JP4001477B2 - Ziegler-Natta catalyst for adjusting MWD of polyolefin, production method, method of use, and polyolefin produced using the same - Google Patents

Description

【００７９】
［式中、Ｒ１およびＲ４は、共に、ケイ素に結合している一級、二級または三級炭素原子を含むアルキルもしくはシクロアルキル基であり、ここで、Ｒ１およびＲ４は同一或は異なっていてもよく、Ｒ２およびＲ３は、アルキルまたはアリール基である］
で表されるシラン化合物から選択する。Ｒ１はメチル、イソプロピル、シクロペンチル、シクロヘキシルまたはｔ−ブチルであってもよく、Ｒ２およびＲ３は、メチル、エチル、プロピルまたはブチル基であってもよく、必ずしも同一でなくてもよく、そしてＲ４もまたメチル、イソプロピル、シクロペンチル、シクロヘキシルまたはｔ−ブチルであってもよい。具体的な外部供与体はシクロヘキシルメチルジメトキシシラン（ＣＭＤＳ）、ジイソプロピルジメトキシシラン（ＤＩＤＳ）、シクロヘキシルイソプロピルジメトキシシラン（ＣＩＤＳ）、ジシクロペンチルジメトキシシラン（ＣＰＤＳ）またはジ−ｔ−ブチルジメトキシシラン（ＤＴＤＳ）である。
【００８０】
上述した触媒を用いて製造したポリエチレンは、少なくとも４．０、好適には少なくとも５．０、より好適には少なくとも６．０、更により好適には少なくとも７．０のＭＷＤ（ＭＷ／ＭＤ）を示すであろう。
【００８１】
【実施例】
本発明を一般的に記述してきたが、以下に示す実施例は単に本発明の特定態様を示す目的で与えるものである。本実施例は説明として与えるものであり、決して本明細書も請求の範囲も限定することを意図するものでないと理解する。
触媒調製
この実施例では制御形態ポリエチレン用触媒（ｃｏｎｔｒｏｌｌｅｄ−ｍｏｒｐｈｏｌｏｇｙ ｐｏｌｙｅｔｈｙｌｅｎｅ ｃａｔａｌｙｓｔ）を説明し、この触媒を用いると、この触媒を用いて得られる重合体の固有分子量分布（ＭＷＤ）を微調整する（ｆｉｎｅ ｔｕｎｉｎｇ）ことができる。このようにＭＷＤを調節することにより、単一の触媒系を用いて多様な品質の重合体を得ることができる、即ち射出成形用重合体（狭いＭＷＤ）からインフレーシヨンフィルム用重合体（幅広いＭＷＤ）の範囲の用途で用いられる多様な品質の重合体を得ることができる。
【００８２】
触媒の調製を下記の如く行った：
工程１
ＢｕＥｔＭｇ／ＤＩＡＥ／ＴＥＡｌ（１：０．６：０．０３）＋２−エチルヘキサノール（２．０９）によって可溶中間体Ａを生成させる。
工程２
中間体＋１．０ ＣｌＴｉ（ＯＰｒ）₃によって可溶中間体Ｂを生成させる。
工程３
中間体Ｂ＋Ｔｉ（ＯＢｕ）₄／ＴｉＣｌ₄（２．０：１．０）によって固体状予備触媒を生成させる。
工程４
予備触媒＋ＴｉＣｌ₄（０．２５）＋ＴＥＡｌによって最終触媒を生成させる。
工程５
次に、前記最終触媒を９０℃で以下の表１に示す如き時間加熱処理する。
重合
エチレンの重合で用いた反応槽（Ｅｎｇｉｎｅｅｒオートクレーブ）は容量が４リットルであり、これには、２つの対向ピッチ混合用プロペラ（ｐｉｔｃｈ ｍｉｘｉｎｇ ｐｒｏｐｅｌｌｅｒｓ）が付いている混合用邪魔板が４枚取り付けられている。エチレンと水素をＴｅｌｅｄｙｎｅ−Ｈａｓｔｉｎｇｓ Ｒａｙｄｉｓｔ質量流量制御装置を経由して反応槽に導入し、この間ドーム充填背圧調節装置（ｄｏｍｅ ｌｏａｄｅｄ ｂａｃｋ−ｐｒｅｓｓｕｒｅ ｒｅｇｕｌａｔｏｒ）で内部の反応圧力を一定に保持する。Ｂａｒｂｅｒ−Ｃｏｌｅｍａｎ ＣｏｎｔｒｏｌｌｅｒにつなげたＫａｍｍｅｒ Ｖａｌｖｅを用いて反応の温度を蒸気および冷水（反応槽のジャケット）で維持する。ヘキサンを希釈剤として用いた。
実験変数：
温度 ８０℃
反応時間 ６０分
圧力 １２５ｐｓｉ
触媒 スラリーを０．２ｃｃ（触媒を約１０ｍｇ）
共触媒 ＴＥＡｌを０．２５ミリモル／Ｌ
流量 Ｈ₂／Ｃ₂を０．２５
【００８３】
【表１】

【００８４】
触媒溶液のサンプリングを２、４、６および２４時間の時に行った。この段階における熱処理によって、表１および図１（ＴＥＡｌが共触媒）のＳＲ５およびＧＰＣデータが示す如く、触媒の固有ＭＷＤが著しく幅広くなる。ここでは、最初の６時間の加熱によりＭＷＤが着実に高くなって行くことが分かる。その時点で幅広くなる度合が横ばいになる（ｌｅｖｅｌｓ ｏｕｔ）。このようなデータは、更に、可能性として本触媒の分子量分布を重合体用途を基にして所望値に微調整することができることを示している。最後に、本触媒に熱処理を行っても、それが示す高い活性も優れた綿毛形態も全く失われないことが分かる。
【００８５】
本発明の説明的具体例を詳細に記述してきたが、本発明の精神および範囲から逸脱しない他のいろいろな修飾形が本分野の技術者に明らかになりかつ容易に成され得ることは理解されるであろう。従って、本明細書に添付する請求の範囲の範囲を本明細書に挙げる実施例および説明に限定することを意図するものでなく、むしろ、本請求の範囲は本発明に帰する特許が与えられ得る新規性を持つ特徴の全部を包含するとして解釈されるべきであり、そのような特徴には、本発明に関係する当業者がそれの均当物であるとして取り扱うであろう特徴の全部が含まれる。
【００８６】
本発明の特徴および態様は以下のとおりである。
【００８７】
１．
ａ）一般式Ｍｇ（ＯＲ”）₂［式中、Ｒ”は、炭素原子数が１から２０のヒドロカルビルもしくは置換ヒドロカルビルである］で表される可溶マグネシウムジアルコキサイド化合物を１個のハロゲンを１個のアルコキサイドと交換し得るハロゲン化剤に接触させて反応生成物Ａを生成させ、
ｂ）反応生成物Ａを１番目のハロゲン化／チタン化剤に接触させて反応生成物Ｂを生成させ、
ｃ）反応生成物Ｂをより強力な２番目のハロゲン化／チタン化剤に接触させて反応生成物Ｃを生成させ、
ｄ）反応生成物Ｃを予備活性化剤である有機アルミニウムに接触させて予備活性化された触媒を生成させ、そして
ｅ）前記予備活性化された触媒を約９０℃から約１５０℃の範囲の温度に約３０分から約２４時間の範囲の時間加熱する、
ことを含んで成る方法で製造したポリオレフィン用触媒。
【００８８】
