜き取り、フタル酸クロライド１．６ｍｌ（１１．１ミリモル）を加え、１１０℃で３０分反応を行った。反応後、固液分離し、トルエン４０ｍｌで２回洗浄を行った。
次いで、フラスコにトルエン１０ｍｌ、フタル酸ジイソブチル０．４５ｍｌ（１．７ミリモル）、ブチルエーテル０．８ｍｌ（６．５ミリモル）、および四塩化チタン１６．０ｍｌ（０．１４６モル）の混合物を加え、１１５℃で３時間反応を行った。反応終了後、同温度で固液分離した後、同温度でトルエン４０ｍｌで２回洗浄を行った。次いで、トルエン１０ｍｌ、ブチルエーテル０．８ｍｌ（６．５ミリモル）、および四塩化チタン８．０ｍｌ（０．０７３モル）の混合物を加え、１１５℃で１時間反応を行った。反応終了後、同温度で固液分離した後、同温度でトルエン４０ｍｌで３回洗浄を行ったのち、ヘキサン４０ｍｌで３回洗浄し、さらに減圧乾燥して固体触媒成分５．８ｇを得た。
固体触媒成分中には、チタン原子が１．２８重量％、フタル酸エステルが５．７５重量％、エトキシ基が１．２重量％、ブトキシ基が０．２重量％含まれていた。
【０１０１】
（ｄ） プロピレンの重合
上記（ｃ）で得た固体触媒成分を３．９ｍｇ用いた以外は、実施例１（ｃ）のプロピレンの重合と同様にしてプロピレンの重合を行った。
重合結果は、ＰＰ／Ｃａｔ＝７，７００（ｇ／ｇ）と重合活性は低く、ＣＸＳ＝１．５６（ｗｔ％）と立体規則性が低かった。また、嵩密度＝０．４２０g/ml、［η］＝１．６１であった。重合条件及び重合結果を表１に示す。
【０１０２】
比較例３
（ｂ） 固体触媒成分の合成
実施例６（ａ）で調製した固体生成物を含むスラリーの量を５０ｍｌ投入し、トルエンを２３．５ｍｌ抜き出し、先にフタル酸クロライド１．６０ｍｌ（１１．１ミリモル：０．２０ｍｌ／１ｇ固体生成物）を加え、その後、ブチルエーテル０．８０ｍｌ（６．４５ミリモル）四塩化チタン１６．０ｍｌ（０．１４６モル）の混合液を加え、１１５℃まで昇温しそのまま３時間攪拌した。反応終了後、同温度で固液分離した後、同温度でトルエン４０ｍｌで２回洗浄を行った。次いで、トルエン１０ｍｌ、フタル酸ジイソブチル０．４５ｍｌ（１．６８ミリモル）、ブチルエーテル０．８０ｍｌ（６．４５ミリモル）、および四塩化チタン８．０ｍｌ（０．０７３モル）の混合物を加え、１１５℃で１時間処理を行った。処理終了後、同温度で固液分離し、同温度でトルエン４０ｍｌで３回洗浄を行ったのち、ヘキサン４０ｍｌで３回洗浄し、さらに減圧乾燥して固体触媒成分７．２７ｇを得た。
固体触媒成分中には、チタン原子が２．２９重量％、フタル酸エステルが１１．０３重量％、エトキシ基が０．２重量％、ブトキシ基が０．１重量％含まれていた。
【０１０３】
（ｃ） プロピレンの重合
上記（ｂ）で得た固体触媒成分を用いた以外は、実施例１（ｃ）のプロピレンの重合と同様にしてプロピレンの重合を行った。
重合結果は、ＰＰ／Ｃａｔ＝２５，８００（ｇ／ｇ）と低活性であった。また、ＣＸＳ＝０．５７（ｗｔ％）、嵩密度＝０．３６５g/ml、［η］＝１．９５であった。重合条件及び重合結果を表１に示す。
【０１０４】
【表１】

【０１０５】
【発明の効果】
本発明によれば、粒径分布が良好でなおかつ触媒残渣および無定形重合体の除去が不必要な、十分高い触媒活性と立体規則性を有するα−オレフィン重合用触媒、ならびに高品質の高立体規則性α−オレフィン重合体の製造方法が提供される。
【図面の簡単な説明】
【図１】図１は、本発明の理解を助けるためのフローチャート図である。本フローチャート図は、本発明の実施態様の代表例であり、本発明は、何らこれに限定されるものではない。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an α-olefin polymerization catalyst and a method for producing an α-olefin polymer. More specifically, by using a novel catalyst having a very high catalytic activity per solid catalyst and per titanium atom, the catalyst residue and the amorphous polymer are very few, and the highly stereoregular α having excellent mechanical properties and processability. The present invention relates to an α-olefin polymerization catalyst for producing an olefin polymer, and a method for producing an α-olefin polymer.
[0002]
[Prior art]
As a method for producing an isotactic polymer of an α-olefin such as propylene and butene-1, a solid catalyst component obtained by using a transition metal compound of Groups 4 to 6 of the periodic table, and 1, 2, 13 It is well known to use so-called Ziegler-Natta catalysts consisting of group III organometallic compounds.
[0003]
When producing an α-olefin polymer, an amorphous polymer is produced as a by-product in addition to the highly stereoregular α-olefin polymer that is industrially highly useful. This amorphous polymer has little industrial utility value, and greatly affects the mechanical properties when the α-olefin polymer is processed into a molded product, film, fiber, or other processed product. In addition, the production of the amorphous polymer causes loss of raw material monomers, and at the same time, a production facility for removing the amorphous polymer is required, which is disadvantageous from an industrial viewpoint. Therefore, it is preferable that the catalyst for producing the α-olefin polymer does not produce such an amorphous polymer at all or is very little.
[0004]
Moreover, in the α-olefin polymer obtained, a catalyst residue composed of a transition metal component and an organometallic component remains. Since this catalyst residue causes problems in various points such as the stability and processability of the α-olefin polymer, a deashing facility for removing and stabilizing the catalyst residue is required.
This drawback can be improved by increasing the catalytic activity represented by the weight of the produced α-olefin polymer per unit weight of the catalyst, and the equipment for removing the catalyst residue is not required. The manufacturing cost can be reduced.
[0005]
In the coexistence of an organosilicon compound, a Ti-Mg composite solid catalyst obtained by reducing a tetravalent titanium compound with an organomagnesium compound to form a eutectic of magnesium and titanium is a co-catalyst organoaluminum compound, It is known that a certain degree of high stereoregularity and high activity polymerization of an α-olefin can be realized by using it in combination with an organosilicon compound as a third component of polymerization (Japanese Patent Publication No. 3-43283, JP-A-1-319508). Issue gazette).
[0006]
In the above-mentioned method, the present applicant firstly has a higher stereoregularity and higher activity polymerization by reducing the tetravalent titanium compound with the organomagnesium compound in the coexistence of the organosilicon compound and further coexisting the ester compound. Has been proposed (Japanese Patent Laid-Open No. 7-206017).
[0007]
In any case, although there is a level at which no extraction and no decalcification process is possible, further improvement is desired. Specifically, in order to improve the quality of the α-olefin polymer, it is desired to realize further highly stereoregular polymerization without sacrificing the particle size distribution or the like. In particular, in applications where high rigidity of the polymer is desired, such as in the field of injection molding, a high stereoregular polymer directly produces high rigidity, so that high stereoregular polymerization ability is achieved. The emergence of a catalyst having such is desired.
[0008]
Further, when a solid catalyst such as a Ziegler-Natta catalyst is used for industrial practical use, its particle shape and particle size distribution are very important for controlling the bulk density, particle size and fluidity of the polymer. With regard to the improvement of the particle shape and the narrowing of the particle size distribution, in the polymerization of ethylene, an attempt has been made to overcome such problems by using a solid catalyst in which a titanium-magnesium compound is supported on silica gel. (Kaisho 54-148098, JP 56-47407).
Japanese Patent Application Laid-Open No. Sho 62-256802 describes that, in the polymerization of propylene, the use of a solid catalyst in which a silica gel is impregnated with a titanium-magnesium compound greatly improves the particle properties.
[0009]
According to these methods, the effect of improving the particle shape is certainly recognized, but since the silica gel used for the carrier remains in the product in a large amount, it causes fish eyes in film use, which is not preferable in terms of quality. Also, the polymerization activity is low and the productivity is not satisfactory. Therefore, there is an urgent need for a solid catalyst component having a high catalyst activity and a high stereoregular polymerization ability with a good catalyst shape and a narrow particle size distribution.
[0010]
[Problems to be solved by the invention]
Under such circumstances, the problem to be solved by the present invention, that is, the object of the present invention, is to produce a highly stereoregular α-olefin polymer with few fine powders and good powder properties, and to produce the α-olefin polymer. Another object of the present invention is to provide an α-olefin polymerization catalyst having a sufficiently high catalytic activity such that removal of catalyst residue and amorphous polymer is unnecessary.
[0011]
[Means for Solving the Problems]
The present inventors have intensively studied to solve such problems. As a result, a Ti—Mg composite obtained by treating a solid product obtained by reducing a tetravalent titanium compound with an organomagnesium compound in the presence of an organosilicon compound and an ester compound with titanium tetrachloride and an organic acid halide compound. The present inventors have found a method using a combination of a solid catalyst component, an organoaluminum compound as a promoter component, and an organosilicon compound as a polymerization third component, and have reached the present invention.
[0012]
That is, the present invention
(A) In the presence of an organosilicon compound having an Si—O bond and an ester compound, the general formula Ti (OR¹)_aX_4-a(R¹Represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and a represents a number of 0 <a ≦ 4. The solid compound obtained by reducing the titanium compound represented by (2) with an organic magnesium compound is treated by adding a mixture of an ether compound and titanium tetrachloride and an organic acid halide compound in this order, and then treating the treated solid with an ether compound. A trivalent titanium compound-containing solid catalyst component obtained by treating with a mixture of benzene and titanium tetrachloride or a mixture of ether compound, titanium tetrachloride and ester compound,
(B) an organoaluminum compound, and
(C) electron donating compound
And a method for producing an α-olefin polymer in which an α-olefin is homopolymerized or copolymerized using the catalyst.
[0013]
The object is achieved by the use of the present catalyst.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be specifically described.
(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)_aX_4-a(R¹Represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and a represents a number of 0 <a ≦ 4. ). R¹Specific examples of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, heptyl group, octyl group, decyl Groups, alkyl groups such as dodecyl group, aryl groups such as phenyl group, cresyl group, xylyl group and naphthyl group, allyl groups such as propenyl group, aralkyl groups such as benzyl group and the like. 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 OR¹It is also possible to use a titanium compound having a group.
[0015]
Examples of the halogen atom represented by X include a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom gives particularly favorable results.
[0016]
General formula Ti (OR¹)_aX_4-aThe value of a of the titanium compound represented by the formula is 0 <a ≦ 4, preferably 2 ≦ a ≦ 4, particularly preferably a = 4.
[0017]
General formula Ti (OR¹)_aX_4-aAs a method for synthesizing the titanium compound represented by the formula, a known method can be used. For example, Ti (OR¹)_FourAnd TiX_FourIn a predetermined ratio, or TiX_FourAnd corresponding alcohols (eg R¹A method of reacting a predetermined amount of (OH) can be used. These titanium compounds may be used after diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.
[0018]
Specifically, the general formula Ti (OR¹)_aX_4-aAs the titanium compound represented by, tetrahalogenated titanium compounds such as titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, methoxy titanium trichloride, ethoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, Trihalogenated alkoxy titanium compounds such as ethoxy titanium tribromide, dihalogenated dialkoxy titanium compounds such as dimethoxy titanium dichloride, diethoxy titanium dichloride, dibutoxy titanium dichloride, diphenoxy titanium dichloride, diethoxy titanium dibromide, trimethoxy titanium chloride , Monohalogenated trials such as triethoxy titanium chloride, tributoxy titanium chloride, triphenoxy titanium chloride, triethoxy titanium bromide Kishichitan compounds, tetramethoxy titanium, tetraethoxy titanium, tetrabutoxy titanium, and the like tetraalkoxy titanium compounds such as tetra-phenoxy titanium.
[0019]
(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, for example, those represented by the following general formula can be used.
Si (OR²)_mR^Three _4-m
R^Four(R^Five ₂SiO)_pSiR⁶ _Three
Or (R⁷ ₂SiO)_q
Where R²Is a hydrocarbon group having 1 to 20 carbon atoms, R^Three, R^Four, R^Five, R⁶And R⁷Is 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.
[0020]
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.
[0021]
Among these organosilicon compounds, preferred are those represented by the general formula Si (OR²)_mR^Three _4-mEmbedded image, preferably 1 ≦ m ≦ 4, and particularly preferably a tetraalkoxysilane compound with m = 4.
[0022]
(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, alicyclic carboxylic acid esters, and aromatic carboxylic acid esters. . 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 , Methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, diphenyl phthalate, etc. it can.
[0023]
Of these ester compounds, unsaturated aliphatic 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.
[0024]
(D) Organomagnesium compound
Next, as the organomagnesium compound used in the present invention, any type of organomagnesium compound containing an Mg-carbon bond can be used. In particular the general formula R⁸MgX (wherein R⁸Represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen atom. And Grignard compounds represented by general formula R⁹R^TenMg (wherein R⁹And R^TenRepresents a hydrocarbon group having 1 to 20 carbon atoms. A dialkylmagnesium compound or a diarylmagnesium compound represented by Where R⁸, R⁹, R^TenMay be the same or different, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, amyl group, isoamyl group, hexyl group, octyl group, 2-ethylhexyl group, phenyl group, benzyl An alkyl group having 1 to 20 carbon atoms such as a group, an aryl group, an aralkyl group, or an alkenyl group is shown.