２． 前記可溶マグネシウムジアルコキサイド化合物が一般式ＭｇＲＲ’［式中、ＲおよびＲ’は、同一もしくは異なっていてもよく、炭素原子数が１−１０のアルキル基である］で表されるアルキルマグネシウム化合物と一般式Ｒ”ＯＨ［式中、Ｒ”は、炭素原子数が４−２０のアルキル基である］で表される線状もしくは分枝アルコールを含んで成る反応の反応生成物である第１項記載の触媒。
【００８９】
３． 前記可溶マグネシウム化合物がマグネシウムジ（２−エチルヘキソキサイド）である第２項記載の触媒。
【００９０】
４． 前記アルキルマグネシウム化合物がジエチルマグネシウム、ジプロピルマグネシウム、ジブチルマグネシウムまたはブチルエチルマグネシウムである第２項記載の触媒。
【００９１】
５． 前記アルコールがエタノール、プロパノール、イソプロパノール、ブタノール、イソブタノールまたは２−エチルヘキサノールである第２項記載の触媒。
【００９２】
６． 前記反応が更にアルキルアルミニウムも含んで成る第２項記載の触媒。
【００９３】
７． 前記アルキルアルミニウムがトリエチルアルミニウムである第６項記載の触媒。
【００９４】
８． 前記アルキルアルミニウムとマグネシウムの比率が０．００１：１から１：１である第７項記載の触媒。
【００９５】
９． 前記触媒が重合製造工程にそぐう綿毛形態を有しかつ均一な粒子サイズ分布を示すことに加えて約１２５ミクロン未満の粒子のレベルが低い第１項記載の触媒。
【００９６】
１０． 前記反応が更に電子供与体も含んで成る第２項記載の触媒。
【００９７】
１１． 前記電子供与体とマグネシウムの比率が約０：１から約１０：１の範囲である第１０項記載の触媒。
【００９８】
１２． 前記電子供与体がエーテルである第１１項記載の触媒。
【００９９】
１３． 前記ハロゲン化剤が一般式ＣｌＡＲ”’_x［式中、Ａは、非還元性で親酸素性の化合物であり、Ｒ”’_xは、炭素原子数が約２から６のヒドロカルビル部分であり、そしてｘは、Ａの原子価から１を引いた値である］で表される第１項記載の触媒。
【０１００】
１４． 穏やかな前記１番目の塩素化／チタン化剤が２種類の四置換チタン化合物のブレンド物であり、ここで、４つの置換基が全部同一でありそしてこれらの置換基がハライドまたは炭素原子数が２から１０のアルコキサイドもしくはフェノキサイドである第１項記載の触媒。
【０１０１】
１５． 穏やかな前記１番目の塩素化／チタン化剤がハロゲン化チタンと有機チタネートのブレンド物である第１４項記載の触媒。
【０１０２】
１６． 穏やかな前記１番目の塩素化／チタン化剤がＴｉＣｌ₄／Ｔｉ（ＯＢｕ）₄が０．５：１から６：１の範囲のＴｉＣｌ₄とＴｉ（ＯＢｕ）₄のブレンド物である第１５項記載の触媒。
【０１０３】
１７． 工程ｂ）が更に一般式ＲＳｉ（ＯＲ’）₃［式中、ＲおよびＲ’は、同一もしくは異なっていてもよく、炭素原子数が１−５のアルキルである］で表される電子供与体も含んで成る第１項記載の触媒。
【０１０４】
１８． 前記電子供与体がメチルシリルトリエトキサイドである第１７項記載の触媒。
【０１０５】
１９． より強力な前記２番目の塩素化／チタン化剤がハロゲン化チタンである第１項記載の触媒。
【０１０６】
２０． より強力な前記２番目の塩素化／チタン化剤が四塩化チタンでありそしてチタンとマグネシウムの範囲が０：１から２：１である第１９項記載の触媒。
【０１０７】
２１． 前記予備活性化剤である有機アルミニウムが式ＡｌＲ＾₃［式中、Ｒ＾は、同一もしくは異なり、炭素原子数が１−８のアルキルまたはハライドであり、そして少なくとも１つのＲ＾はアルキルである］で表されるアルキルアルミニウムである第１項記載の触媒。
【０１０８】
２２． 前記予備活性化剤である有機アルミニウムがトリアルキルアルミニウムである第２１項記載の触媒。
【０１０９】
２３． アルミニウムとチタンの比率が０．１：１から２：１の範囲である第２２項記載の触媒。
【０１１０】
２４．
ａ）ｉ）一般式Ｍｇ（ＯＲ”）₂［式中、Ｒ”は、炭素原子数が１から２０のヒドロカルビルもしくは置換ヒドロカルビルである］で表される可溶マグネシウムジアルコキサイド化合物を１個のハロゲンを１個のアルコキサイドと交換し得るハロゲン化剤に接触させて反応生成物Ａを生成させ、
ｉｉ）反応生成物Ａを１番目のハロゲン化／チタン化剤に接触させて反応生成物Ｂを生成させ、
ｉｉｉ）反応生成物Ｂをより強力な２番目のハロゲン化／チタン化剤に接触させて反応生成物Ｃを生成させ、
ｉｖ）反応生成物Ｃを予備活性化剤である有機アルミニウムに接触させて予備活性化された触媒を生成させ、そして
ｖ）前記予備活性化された触媒を約９０℃から約１５０℃の範囲の温度に約３０分から約２４時間の範囲の時間加熱する、
ことにより製造した触媒の存在下で１種以上のα−オレフィン単量体を共に重合条件下で接触させる、
ことを含んで成る方法により製造された重合体。
【０１１１】
２５． 前記単量体がエチレン単量体でありそして前記重合体がポリエチレンである第２４項記載の重合体。
【０１１２】
２６． 前記ポリエチレンが約４．０を超える分子量分布を示す第２５項記載の重合体。
【０１１３】
２７． 前記重合が塊状、スラリーまたは気相重合である第２４項記載の重合体。
【０１１４】
２８． 前記可溶マグネシウムジアルコキサイド化合物が一般式ＭｇＲＲ’［式中、ＲおよびＲ’は、同一もしくは異なっていてもよく、炭素原子数が１−１０のアルキル基である］で表されるアルキルマグネシウム化合物と一般式Ｒ”ＯＨ［式中、Ｒ”は、炭素原子数が４−２０のアルキル基である］で表される線状もしくは分枝アルコールを含んで成る反応の反応生成物である第２４項記載の重合体。
【０１１５】
２９． 前記可溶マグネシウム化合物がマグネシウムジ（２−エチルヘキソキサイド）であり、前記アルキルマグネシウム化合物がジエチルマグネシウム、ジプロピルマグネシウム、ジブチルマグネシウムおよびブチルエチルマグネシウムから成る群から選択されそして前記アルコールがエタノール、プロパノール、イソプロパノール、ブタノール、イソブタノールおよび２−エチルヘキサノールから成る群から選択される第２４項記載の重合体。
【０１１６】
３０． 前記反応が更にアルキルアルミニウムも含んで成りそして前記アルキルアルミニウムとマグネシウムの比率が０．００１：１から１：１である第２５項記載の重合体。
【０１１７】
３１． 工程ｉ）−ｖ）のいずれか１工程が更に電子供与体も含んで成りそして前記電子供与体とマグネシウムの比率が約０：１から約１０：１の範囲である第２５項記載の重合体。
【０１１８】
３２． 前記電子供与体がエーテルである第３１項記載の重合体。