[0025]
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 R⁹R^TenExamples 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.
[0026]
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, tetrahydropyran and the like are usually 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 is also used.
[0027]
In the present invention, the organic magnesium compound is preferably used in the form of an ether solution. In this case, the ether compound includes 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 R⁸It is preferable from the viewpoint of catalyst performance to use a Grignard compound represented by MgX in the state of an ether solution.
[0028]
Moreover, the hydrocarbon soluble complex of said organomagnesium compound and organometallic compound can also be used. Examples of such an organometallic compound include an organic compound of Li, Be, B, Al, or Zn.
[0029]
(E) Ether compound
Next, as ether compounds used in the present invention, 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.
[0030]
(F) Organic acid halide compound
As the organic acid halide compound used in the present invention, mono- and polyvalent carboxylic acid halides are used, and examples thereof include aliphatic carboxylic acid halides, alicyclic carboxylic acid halides, and aromatic carboxylic acid halides. Can do. Specific examples include acetyl chloride, propionic acid chloride, butyric acid chloride, valeric acid chloride, acrylic acid chloride, methacrylic acid chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, succinic acid chloride, malonic acid chloride, maleic acid chloride, Itaconic acid chloride, phthalic acid chloride and the like can be mentioned.
[0031]
Of these organic acid halide compounds, aromatic carboxylic acid chlorides such as benzoyl chloride, toluic acid chloride, and phthalic acid chloride are preferable, and phthalic acid chloride is particularly preferable.
[0032]
(G) Synthesis of solid catalyst component
The solid catalyst component (A) of the present invention comprises a solid product obtained by reducing a titanium compound with an organomagnesium compound in the presence of an organosilicon compound and an ester compound, a mixture of an ether compound and titanium tetrachloride, and then an organic acid. After the halide compounds are added and treated in this order, the treated solid is treated with a mixture of an ether compound and titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound. All of these synthesis reactions are usually carried out in an inert gas atmosphere such as nitrogen or argon.
[0033]
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 catalytic activity.
[0034]
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.
[0035]
The reduction reaction temperature is usually in the temperature range of −50 to 70 ° C., preferably −30 to 50 ° C., particularly preferably −25 to 35 ° C. If the reduction reaction temperature is too high, the catalytic activity is lowered.
[0036]
In the reduction reaction, a porous substance such as an inorganic oxide or an organic polymer can be coexisted, and the porous product can be impregnated with the solid product. As such a porous substance, those having a pore volume at a pore radius of 20 to 200 nm of 0.3 ml / g or more and an average particle diameter of 5 to 300 μm are preferable.
[0037]
As the porous inorganic oxide, SiO₂, Al₂O_Three, MgO, TiO₂, ZrO₂, SiO₂・ Al₂O_ThreeComposite oxide, MgO / Al₂O_ThreeComposite oxide, MgO / SiO₂・ Al₂O_ThreeExamples 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, Al₂O_ThreeA styrene-divinylbenzene copolymer is preferably used.
[0038]
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.
[0039]
The amount of the organosilicon compound used is the atomic ratio of silicon atoms to titanium atoms in the titanium compound, and usually Si / Ti = 1 to 50, preferably 3 to 30, particularly preferably 5 to 25. Moreover, the usage-amount of an ester compound is the molar ratio of the ester compound with respect to the titanium atom of a titanium compound, and usually ester compound / Ti = 0.05-10, Preferably it is 0.1-6, Most preferably, it is 0.2-3. Range. Further, the amount of the organomagnesium compound used is the atomic ratio of the sum of titanium atoms and silicon atoms and magnesium atoms, usually Ti + Si / Mg = 0.1-10, preferably 0.2-5.0, particularly preferably. , 0.5 to 2.0.
[0040]
The solid product obtained by the reduction reaction is usually subjected to solid-liquid separation and washed several times with an inert hydrocarbon solvent such as hexane or heptane. The reduced solid product thus obtained contains trivalent titanium, magnesium and hydrocarbyloxy groups, and is generally amorphous or very weakly crystalline. From the viewpoint of catalyst performance, an amorphous structure is particularly preferable.
[0041]
In the present invention, the reduction solid product is added in the order of a mixture of an ether compound and titanium tetrachloride and then an organic acid halide compound. By using the organic acid halide compound, the amount of the cold xylene soluble part, which is an amorphous polymer having little industrial utility value, is reduced. At the same time, the polymerization activity and the bulk density of the polymer powder are improved, and the productivity is improved.
[0042]
The usage-amount of an ether compound is 0.1-100 mol normally with respect to 1 mol of titanium atoms contained in a reduction | restoration solid product, Preferably it is 0.5-50 mol, Most preferably, it is 1-20 mol. The amount of titanium tetrachloride added is usually 1 to 1000 mol, preferably 3 to 500 mol, particularly preferably 10 to 300 mol, per 1 mol of titanium atoms contained in the reduced solid product. Moreover, the addition amount of titanium tetrachloride with respect to 1 mol of ether compounds is 1-100 mol normally, Preferably it is 1.5-75 mol, Most preferably, it is 2-50 mol.
The amount of the organic acid halide compound used is usually 0.1 to 50 mol, more preferably 0.3 to 20 mol, particularly preferably 0.5 to 10 mol per mol of titanium atom in the reduced solid product. . Moreover, the usage-amount of the organic acid halide compound per mol of magnesium atoms in a solid product is 0.01-1.0 mol normally, Preferably it is 0.03-0.5 mol. When the amount of the organic acid halide compound used is excessively large, particle collapse may occur.
[0043]
The treatment of the reduced solid product with the mixture of the ether compound and titanium tetrachloride and the organic acid halide compound can be carried out by any known method such as a slurry method or a mechanical pulverizing means such as a ball mill. A slurry method in which both are brought into contact in the presence of a diluent is preferred.
[0044]
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.
[0045]
The amount of the diluent used is usually 0.1 ml to 1000 ml, preferably 1 ml to 100 ml, per 1 g of the reduced solid product. Processing temperature is -50-150 degreeC normally, Preferably it is 0-120 degreeC. The treatment time is usually 30 minutes or longer, but preferably 1 to 10 hours. After completion of the normal treatment, the mixture is allowed to stand, and after solid-liquid separation, washing with an inert hydrocarbon solvent is performed several times to obtain an organic acid halide-treated solid.
[0046]
Next, the obtained organic acid halide-treated solid is treated with a mixture of an ether compound and titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound. 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.
[0047]
The slurry concentration is preferably 0.05 to 0.7 g solid / ml solvent, particularly preferably 0.1 to 0.5 g solid / ml solvent. The reaction temperature is usually 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.
[0048]
As a method for supplying the organic acid halide-treated solid, ester compound, ether compound and titanium tetrachloride, a method of adding the ester compound, ether compound and titanium tetrachloride to the organic acid halide-treated solid, conversely ester compound, ether compound and tetra Any method of adding an organic acid halide-treated solid to a solution of titanium chloride may be used. In the method of adding an ester compound, an ether compound and titanium tetrachloride to an organic acid halide-treated solid, a method of adding titanium tetrachloride after adding the ester compound and ether compound, adding the ester compound, ether compound and titanium tetrachloride simultaneously. A method is preferred, and a method of adding a mixture of an ester compound, an ether compound and titanium tetrachloride prepared in advance to an organic acid halide-treated solid is particularly preferred.
[0049]
The treatment with an organic acid halide-treated solid ether compound and titanium tetrachloride, or the treatment with a mixture of an ester compound, an ether compound and titanium tetrachloride may be repeated one or more times. The treatment is preferably repeated at least twice from the viewpoint of catalytic activity and stereoregularity.
[0050]
The usage-amount of an ether compound is 0.1-100 mol normally with respect to 1 mol of titanium atoms contained in organic acid halide processing solid, Preferably it is 0.5-50 mol, Most preferably, it is 1-20 mol. . The amount of titanium tetrachloride added is usually 1 to 1000 mol, preferably 3 to 500 mol, particularly preferably 10 to 300 mol, per 1 mol of titanium atoms contained in the organic acid halide-treated solid. Moreover, the addition amount of titanium tetrachloride with respect to 1 mol of ether compounds is 1-100 mol normally, Preferably it is 1.5-75 mol, Most preferably, it is 2-50 mol.
[0051]
When the ester compound coexists, 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 the titanium atom contained in the organic acid halide-treated solid.
[0052]
The solid catalyst component (A) obtained by the above method is usually subjected to solid-liquid separation, then washed several times with an inert hydrocarbon solvent such as hexane and heptane, and then used for polymerization. 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. After repeated washing, it is preferable to use for polymerization in view of catalytic activity and stereoregularity.
[0053]
In general, there is a constant N in the particle size distribution function of Rosin-Ramler (Rosin, P. and E. Rammler: J. Inst. Fuel, 7, as an index representing the width of the particle size distribution of solid particles. P29 (1933). And Handbook of Chemical Engineering, 3rd revised edition, pages 361-362).
R (Dp) = 100exp {-(Dp / De)^N}
Here, R (Dp) is a residual rate distribution, and the ratio between the total amount and the total amount of a particle group larger than a certain particle size Dp is shown as a residual rate curve with respect to the particle size. De represents the particle diameter at R (Dp) = 36.8%.
The larger the value of N, the narrower the distribution tends to be. The solid catalyst component having a large value has a narrow particle size distribution, and the resulting polymer has a high bulk density and is industrially preferable.
[0054]
The solid catalyst component of the present invention obtained as described above is usually 5 or more as the value of the constant N in the particle size distribution function of the above-mentioned Rosin-Rammler, and the particle size distribution is narrow. The solid catalyst component of the present invention preferably has a value of N of 6.0 or more, more preferably 6.2 or more, and even more preferably 6.4 or more.
[0055]
(H) Organoaluminum compound
The organoaluminum compound (B) 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.
R¹¹ _rAlY_3-r
R¹²R¹³Al-O-AlR¹⁴R¹⁵
(Wherein R¹¹~ R¹⁵Is a hydrocarbon group having 1 to 20 carbon atoms, Y is a halogen, hydrogen or alkoxy group, and r is a number represented by 2 ≦ r ≦ 3. )
Specific examples of the organic aluminum compound include trialkylaluminum such as triethylaluminum, triisobutylaluminum and trihexylaluminum, dialkylaluminum hydride such as diethylaluminum hydride and diisobutylaluminum hydride, dialkylaluminum halide such as diethylaluminum chloride, triethylaluminum and Examples thereof include a mixture of a trialkylaluminum and a dialkylaluminum halide such as a mixture of diethylaluminum chloride, and an alkylalumoxane such as tetraethyldialumoxane and tetrabutyldialumoxane.
[0056]
Of 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.
[0057]
The amount of the organoaluminum compound used can be selected in a wide range such as usually 0.5 to 1000 mol per 1 mol of titanium atom in the solid catalyst, but the range of 1 to 600 mol is particularly preferable.
[0058]
(I) electron donating compound
Examples of the electron donating compound (C) used in the polymerization in the present invention include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides. And oxygen-containing electron donors such as ammonia, nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates. Of these electron donors, inorganic acid esters and ethers are preferably used.
[0059]
Preferably, the inorganic acid esters are represented by the general formula R¹⁶ _nSi (OR¹⁷)_4-n(Wherein 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, tert-butyltrimethoxysilane, isopropyltrimethoxysilane. Methoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, propylmethyldimethoxysilane, diisopropyldimethoxysilane, dibutyldimethoxysilane, diisobutyldimethoxysilane, di- tert-butyldimethoxysilane, butylmethyldimethoxysilane, butylethyldimethoxysilane tert-butylmethyldimethoxysilane, isobutylisopropyldimethoxysilane, tert-butylisopropyldimethoxysilane, hexylmethyldimethoxysilane, hexylethyldimethoxysilane, dodecylmethyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, cyclopentyl Isopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, Cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, Vinylmethyldimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, tert-butyltriethoxysilane, isopropyltriethoxysilane, cyclohexyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxy Silane, dimethyldiethoxysilane Run, diethyldiethoxysilane, dipropyldiethoxysilane, propylmethyldiethoxysilane, diisopropyldiethoxysilane, dibutyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, butylmethyldiethoxysilane, butyl Ethyldiethoxysilane, tert-butylmethyldiethoxysilane, hexylmethyldiethoxysilane, hexylethyldiethoxysilane, dodecylmethyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyl Diethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, vinylmethyldiethoxysilane, ethyltriisopropyl Examples include xyloxysilane, vinyltributoxysilane, phenyltri-tert-butoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, trimethylphenoxysilane, methyltriallyloxysilane, and the like. it can.
[0060]
Further, the ethers are preferably dialkyl ethers, general formula

(Wherein R¹⁸~ R^{twenty one}Is a linear or branched alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group, an aryl group, or an aralkyl group, and R¹⁸Or R¹⁹May be a hydrogen atom. And a diether compound represented by 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.
[0061]
Of these electron donating compounds, the general formula R^{twenty two}R^{twenty three}Si (OR^{twenty four})₂An organosilicon compound represented by the formula is particularly preferably used. Where R^{twenty two}Is a hydrocarbon group having 3 to 20 carbon atoms in which the carbon atom adjacent to Si is secondary or tertiary, specifically, isopropyl group, sec-butyl group, tert-butyl group, tert-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, R^{twenty three}Is a hydrocarbon group having 1 to 20 carbon atoms, specifically, a linear alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, isopropyl group, sec-butyl group, tert- Examples thereof include branched alkyl groups such as butyl group and tert-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. Further, in the formula, R^{twenty four}Is a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms.