【０１１９】
３３． 前記ハロゲン化剤が一般式ＣｌＡＲ”’_x［式中、Ａは、非還元性で親酸素性の化合物であり、Ｒ”’_xは、炭素原子数が約２から６のヒドロカルビル部分であり、そしてｘは、Ａの原子価から１を引いた値である］で表される第２４項記載の重合体。
【０１２０】
３４． 穏やかな前記１番目の塩素化／チタン化剤がＴｉＣｌ₄／Ｔｉ（ＯＢｕ）₄が０．５：１から６：１の範囲のＴｉＣｌ₄とＴｉ（ＯＢｕ）₄のブレンド物である第２４項記載の重合体。
【０１２１】
３５． より強力な前記２番目の塩素化／チタン化剤が四塩化チタンでありそしてチタンとマグネシウムの範囲が０：１から２：１である第２４項記載の重合体。
【０１２２】
３６． 前記予備活性化剤である有機アルミニウムが式ＡｌＲ＾₃［式中、Ｒ＾は、同一もしくは異なり、炭素原子数が１−８のアルキルまたはハライドであり、そして少なくとも１つのＲ＾はアルキルである］で表されるアルキルアルミニウムでありそしてＡｌとチタンの比率が０．１：１から２：１の範囲である第２４項記載の重合体。
【０１２３】
３７．
ａ）一般式Ｍｇ（ＯＲ”）₂［式中、Ｒ”は、炭素原子数が１から２０のヒドロカルビルもしくは置換ヒドロカルビルである］で表される可溶マグネシウムジアルコキサイド化合物を１個のハロゲンを１個のアルコキサイドと交換し得るハロゲン化剤に接触させて反応生成物Ａを生成させ、
ｂ）反応生成物Ａを１番目のハロゲン化／チタン化剤に接触させて反応生成物Ｂを生成させ、
ｃ）反応生成物Ｂをより強力な２番目のハロゲン化／チタン化剤に接触させて反応生成物Ｃを生成させ、
ｄ）反応生成物Ｃを予備活性化剤である有機アルミニウムに接触させて予備活性化された触媒を生成させ、そして
ｅ）前記予備活性化された触媒を約９０℃から約１５０℃の範囲の温度に約３０分から約２４時間の範囲の時間加熱する、
ことを含んで成る触媒の製造方法。
【０１２４】
３８． 前記可溶マグネシウムジアルコキサイド化合物が一般式ＭｇＲＲ’［式中、ＲおよびＲ’は、同一もしくは異なっていてもよく、炭素原子数が１−１０のアルキル基である］で表されるアルキルマグネシウム化合物と一般式Ｒ”ＯＨ［式中、Ｒ”は、炭素原子数が４−２０のアルキル基である］で表される線状もしくは分枝アルコールを含んで成る反応の反応生成物である第３７項記載の方法。
【０１２５】
３９． 前記可溶マグネシウム化合物がマグネシウムジ（２−エチルヘキソキサイド）である第３７項記載の方法。
【０１２６】
４０． 前記アルキルマグネシウム化合物がジエチルマグネシウム、ジプロピルマグネシウム、ジブチルマグネシウムまたはブチルエチルマグネシウムである第３８項記載の方法。
【０１２７】
４１． 前記アルコールがエタノール、プロパノール、イソプロパノール、ブタノール、イソブタノールまたは２−エチルヘキサノールである第３８項記載の方法。
【０１２８】
４２． 前記反応が更にアルキルアルミニウムも含む第３８項記載の方法。
【０１２９】
４３． 前記アルキルアルミニウムがトリエチルアルミニウムである第４２項記載の方法。
【０１３０】
４４． 前記アルキルアルミニウムとマグネシウムの比率が０．００１：１から１：１である第４３記載の方法。
【０１３１】
４５． 前記触媒が重合製造工程にそぐう綿毛形態を有しかつ均一な粒子サイズ分布を示すことに加えて約１２５ミクロン未満の粒子のレベルが低い第３７項記載の方法。
【０１３２】
４６． 前記反応が更に電子供与体も含む第３８項記載の方法。
【０１３３】
４７． 前記電子供与体とマグネシウムの比率が約０：１から約１０：１の範囲である第４６項記載の方法。
【０１３４】
４８． 前記ハロゲン化剤が一般式ＣｌＡＲ”’_x［式中、Ａは、非還元性で親酸素性の化合物であり、Ｒ”’_xは、炭素原子数が約２から６のヒドロカルビル部分であり、そしてｘは、Ａの原子価から１を引いた値である］で表される第３７項記載の方法。
【０１３５】
４９． 前記ハロゲン化剤がＣｌＴｉ（ＯⁱＰｒ）₃である第４８項記載の方法。
【０１３６】
５０． 前記マグネシウムに対するチタンの比率が約０．５から約５．０の範囲である第４９項記載の方法。
【０１３７】
５１． 穏やかな前記１番目の塩素化／チタン化剤が２種類の四置換チタン化合物のブレンド物であり、ここで、４つの置換基が全部同一でありそしてこれらの置換基がハライドまたは炭素原子数が２から１０のアルコキサイドもしくはフェノキサイドである第３７項記載の方法。
【０１３８】
５２． 穏やかな前記１番目の塩素化／チタン化剤がハロゲン化チタンと有機チタネートのブレンド物である第５１項記載の方法。
【０１３９】
５３． 穏やかな前記１番目の塩素化／チタン化剤がＴｉＣｌ₄／Ｔｉ（ＯＢｕ）₄が０．５：１から６：１の範囲のＴｉＣｌ₄とＴｉ（ＯＢｕ）₄のブレンド物である第５１項記載の方法。
【０１４０】
５４． 前記反応が更に電子供与体も含む第３７項記載の方法。
【０１４１】
５５． より強力な前記２番目の塩素化／チタン化剤がハロゲン化チタンである第３７項記載の方法。
【０１４２】
５６． より強力な前記２番目の塩素化／チタン化剤が四塩化チタンでありそしてチタンとマグネシウムの範囲が０：１から２：１である第５５項記載の方法。
【０１４３】
５７． 四塩化チタンが約０．１から約５．０当量の範囲で存在する第５６項記載の方法。
【０１４４】
５８． 前記予備活性化剤である有機アルミニウムが式ＡｌＲ＾₃［式中、Ｒ＾は、同一もしくは異なり、炭素原子数が１−８のアルキルまたはハライドであり、そして少なくとも１つのＲ＾はアルキルである］で表されるアルキルアルミニウムである第３７項記載の方法。
【０１４５】
５９． 前記予備活性化剤である有機アルミニウムがトリアルキルアルミニウムである第５８項記載の方法。
【０１４６】
６０． アルミニウムとチタンの比率が０．１：１から２：１の範囲である第５９項記載の方法。
【０１４７】
６１． 前記予備活性化剤である有機アルミニウムがＴＥＡｌである第６０項記載の方法。
【０１４８】
６２． 電子供与体が工程ａ）、ｂ）、ｃ）またはｄ）のいずれか１工程に存在しそして電子供与体と金属の比率が約０：１から約１０：１の範囲である第３７項記載の方法。
【０１４９】
６３． 前記触媒が所望の分子量分布を示すポリエチレンの製造で用いるに有用である第３７項記載の方法。
【０１５０】
６４．