[0062]
Specific examples of the organosilicon compound used as such an electron donating compound include diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert -Butyl-n-propyldimethoxysilane, tert-butyl-n-butyldimethoxysilane, tert-amylmethyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amyl-n-propyldimethoxysilane, tert-amyl-n-butyl Dimethoxysilane, isobutylisopropyldimethoxysilane, tert-butylisopropyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyl Dimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexyl Cyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, di Sopropyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, tert-butylmethyldiethoxysilane, tert-butylethyldiethoxysilane, tert-butyl-n-propyldiethoxysilane, tert-butyl -N-butyldiethoxysilane, tert-amylmethyldiethoxysilane, tert-amylethyldiethoxysilane, tert-amyl-n-propyldiethoxysilane, tert-amyl-n-butyldiethoxysilane, dicyclopentyldiethoxy Silane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, 2-norbornamme Examples thereof include tildimethoxysilane.
[0063]
(J) Olefin polymerization method
The α-olefin applicable to the present invention is an α-olefin having 3 or more carbon atoms, preferably an α-olefin having 3 to 10 carbon atoms. Specific examples include linear monoolefins such as propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1 and decene-1, 3-methylbutene-1, 3-methylpentene-1 Branched monoolefins such as 4-methylpentene-1, vinylcyclohexane and the like. One type of these α-olefins may be used, or two or more types may be used in combination. Among these α-olefins, it is preferable to carry out homopolymerization using propylene or butene-1, or to carry out copolymerization using a mixed olefin containing propylene or butene-1 as the main component. It is particularly preferable to perform homopolymerization 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 α-olefin 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.
[0064]
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.
[0065]
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.
[0066]
In the present invention, it is possible to carry out olefin polymerization in the presence of the above-mentioned catalyst, but prepolymerization described below may be carried out before such polymerization (main polymerization).
[0067]
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.
[0068]
The amount of the organoaluminum compound used in the prepolymerization can be selected within a wide range, usually 0.5 to 700 mol, per mol of titanium atom in the solid catalyst component, preferably 0.8 to 500 mol. ˜200 mol is particularly preferred.
[0069]
The amount of olefin to be prepolymerized is usually 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.
[0070]
The slurry concentration during the prepolymerization is preferably 1 to 500 g-solid catalyst component / liter-solvent, and more preferably 3 to 300 g-solid catalyst component / liter-solvent. The prepolymerization temperature is preferably -20 to 100 ° C, particularly preferably 0 to 80 ° C. The partial pressure of olefin in the gas phase during prepolymerization is 0.01 to 20 kg / cm.²In particular, 0.1 to 10 kg / cm²However, this is not the case for olefins that are liquid at the prepolymerization pressure and temperature. Further, the prepolymerization time is not particularly limited, but usually 2 minutes to 15 hours is preferable.
[0071]
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.
[0072]
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 used is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, particularly preferably 0.03 to 100 mol, per 1 mol of titanium atoms contained in the solid catalyst component (A). Yes, with respect to the organoaluminum compound (B), it is usually 0.003 to 5 mol, preferably 0.005 to 3 mol, and particularly preferably 0.01 to 2 mol.
[0073]
There is no particular limitation on the method for supplying the electron donating compound (C) in the prepolymerization, and the electron donating compound (C) may be supplied separately from the organoaluminum compound (B) or may be supplied in contact with the organic aluminum compound (B). Further, the olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization.
[0074]
After pre-polymerization as described above or without pre-polymerization, for α-olefin polymerization comprising the above-mentioned solid catalyst component (A), organoaluminum compound (B) and electron-donating compound (C) The main polymerization of the α-olefin can be carried out in the presence of a catalyst.
[0075]
The amount of the organoaluminum compound used in the main polymerization can be selected in a wide range such as usually from 1 to 1000 mol per 1 mol of the titanium atom in the solid catalyst component (A). .
[0076]
The electron donating compound (C) used in the main polymerization is usually 0.1 to 2000 mol, preferably 0.3 to 1000 mol, per 1 mol of titanium atom contained in the solid catalyst component (A). Particularly preferably, the amount is from 0.5 to 800 mol, and is usually from 0.001 to 5 mol, preferably from 0.005 to 3 mol, particularly preferably from 0.01 to 1 mol, based on the organoaluminum compound.
[0077]
Although this superposition | polymerization can be implemented over -30-300 degreeC normally, 20-180 degreeC is preferable. The polymerization pressure is not particularly limited, but is generally from normal pressure to 100 kg / cm in that it is industrial and economical.², Preferably 2-50 kg / cm²A degree of pressure is employed. 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, bulk polymerization using a liquid olefin as a medium at the polymerization temperature, or gas phase polymerization is possible.
[0078]
During the main polymerization, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer.
[0079]
【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. In the examples, evaluation methods for various physical properties of the polymer are as follows.
[0080]
(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, dried under reduced pressure at 60 ° C., and a polymer soluble in xylene at 20 ° C. is collected and weighed, and the weight percentage with respect to the total polymer is determined.
CXS indicates that the smaller the value, the less the amorphous polymer and the higher the stereoregularity.
[0081]
(2) Intrinsic viscosity (hereinafter abbreviated as [η]): Measured with an Ubbelohde viscometer at 135 ° C. in a tetralin solvent.
[0082]
(3) N in the Rosin-Rammler formula: After measuring the frequency distribution using an ultracentrifugal automatic particle size distribution measuring apparatus CAPA-700 manufactured by Horiba, Ltd., the obtained data is used as the following Rosin-Lambler formula (Rosin, P. and E. Rammler: J. Inst. Fuel, 7, P29 (1933). And Chemical Engineering Handbook, Rev. 3 361-362).
R (Dp) = 100exp {-(Dp / De)^N}
Here, R (Dp) is a residual rate distribution, and the ratio between the total amount and the total amount of a particle group larger than a certain particle size Dp is shown as a residual rate curve with respect to the particle size. De represents the particle diameter at R (Dp) = 36.8%.
The larger the value of N, the narrower the distribution tends to be. The solid catalyst component having a large value has a narrow particle size distribution, and the resulting polymer has a high bulk density and is industrially preferable.
[0083]
Example 1
(A) Synthesis of reduced solid product
A 500 ml flask equipped with a stirrer and a dropping funnel was replaced with nitrogen, 290 ml of hexane, 8.9 ml of tetrabutoxytitanium (8.9 g, 26.1 mmol), 3.1 ml of diisobutyl phthalate (3.3 g, 11 .8 mmol) and 87.4 ml (81.6 g, 392 mmol) of tetraethoxysilane were added to obtain a homogeneous solution. Next, 199 ml of a di-n-butyl ether solution of n-butylmagnesium chloride (Organic Synthetic Chemical Co., Ltd., n-butylmagnesium chloride concentration 2.1 mmol / ml) was added to the dropping funnel while maintaining the temperature in the flask at 6 ° C. And then gradually dropped over 5 hours. After completion of the dropwise addition, the mixture was further stirred at 6 ° C. for 1 hour, and further stirred at room temperature for 1 hour. Thereafter, solid-liquid separation was performed, and washing was repeated three times with 260 ml of toluene, and then an appropriate amount of toluene was added to obtain a slurry concentration of 0.176 g / ml.
A part of the solid product slurry was sampled and subjected to composition analysis. As a result, the solid product contained 1.96% by weight of titanium atoms, 0.12% by weight of phthalates, and 37.2% by weight of ethoxy groups. And 2.8% by weight of butoxy groups.
[0084]
(B) Synthesis of solid catalyst component
After replacing a 100 ml flask equipped with a stirrer, a dropping funnel and a thermometer with nitrogen, 52 ml of the slurry containing the solid product obtained in the above (a) was added, 25.5 ml of the supernatant was taken out, and butyl ether was added in an amount of 0.5 ml. A mixture of 80 ml (6.45 mmol) and 16.0 ml (0.146 mol) of titanium tetrachloride is added, followed by 1.6 ml of phthalic acid chloride (11.1 mmol: 0.20 ml / 1 g solid product). The temperature was raised to 115 ° C. and stirred as such for 3 hours. After completion of the reaction, the solid and liquid were separated at the same temperature, and then washed twice with 40 ml of toluene at the same temperature. Then a mixture of 10.0 ml toluene, 0.45 ml (1.68 mmol) diisobutyl phthalate, 0.80 ml (6.45 mmol) butyl ether and 8.0 ml (0.073 mol) titanium tetrachloride was added and 115 The treatment was performed at 0 ° C. for 1 hour. After completion of the reaction, solid-liquid separation was performed at the same temperature, followed by washing with 40 ml of toluene three times at the same temperature, followed by washing with 40 ml of hexane three times and further drying under reduced pressure to obtain 7.36 g of a solid catalyst component.
The solid catalyst component contained 2.18 wt% titanium atom, 11.37 wt% phthalate ester, 0.3 wt% ethoxy group, and 0.1 wt% butoxy group. Further, when the solid catalyst component was observed with a stereomicroscope, it had good particle properties without fine powder.
[0085]
(C) Polymerization of propylene
A 3 liter stirred stainless steel autoclave was purged with argon, charged with 2.6 mmol of triethylaluminum, 0.26 mmol of cyclohexylethyldimethoxysilane, and 5.7 mg of the solid catalyst component synthesized in (b), 0.33 kg / cm²Hydrogen corresponding to the partial pressure of was added. Next, 780 g of liquefied propylene was charged, the temperature of the autoclave was raised to 80 ° C., and polymerization was carried out at 80 ° C. for 1 hour. After the polymerization was completed, unreacted monomers were purged. The produced polymer was dried under reduced pressure at 60 ° C. for 2 hours to obtain 231 g of polypropylene powder.
Therefore, the yield of polypropylene per 1 g of the solid catalyst component (hereinafter abbreviated as PP / Cat) was PP / Cat = 40,600 (g / g). Further, the proportion of components soluble in 20 ° C. xylene in the total polymer yield is CXS = 0.49 (wt%), the intrinsic viscosity of the polymer is [η] = 1.96, and the bulk density = 0.385 g / ml. The polymerization conditions and polymerization results are shown in Table 1.
[0086]
Comparative Example 1
(A) Synthesis of reduced solid product
The amounts of reagents used were 7.5 ml (7.5 g, 22 mmol) tetrabutoxytitanium, 2.5 ml (2.6 g, 9.3 mmol) diisobutyl phthalate and 74.8 ml (70.3 g, 338 mmol) tetraethoxysilane. The reaction was conducted in the same manner as in (a) of Example 1 except that the organic magnesium compound solution was 173 ml. The solid product obtained by solid-liquid separation was washed three times with 300 ml of hexane and three times with 300 ml of toluene, and then 270 ml of toluene was added.
A part of the solid product slurry was sampled and subjected to composition analysis. As a result, the solid product contained 1.80% by weight of titanium atoms, 0.1% by weight of phthalates, and 35.0% by weight of ethoxy groups. The butoxy group contained 3.2% by weight.
[0087]
(B) Synthesis of solid catalyst component
After replacing a 200 ml flask equipped with a stirrer, a dropping funnel and a thermometer with argon, 84 ml of the slurry containing the solid product obtained in the above (a) was added, and 12.1 ml of the supernatant was withdrawn. 7.8 ml (29 mmol) of diisobutyl acid was added and reacted at 95 ° C. for 30 minutes. After the reaction, it was separated into solid and liquid and washed twice with 59 ml of toluene.
Then a mixture of 15.3 ml toluene, 0.66 ml (2.5 mmol) diisobutyl phthalate, 1.2 ml (6.9 mmol) butyl ether, and 23.4 ml (0.213 mol) titanium tetrachloride was added to the flask. The treatment was performed at 105 ° C. for 3 hours. After completion of the treatment, solid-liquid separation was performed at the same temperature, followed by washing twice with 59 ml of toluene at the same temperature. Next, a mixture of 12.0 ml of toluene, 1.2 ml (6.9 mmol) of butyl ether, and 11.7 ml (0.106 mol) of titanium tetrachloride was added, and a treatment was performed at 105 ° C. for 1 hour. After the treatment, solid-liquid separation was performed at the same temperature. After washing 3 times with 59 ml of toluene at the same temperature, it was washed 3 times with 59 ml of hexane and further dried under reduced pressure to obtain 8.1 g of a solid catalyst component.
The solid catalyst component contained 1.5% by weight of titanium atoms, 8.9% by weight of phthalates, 0.4% by weight of ethoxy groups, and 0.1% by weight of butoxy groups.
[0088]
(C) Polymerization of propylene
In the polymerization of propylene of Example 1 (c), propylene was polymerized in the same manner except that 4.0 mg of the solid catalyst component obtained in the above (c) was used.
As a result of the polymerization, PP / Cat = 30,000 (g / g), the polymerization activity was low, and CXS = 0.74 (wt%), and the stereoregularity was low. The bulk density was 0.360 g / ml and [η] was 2.01. The polymerization conditions and polymerization results are shown in Table 1.
[0089]
Example 2
(C) Polymerization of propylene
Similar to the polymerization of propylene of Example 1 (c) except that the solid catalyst component prepared in Example 1 (b) was used and tert-butyl-n-propyldimethoxysilane was used instead of cyclohexylethyldimethoxysilane. Polymerization was performed.
The polymerization results were PP / Cat = 55,700 (g / g), CXS = 0.33 (wt%), bulk density = 0.405 g / ml, and [η] = 2.69. The polymerization conditions and polymerization results are shown in Table 1.