ａ）ｉ）一般式Ｍｇ（ＯＲ”）₂［式中、Ｒ”は、炭素原子数が１から２０のヒドロカルビルもしくは置換ヒドロカルビルである］で表される可溶マグネシウムジアルコキサイド化合物を１個のハロゲンを１個のアルコキサイドと交換し得るハロゲン化剤に接触させて反応生成物Ａを生成させ、
ｉｉ）反応生成物Ａを１番目のハロゲン化／チタン化剤に接触させて反応生成物Ｂを生成させ、
ｉｉｉ）反応生成物Ｂをより強力な２番目のハロゲン化／チタン化剤に接触させて反応生成物Ｃを生成させ、
ｉｖ）反応生成物Ｃを予備活性化剤である有機アルミニウムに接触させて予備活性化された触媒を生成させ、そして
ｖ）前記予備活性化された触媒を約９０℃から約１５０℃の範囲の温度に約３０分から約２４時間の範囲の時間加熱する、
ことにより製造した触媒の存在下で１種以上のα−オレフィン単量体を共に重合条件下で接触させる、
ことを含んで成るα−オレフィンの重合方法。
【０１５１】
６５． 更に
ｂ）ポリオレフィン重合体を抽出する、
ことを含んで成る第６４項記載の方法。
【０１５２】
６６． 前記単量体がエチレン単量体でありそして前記重合体がポリエチレンである第６４項記載の方法。
【０１５３】
６７． 前記ポリエチレンが少なくとも約４．０の分子量分布を示す第６６項記載の方法。
【０１５４】
６８． 前記重合が塊状、スラリーまたは気相重合である第６４項記載の方法。
【０１５５】
６９． 前記ハロゲン化剤が一般式ＣｌＡＲ”’_x［式中、Ａは、非還元性で親酸素性の化合物であり、Ｒ”’_xは、炭素原子数が約２から６のヒドロカルビル部分である］で表される第６４項記載の方法。
【０１５６】
７０． 前記ハロゲン化剤がＣｌＴｉ（ＯｉＰｒ）₃である第６９項記載の方法。
【０１５７】
７１． 前記１番目のハロゲン化／チタン化剤が２種類の四置換チタン化合物のブレンド物であり、これが一般式ＴｉＣｌ₄／Ｔｉ（ＯＲ””）₄［式中、Ｒ””₄は、炭素原子数が２から６のヒドロカルビル部分である］で表される第６４項記載の方法。
【０１５８】
７２． 前記１番目のハロゲン化／チタン化剤がＴｉＣｌ₄とＴｉ（ＯＢｕ）₄のブレンド物でありそしてＴｉＣｌ₄とＴｉ（ＯＢｕ）₄の比率が約０．５：１から約６：１の範囲である第７１項記載の方法。
【０１５９】
７３． 工程（ｉｉ）に存在するマグネシウムに対するチタンの比率が約０．５から約５．０の範囲である第７２項記載の方法。
【０１６０】
７４． より強力な前記２番目のハロゲン化／チタン化剤がＴｉＣｌ₄である第６４項記載の方法。
【０１６１】
７５． ＴｉＣｌ₄を約０．１から約５．０当量の範囲で存在する第７４項記載の方法。
【０１６２】
７６． 前記予備活性化剤である有機アルミニウムがＴＥＡｌである第６４項記載の方法。
【０１６３】
７７． 電子供与体を工程ｉ−ｉｖのいずれか１工程に存在しそして電子供与体と金属の比率が約０：１から約１０：１の範囲である第６４項記載の方法。
【図面の簡単な説明】
【図１】図１は、熱処理が触媒の固有ＭＷＤに対して与える影響を示す棒グラフである。[0001]
[See related applications]
This application is filed on January 28, 1997, entitled “Ziegler-Natta Catalysts for Olefin Polymerization”, U.S. Patent Application Serial No. 08 / 789,862 (incorporated herein by reference). This is a continuous continuation application
[0002]
BACKGROUND OF THE INVENTION
1.Field of Invention
The present invention relates to a catalyst, a method for producing the catalyst, a method for using the catalyst, a polymerization method, and a polymer produced using the catalyst. In another aspect, the present invention relates to a catalyst for polyolefin, a method for producing the catalyst, a method for using the catalyst, polymerization of polyolefin, and polyolefin. In still another aspect, the present invention relates to a Ziegler-Natta catalyst, a method for producing the catalyst, a method for using the catalyst, polymerization of polyolefin, and polyolefin.
2.Explanation of related technology
From the beginning of the 1950s, Ziegler type polyolefin catalysts, their general production methods and their subsequent use have become well known in the polymerization arts.
[0003]
However, much has been known about Ziegler-type catalysts, which improve the polymer yield, catalyst life, catalytic activity and ability to produce polyolefins with specific properties when using them. Research on this is ongoing.
[0004]
U.S. Pat. No. 4,255,544 issued on March 10, 1981 to Kimura et al. Comprises (A) a reaction product of a magnesium compound and a titanium halide and (B) an organoaluminum compound. A method of polymerizing ethylene using a catalyst is disclosed, wherein the preparation of component A is carried out by reacting magnesium dialkoxide, a halogen-containing silicon compound and an alcohol to produce solid physical properties, and In the presence of an alkoxy-containing silicon compound in the presence of an alkoxy-containing silicon compound.
[0005]
U.S. Pat. No. 4,914,069 issued Apr. 3, 1990 to Job et al. Discloses the preparation of a catalyst component for olefin polymerization that exhibits improved activity and selectivity. The catalyst component is prepared by (a) halogenating a magnesium compound containing at least one aryloxy, alkyl, carbonate or alkyloxy group using the first tetravalent titanium halide and the first electron donor. (B) contacting the resulting product with a second tetravalent titanium halide and (c) washing the resulting treated halogenated product with an inert hydrocarbon liquid. Yes. In such a method, a second electron donor is used in step (a) or (b), and the product of step (b) is converted to the third tetravalent titanium halide in step (b2). After contact at a temperature of from 0 to 140 ° C., the product thus treated is washed in step (c).
[0006]
U.S. Pat. No. 5,155,187 issued to Shelly dated October 13, 1992 generally describes silicon-containing compounds, dialkylmagnesium, alcohols, halide-containing metal compounds, aluminum alkoxides, and a second halide. A polymerization method using a catalyst which is a reaction product of a contained metal compound is disclosed.
[0007]
US Pat. No. 5,610,246 issued to Buehler et al. On March 11, 1997 discloses a process for polymerizing propylene using a catalyst supported on silica. The catalyst is selected from the group consisting of (1) at least one magnesium-containing compound soluble in hydrocarbon and (2) silicon halide, boron halide, aluminum halide and mixtures thereof in any order. A product obtained by contacting with the first specific modifying compound and then with the second specific modifying compound.
[0008]
U.S. Pat. No. 5,631,334 issued to Zandona on May 20, 1997 discloses a process for producing a catalytic solid for the (co) polymerization of at least one olefin. And the method comprises co-precipitation of magnesium and at least one transition metal.
[0009]
However, despite such developments in the prior art, any such prior art literature does not disclose or suggest that a preactivated polyolefin catalyst is heat treated. Not done.
[0010]
Furthermore, the disclosure also suggests that any such prior art literature will have some effect on the molecular weight distribution ("MWD") of the polymer when the preactivated polyolefin catalyst is heat treated. It is not made.
[0011]
Thus, there is a need in the art for polyolefin catalysts.