[0090]
Example 3
(B) Synthesis of solid catalyst component
46 ml of the slurry containing the solid product prepared in (a) of Example 1 was added, 22.5 ml of the supernatant was withdrawn, 0.71 ml (5.73 mmol) of butyl ether, and 11.4 ml of titanium tetrachloride (0 .104 mol) was added, followed by addition of 1.42 ml of phthalic acid chloride (9.86 mmol: 0.20 ml / 1 g solid product), and the mixture was heated to 115 ° C. and stirred for 3 hours. After completion of the treatment, solid-liquid separation was performed at the same temperature, followed by washing twice with 36 ml of toluene at the same temperature. A mixture of 9.0 ml toluene, 0.40 ml (1.49 mmol) diisobutyl phthalate, 0.71 ml (5.73 mmol) butyl ether, and 5.7 ml (0.052 mol) titanium tetrachloride was then added. The reaction was carried out at 1 ° C. for 1 hour. After completion of the reaction, solid-liquid separation was performed at the same temperature, followed by washing with 36 ml of toluene three times at the same temperature, followed by washing three times with 36 ml of hexane and further drying under reduced pressure to obtain 6.53 g of a solid catalyst component.
The solid catalyst component contained 2.34% by weight of titanium atoms, 10.57% by weight of phthalates, 0.4% by weight of ethoxy groups, and 0.1% by weight of butoxy groups. Further, when the solid catalyst component was observed with a stereomicroscope, it had good particle properties without fine powder.
[0091]
(C) Polymerization of propylene
Polymerization of propylene was carried out in the same manner as the polymerization of propylene in Example 1 (c) except that the solid catalyst component obtained in (b) above was used.
The polymerization results were PP / Cat = 46,700 (g / g), CXS = 0.46 (wt%), bulk density = 0.396 g / ml, and [η] = 1.95. The polymerization conditions and polymerization results are shown in Table 1.
[0092]
Example 4
(B) Synthesis of solid catalyst component
The solid catalyst component was synthesized in the same manner as in Example 1 (b) except that 0.22 ml of diisobutyl phthalate was used.
The solid catalyst component contained 2.22% by weight of titanium atoms, 10.20% by weight of phthalates, 0.37% by weight of ethoxy groups, and 0.14% by weight of butoxy groups. Further, when the solid catalyst component was observed with a stereomicroscope, it had good particle properties without fine powder.
[0093]
(C) Polymerization of propylene
Polymerization of propylene was carried out in the same manner as the polymerization of propylene in Example 1 (c) except that the solid catalyst component obtained in (b) above was used.
The polymerization results were PP / Cat = 49,100 (g / g), CXS = 0.50 (wt%), bulk density = 0.399 g / ml, and [η] = 1.90. The polymerization conditions and polymerization results are shown in Table 1.
[0094]
Example 5
(C) Polymerization of propylene
Polymerization was carried out in the same manner as the polymerization of propylene in Example 4 (c) except that tert-butyl-n-propyldimethoxysilane was used in place of cyclohexylethyldimethoxysilane.
The polymerization results were PP / Cat = 57,500 (g / g), CXS = 0.47 (wt%), bulk density = 0.406 g / ml, and [η] = 2.67. The polymerization conditions and polymerization results are shown in Table 1.
[0095]
Example 6
(A) Synthesis of reduced solid product
A solid product was synthesized in the same manner as in Example 1 (a). The slurry concentration of the obtained solid product was 0.184 g / ml.
A part of the solid product slurry was sampled and analyzed for composition. As a result, the solid product contained 1.94% by weight of titanium atoms, 0.18% by weight of phthalate ester, and 34.6% by weight of ethoxy groups. The butoxy group contained 3.2% by weight.
[0096]
(B) Synthesis of solid catalyst component
50 ml of the slurry containing the solid product prepared in (a) above was added, 23.5 ml of the supernatant liquid was taken out, 0.80 ml (6.45 mmol) of butyl ether and 16.0 ml (0.146 mol) of titanium tetrachloride. Then, 1.60 ml (11.1 mmol: 0.20 ml / 1 g solid product) of phthalic acid chloride was added, and the temperature was raised to 115 ° C. and stirred as it was for 3 hours. After completion of the treatment, solid-liquid separation was performed at the same temperature, followed by washing twice with 40 ml of toluene at the same temperature. Then, a mixture of 10 ml of toluene, 0.45 ml (1.68 mmol) of diisobutyl phthalate, 0.80 ml (6.45 mmol) of butyl ether, and 8.0 ml (0.073 mol) of titanium tetrachloride was added at 115 ° C. The treatment was performed for 1 hour. After completion of the treatment, solid-liquid separation was performed at the same temperature, followed by washing twice with 40 ml of toluene at the same temperature. Then, a mixture of 10 ml of toluene, 0.45 ml (1.68 mmol) of diisobutyl phthalate, 0.80 ml (6.45 mmol) of butyl ether, and 8.0 ml (0.073 mol) of titanium tetrachloride was added at 115 ° C. The treatment was performed for 1 hour. After completion of the treatment, solid-liquid separation was performed at the same temperature, followed by washing with 40 ml of toluene three times at the same temperature, followed by washing with 40 ml of hexane three times and further drying under reduced pressure to obtain 7.07 g of a solid catalyst component.
The solid catalyst component contained 2.13 wt% titanium atom, 12.37 wt% phthalate ester, 0.1 wt% ethoxy group, and 0.1 wt% butoxy group. Further, when the solid catalyst component was observed with a stereomicroscope, it had good particle properties without fine powder.
[0097]
(C) Polymerization of propylene
Polymerization of propylene was carried out in the same manner as the polymerization of propylene in Example 1 (c) except that the solid catalyst component obtained in (b) above was used.
The polymerization results were PP / Cat = 41,300 (g / g), CXS = 0.41 (wt%), bulk density = 0.400 g / ml, and [η] = 1.93. The polymerization conditions and polymerization results are shown in Table 1.
[0098]
Example 7
(B) Synthesis of solid catalyst component
50 ml of the slurry containing the solid product prepared in Example 6 (a) was added, 23.5 ml of the supernatant was taken out, 0.80 ml (6.45 mmol) of butyl ether and 16.0 ml (0.146) of titanium tetrachloride. Mol) was added, and then 1.60 ml (11.1 mmol: 0.20 ml / 1 g solid product) of phthalic acid chloride was added, and the mixture was heated to 115 ° C. and stirred for 3 hours. After completion of the treatment, solid-liquid separation was performed at the same temperature, followed by washing twice with 40 ml of toluene at the same temperature. Then, a mixture of 10 ml of toluene, 0.45 ml (1.68 mmol) of diisobutyl phthalate, 0.80 ml (6.45 mmol) of butyl ether, and 8.0 ml (0.073 mol) of titanium tetrachloride was added at 115 ° C. The treatment was performed for 1 hour. After completion of the treatment, solid-liquid separation was performed at the same temperature, followed by washing twice with 40 ml of toluene at the same temperature. Next, a mixture of 10 ml of toluene, 0.80 ml (6.45 mmol) of butyl ether, and 6.4 ml (0.058 mol) of titanium tetrachloride was added and treated at 115 ° C. for 1 hour. After completion of the treatment, solid-liquid separation was performed at the same temperature, followed by washing twice with 40 ml of toluene at the same temperature. Next, a mixture of 10 ml of toluene, 0.80 ml (6.45 mmol) of butyl ether, and 6.4 ml (0.058 mol) of titanium tetrachloride was added and treated at 115 ° C. for 1 hour. After completion of the treatment, solid-liquid separation was carried out at the same temperature, followed by washing with 40 ml of toluene three times at the same temperature, followed by washing with 40 ml of hexane three times and further drying under reduced pressure to obtain 6.58 g of a solid catalyst component. The solid catalyst component contained 1.78 wt% titanium atom, 8.66 wt% phthalate ester, 0.1 wt% ethoxy group, and 0.2 wt% butoxy group. Further, when the solid catalyst component was observed with a stereomicroscope, it had good particle properties without fine powder.