[0012]
There is also a need in the art for a method for producing a polyolefin catalyst.
[0013]
There is a further need in the art for a method of polymerizing olefins.
[0014]
Furthermore, there is a need in the art for polyolefins that exhibit various MWD.
[0015]
In addition, there is a need in the art for polyolefin catalysts that exhibit high activity and excellent fluff morphology in addition to the ability to produce polyolefins exhibiting various MWDs.
[0016]
Furthermore, there is a need in the art for a method that pre-activates the polyolefin catalyst used and affects the MWD of the polyolefin by heat treatment.
[0017]
Review of the specification and claims, including this figure, will make these and other needs in the art apparent to those skilled in the art.
[0018]
SUMMARY OF THE INVENTION
One object of the present invention is to provide a catalyst for polyolefins.
[0019]
Another object of the present invention is to provide a process for preparing a catalyst for polyolefins.
[0020]
Still another object of the present invention is to provide a method for polymerizing olefins.
[0021]
Yet another object of the present invention is to provide polyolefins exhibiting various MWD.
[0022]
Yet another object of the present invention is to provide a catalyst for polyolefins that can produce polyolefins exhibiting various MWDs and also exhibits high activity and excellent fluff morphology.
[0023]
It is yet another object of the present invention to provide a method of using a pre-activated polyolefin catalyst that is heat treated to affect the MWD of the polyolefin.
[0024]
In accordance with one aspect of the present invention, a polyolefin catalyst is provided. This catalyst comprises a) a reaction product comprising a dialkylmagnesium represented by the general formula MgRR ′ and an alcohol represented by the general formula R ″ OH as a general formula Mg (OR ″).₂[Wherein R, R ′ and R ″ are each a hydrocarbyl having 1 to 20 carbon atoms or a substituted hydrocarbyl, wherein R, R ′ and R ′ are Any two or more of "may be the same or different], b) the magnesium dialkoxide compound as a mild halogenating agent capable of exchanging one halogen for one alkoxide. Contacting to produce reaction product “A”; c) contacting reaction product “A” with a first halogenating / titanating agent to produce reaction product “B”. D) contacting the reaction product “B” with a stronger second halogenation / titanating agent to give the reaction product “C”. E) contacting the reaction product “C” with a pre-activator, organoaluminum preactivating agent, to form a pre-activated catalyst, and f) heating the pre-activated catalyst. Is produced by a method comprising the steps of: The preactivated catalyst is heated in step f) to a temperature in the range of about 90 ° C. to about 150 ° C. for a time in the range of about 30 minutes to about 24 hours.
[0025]
In another aspect of the invention, a polyolefin polymer is provided. The polymer is prepared by a process comprising contacting one or more α-olefin monomers together under polymerization conditions in the presence of the catalyst of the present invention. Generally, the monomer is an ethylene monomer and the polymer is a polyethylene polymer.
[0026]
Yet another embodiment of the present invention provides a catalyst system comprising the polyolefin catalyst of the present invention and an inert support. The inert support is generally a magnesium compound.
[0027]
In yet another aspect of the invention, a method for producing a catalyst is provided. This method generally comprises a) a general formula Mg (OR ″) as a reaction product comprising a dialkylmagnesium represented by the general formula MgRR ′ and an alcohol represented by the general formula R ″ OH.₂[Wherein R, R ′ and R ″ are each a hydrocarbyl having 1 to 20 carbon atoms or a substituted hydrocarbyl, wherein R, R ′ and R ′ are Any two or more of "may be the same or different], b) contacting the magnesium dialkoxide compound with a mild halogenating agent capable of exchanging one halogen for one alkoxide. Reaction product “A” is produced, c) Reaction product “A” is contacted with the first halogenation / titanating agent to produce reaction product “B”, and d) Reaction product “B”. Is contacted with a more powerful second halogenation / titanating agent to produce reaction product “C”, and e) the reaction product “C” is contacted with pre-activator organoaluminum for pre-activation. Catalyst It is generated and f) comprising the step of heating the preactivated catalyst. The preactivated catalyst is heated in step f) to a temperature in the range of about 90 ° C. to about 150 ° C. for a time in the range of about 30 minutes to about 24 hours.
[0028]
Yet another aspect of the present invention provides a process for polymerizing α-olefins. This process generally comprises the steps of a) contacting one or more α-olefin monomers together in the presence of a catalyst under polymerization conditions and b) extracting the polyolefin polymer. Preferably, the monomer is an ethylene monomer and the polymer is polyethylene. The catalyst used in this method is (i) a dialkylmagnesium represented by the general formula MgRR ′ and an alcohol represented by the general formula R ″ OH.₂[Wherein R, R ′ and R ″ are each a hydrocarbyl having 1 to 20 carbon atoms or a substituted hydrocarbyl, wherein R, R ′ and R ″ Any two may be the same or different], (ii) contacting the magnesium dialkoxide compound with a mild halogenating agent capable of exchanging one halogen for one alkoxide. (Iii) contacting the reaction product “A” with the first halogenation / titanating agent to form the reaction product “B”; and (iv) the reaction product “B”. Is contacted with a stronger second halogenation / titanating agent to produce reaction product “C”, and (v) reaction product “C” is contacted with pre-activator organoaluminum to prepare Activated Catalyst to generate and (vi) prepared in the step of heating the preactivated catalyst.
[0029]
Review of the specification and claims, including this figure, will reveal the above and other objects of the invention to those skilled in the art.
[0030]
Detailed Description of the Invention
The method of the present invention for producing a catalyst component generally involves producing a metal dialkoxide from a dialkyl metal and an alcohol, halogenating the metal dialkoxide, and performing halogenation / titanation in one or more steps. The catalyst component is treated with a pre-activator such as organoaluminum to produce a pre-activated catalyst, and the pre-activated catalyst is heat treated.
[0031]
The proposed mechanism for the method of the present invention is generally as follows:
1. MRR ′ + 2R ″ OH → M (OR ″)₂;
2. M (OR ")₂+ ClAR ”’_x→ "A";
3. "A" + TiCl_Four/ Ti (OR "")_Four→ "B";
4). “B” + TiCl_Four→ "C" (catalyst component);
5. “C” + TEAl → preactivated catalyst; and
6). Heat treatment of the preactivated catalyst.
[0032]
In the above formula, M may be any suitable metal, preferably a Group IIA metal, most preferably Mg. Wherein R, R ′, R ″, R ″ ′ and R ″ ″ are each independently a hydrocarbyl or substituted hydrocarbyl moiety, wherein R and R ′ are 1 to 20 carbon atoms, preferably Has 1 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbon atoms, R ″ generally contains 3 to 20 carbon atoms, R "" Typically contains 2-6 carbon atoms and R "" typically contains 2-6 carbon atoms and is generally butyl. When any two or more of R, R ′, R ″, R ″ ′ and R ″ ″ are combined, they may be the same or different.
[0033]
The formula ClAR ""_xIn which A is preferably a non-reducing and oxyphilic compound capable of exchanging one chloride for alkoxide, R ″ ′ is preferably alkyl, and x is A 1 is subtracted from 1. Examples of A include titanium, silicon, aluminum, carbon, tin and germanium, of which titanium is most preferred, where x is 3 Examples of R ″ ′ include methyl, ethyl, propyl, isopropyl, etc., and these carbon atoms have 2-6.
[0034]
The exact composition of product “A” is unknown, but is believed to contain a partially chlorinated metal compound, an example of such a compound could be ClMg (OR ″). The second halogenation / titanation step produces product “B”, which is probably a complex of a chlorinated metal, a partially chlorinated metal and a titanium compound, which is For example (MCl₂)_y'・ (TiCl_x(OR)_4-x)_zCan be indicated by '. A second chlorination / titanation produces the product “C”, which is also likely a complex of a chlorinated metal, a partially chlorinated metal and a titanium compound. Unlike the product “B”, this is probably (MCl₂)_y・ (TiCl_x'(OR)_4-x')_zCan be indicated by '. It is expected that the degree of chlorination of “Product C” will be greater than that of Product “B”. Thus, different degrees of chlorination will produce different complexes of different compounds. While such a description of the reaction product suggests the presently most reasonable explanation of its chemistry, such theoretical mechanism is not intended to limit the invention as described in the claims.
[0035]
Dialkyl metals suitable for use in the present invention and the resulting metal dialkoxides include any dialkyl metal and metal dialkoxide that will produce a suitable polyolefin catalyst when used in the present invention. Suitable metal dialkoxides and dialkyl metals include group IIA metal dialkoxides and dialkyls. Such metal dialkoxide or dialkyl metal is most preferably magnesium dialkoxide or dialkylmagnesium.
[0036]
The dialkylmagnesium [MgRR '] (R and R' are as described above) used in the present invention may be any dialkylmagnesium. Of course, R and R 'may be the same or different. Non-limiting examples of suitable dialkyl magnesium include diethyl magnesium, dipropyl magnesium, dibutyl magnesium, butyl ethyl magnesium, and the like. Butyl ethyl magnesium (BEM) is the preferred dialkyl magnesium.
[0037]
The metal dialkoxide used in the present invention preferably has the general formula Mg (OR ")₂[Wherein R ″ is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms]. This magnesium dialkoxide compound has a general formula MgRR ′ [wherein R and R R ′ may be the same or different and is an alkyl group having 1 to 10 carbon atoms] and a general formula R ″ OH [wherein R ″ has 4 carbon atoms. It is a reaction product obtained by reacting a linear or branched alcohol represented by -20.
[0038]
Such metal dialkoxides are most preferably soluble and non-reducing. A non-reducing compound is an insoluble Ti produced by reduction of a compound such as MgRR '.⁺³MgCl rather than seed (which tends to produce a catalyst with a broad particle size distribution)₂Has the advantage of generating. In addition, Mg (OR ")₂Is less reactive than MgRR ', so chlorination with a mild chlorinating agent followed by chlorination / titanation with a mild reactant and a second chlorination / titanium with a stronger reactant The conversion proceeds slowly and the reaction becomes progressively stronger, resulting in a more uniform product, ie a catalyst with larger catalyst particles and a more uniform particle size distribution.
[0039]
Non-limiting examples of suitable species of useful metal dialkoxides include magnesium butoxide, magnesium pentoxide, magnesium hexoxide, magnesium di (2-ethylhexoxide), and such systems. Any alkoxide suitable for dissolution is included. The most preferred metal alkoxide species is magnesium di (2-ethylhexoxide).
[0040]
As a non-limiting example, the following formula:
MgRR ′ + 2R ″ OH → Mg (OR ″)₂+ RH + R'H
As shown in the figure, a magnesium dialkoxide such as magnesium di (2-ethyl) is produced by reacting an alkylmagnesium compound (MgRR ′) such as butylethylmagnesium (BEM) with an alcohol (ROH) such as 2-ethylhexanol. Hexoxide) and the like can be generated.
[0041]
In the case of BEM, RH and R'H are butane and ethane, respectively. This reaction occurs at room temperature and the reactants form a solution. Any two or more R groups may be the same or all of the R groups may be different from each other.
[0042]
In practicing the present invention, any alcohol that produces the desired metal dialkoxide can be used. Such alcohol may be any alcohol represented by the general formula R ″ OH, where R ″ is an alkyl group having 4-20 carbon atoms, as a non-limiting example. The alcohol may be linear or branched. Non-limiting examples of such alcohols include butanol, isobutanol, 2-ethylhexanol and the like. A preferred alcohol is 2-ethylhexanol.
[0043]
The amount of such alcohol added is generally in the range of about 0.5 equivalents to about 4 equivalents (equivalents based on magnesium or metal compound throughout), preferably in the range of about 1 to 3 equivalents. Although it is considered that almost any alcohol can be used, it is preferable to use a higher order branched alcohol such as 2-ethyl-1-hexanol. The number of carbon atoms of the alcohol used is generally at least 3, preferably at least 4, more preferably at least 5, and most preferably at least 6.