[0099]
(C) Polymerization of propylene
Polymerization of propylene was carried out in the same manner as the polymerization of propylene in Example 1 (c) except that the solid catalyst component obtained in (b) above was used.
The polymerization results were PP / Cat = 51,200 (g / g), CXS = 0.44 (wt%), bulk density = 0.407 g / ml, and [η] = 1.95. The polymerization conditions and polymerization results are shown in Table 1.
[0100]
Comparative Example 2
(B) Synthesis of solid catalyst component
After replacing a 100 ml flask equipped with a stirrer, a dropping funnel and a thermometer with argon, 50 ml of the slurry containing the solid product prepared in Example 6 (a) was added, and 23.5 ml of the supernatant was withdrawn. Then, 1.6 ml (11.1 mmol) of phthalic acid chloride was added, and the reaction was performed at 110 ° C. for 30 minutes. After the reaction, it was separated into solid and liquid and washed twice with 40 ml of toluene.
A mixture of 10 ml toluene, 0.45 ml (1.7 mmol) diisobutyl phthalate, 0.8 ml (6.5 mmol) butyl ether, and 16.0 ml (0.146 mol) titanium tetrachloride was then added to the flask. The reaction was carried out at 3 ° C. for 3 hours. After completion of the reaction, the solid and liquid were separated at the same temperature, and then washed twice with 40 ml of toluene at the same temperature. Subsequently, a mixture of 10 ml of toluene, 0.8 ml (6.5 mmol) of butyl ether, and 8.0 ml (0.073 mol) of titanium tetrachloride was added, and the reaction was performed at 115 ° C. for 1 hour. After completion of the reaction, solid-liquid separation was performed at the same temperature, followed by washing with 40 ml of toluene three times at the same temperature, followed by washing with 40 ml of hexane three times and further drying under reduced pressure to obtain 5.8 g of a solid catalyst component.
The solid catalyst component contained 1.28 wt% titanium atom, 5.75 wt% phthalate ester, 1.2 wt% ethoxy group, and 0.2 wt% butoxy group.
[0101]
(D) Polymerization of propylene
Polymerization of propylene was carried out in the same manner as the polymerization of propylene of Example 1 (c) except that 3.9 mg of the solid catalyst component obtained in (c) above was used.
As a result of polymerization, PP / Cat = 7,700 (g / g), the polymerization activity was low, and CXS = 1.56 (wt%), and the stereoregularity was low. The bulk density was 0.420 g / ml and [η] = 1.61. The polymerization conditions and polymerization results are shown in Table 1.
[0102]
Comparative Example 3
(B) Synthesis of solid catalyst component
50 ml of the slurry containing the solid product prepared in Example 6 (a) was added, 23.5 ml of toluene was withdrawn, and 1.60 ml (11.1 mmol: 0.20 ml / 1 g solid product of phthalic acid chloride was formed first. Then, a mixed liquid of 0.80 ml (6.45 mmol) of butyl ether and 16.0 ml (0.146 mol) of titanium tetrachloride was added, the temperature was raised to 115 ° C., and the mixture was stirred as it was for 3 hours. After completion of the reaction, the solid and liquid were separated at the same temperature, and then washed twice with 40 ml of toluene at the same temperature. Then, a mixture of 10 ml of toluene, 0.45 ml (1.68 mmol) of diisobutyl phthalate, 0.80 ml (6.45 mmol) of butyl ether, and 8.0 ml (0.073 mol) of titanium tetrachloride was added at 115 ° C. The treatment was performed for 1 hour. After completion of the treatment, solid-liquid separation was performed at the same temperature, followed by washing with 40 ml of toluene three times at the same temperature, followed by washing with 40 ml of hexane three times and further drying under reduced pressure to obtain 7.27 g of a solid catalyst component.
The solid catalyst component contained 2.29 wt% titanium atom, 11.03 wt% phthalate ester, 0.2 wt% ethoxy group, and 0.1 wt% butoxy group.
[0103]
(C) Polymerization of propylene
Polymerization of propylene was carried out in the same manner as the polymerization of propylene in Example 1 (c) except that the solid catalyst component obtained in (b) above was used.
The polymerization result was as low as PP / Cat = 25,800 (g / g). CXS = 0.57 (wt%), bulk density = 0.365 g / ml, and [η] = 1.95. The polymerization conditions and polymerization results are shown in Table 1.
[0104]
[Table 1]

[0105]
【The invention's effect】
According to the present invention, an α-olefin polymerization catalyst having a sufficiently high catalyst activity and stereoregularity, which has a good particle size distribution and does not require removal of catalyst residues and amorphous polymers, and a high quality, high stericity. A method for producing an ordered α-olefin polymer is provided.
[Brief description of the drawings]
FIG. 1 is a flowchart for helping understanding of the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

Claims (3)

  In the presence of an organosilicon compound having an Si—O bond and 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. The solid compound obtained by reducing the titanium compound represented by) with an organomagnesium compound is treated by adding a mixture of an ether compound and titanium tetrachloride and an organic acid halide compound in this order, and then treating the treated solid with an ether compound. And a trivalent titanium compound-containing solid catalyst component obtained by treatment with a mixture of titanium tetrachloride and a mixture of an ether compound, titanium tetrachloride and an ester compound. (A) In the presence of an organosilicon compound having an Si—O bond and an ester compound, the general formula Ti (OR ¹ ) _a X _4-a (R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, and X is a halogen atom. , A represents a number of 0 <a ≦ 4.) A solid product obtained by reducing a titanium compound represented by an organic magnesium compound, a mixture of an ether compound and titanium tetrachloride, and an organic acid halide compound in this order. A trivalent titanium compound-containing solid catalyst component obtained by treating the treated solid with a mixture of an ether compound and titanium tetrachloride or a mixture of an ether compound, titanium tetrachloride and an ester compound,
An α-olefin polymerization catalyst comprising (B) an organoaluminum compound and (C) an electron donating compound. A method for producing an α-olefin polymer, comprising homopolymerizing an α-olefin or copolymerizing an α-olefin and ethylene or another α-olefin using the α-olefin polymerization catalyst according to claim 2. .

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