[0044]
Alkyl metal compounds are very easy to associate because they have electron deficient bonds, resulting in high molecular weight species that exhibit very high viscosity in solution. By adding alkylaluminum that breaks the association between individual alkyl metal molecules, such as triethylaluminum, such high viscosity can be reduced. The preferred ratio of alkylaluminum to metal is 0.001: 1 to 1: 1, more preferably 0.01 to 0.1: 1, most preferably 0.03: 1 to 0.05: 1. . In addition, an electron donor such as an ether such as diisoamyl ether (DIAE) can be used to further reduce the viscosity of the alkyl metal. A suitable ratio of electron donor to metal is in the range of about 0: 1 to about 10: 1, more preferably in the range of about 0.1: 1 to about 1: 1.
[0045]
Agents useful in the halogenation step of halogenating the metal alkoxide include any halogenating agent that will produce a suitable polyolefin catalyst when used in the present invention. This halogenation step is preferably a chlorination step, and the preferred halogenating agent is chloride.
[0046]
The preferred halogenating agent chloride (“chlorinating agent”) is preferably a monochloride compound that partially chlorinates the magnesium alkoxide. Suitable chlorinating agents are of the general formula ClAR ""_xOr ClAOR ’’_x[Wherein A is a non-reducing, oxyphilic compound capable of exchanging one chloride for alkoxide, R ″ ′ is alkyl, and x is 1 minus the valence of A. Examples of A are titanium, silicon, aluminum, carbon, tin, and germanium, of which titanium and silicon are most preferred, and x in this case is 3. Examples of R ″ ′ are methyl, ethyl, propyl, isopropyl, etc., and these carbon atoms have 2-6. Examples of chlorinating agents useful in the present invention are ClTi (OⁱPr)_ThreeAnd ClSi (Me)_ThreeIt is.
[0047]
The halogenation of the metal alkoxide compound is generally carried out in a hydrocarbon solvent under an inert atmosphere. Non-limiting examples of suitable solvents include toluene, heptane, hexane, octane and the like. A preferred solvent is hexane.
[0048]
In this halogenation step, the molar ratio of metal alkoxide to halogenating agent is generally in the range of about 6: 1 to about 1: 3, preferably in the range of about 3: 1 to about 1: 2, more preferably about 2. : 1 to about 1: 2, most preferably about 1: 1.
[0049]
This halogenation step is generally carried out at a temperature in the range of about 0 ° C. to about 100 ° C. for a reaction time in the range of about 0.5 to about 24 hours. This halogenation step is preferably carried out at a temperature in the range of about 20 ° C. to about 90 ° C. for a reaction time in the range of about 1 to about 4 hours.
[0050]
After carrying out this halogenation step to halogenate the metal dialkoxide, the product “A” is subjected to halogenation / titanium treatment at least once.
[0051]
The halogenation / titanating agent used in the one or more halogenation / titanation steps is preferably a tetrasubstituted titanium compound (wherein the four substituents may all be the same and these substitutions The group may be a halide or an alkoxide or phenoxide having 2 to 10 carbon atoms), for example TiCl_FourOr Ti (OR)_FourEtc. The halogenation / titanium agent is preferably a chlorination / titanium agent.
[0052]
The suitable chlorinating / titanating agent may be a single compound or a combination of compounds. The process of the present invention produces a catalyst that remains active even after the first chlorination / titanation step, however, the chlorination / titanation is preferably carried out at least twice, and in each of these steps Different compounds or combinations of compounds may be used, including in this case the chlorination / titanation used in each of the sequential chlorination / titanation steps is progressively stronger.
[0053]
The first chlorination / titanating agent is preferably a mild titanating agent, such as a blend of titanium halide and organic titanate. This first chlorination / titanating agent is more preferably TiCl_Four/ Ti (OBu)_FourTiCl in the range of about 0.5: 1 to 6: 1, most preferably in the range of about 2: 1 to 3: 1._FourAnd Ti (OBu)_FourIs a blend of Such a blend of titanium halide and organic titanate reacts with an alkoxy halide of titanium, ie Ti (OR)._aX_b[Wherein OR and X are alkoxide and halide, respectively, a + b is the valence of titanium, typically 4, and a and b are both fractional, eg, a = 2.5 And b may be 1.5].
[0054]
Alternatively, the first chlorination / titanating agent may be a single compound. An example of the first chlorination / titanating agent as a single compound is Ti (OC₂H_Five)₂Cl₂, Ti (OC₂H_Five)_ThreeCl, Ti (OC_ThreeH₇)₂Cl₂, Ti (OC_ThreeH₇)_ThreeCl, Ti (OC_FourH₉) Cl_Three, Ti (OC₆H₁₃)₂Cl₂, Ti (OC₂H_Five)₂Br₂And Ti (OC₁₂H_{twenty five}) Cl_ThreeIt is.
[0055]
The first halogenation / titanation step is generally carried out in a hydrocarbon solvent. Non-limiting examples of suitable hydrocarbon solvents include heptane, hexane, toluene, octane and the like. A preferred solvent is hexane.
[0056]
When the first halogenating / titanating agent is added to the soluble product “A”, the solid product “B” precipitates at room temperature.
[0057]
The amount of halogenation / titanating agent used must be sufficient to allow the solid product to precipitate from the solution. The amount of halogenation / titanating agent used is generally in the range of about 0.5 to about 5, preferably in the range of about 1 to about 4, most preferably based on the ratio of titanium to metal. It is preferably in the range of about 1.5 to about 2.5.
[0058]
The solid product “B” precipitated in the first titanation step is then recovered using any suitable recovery technique and then washed with a hydrocarbon solvent.
[0059]
Compounds suitable for use as the second halogenation / titanium agent include the halogenation / titanium agent suitable for use as the first halogenation / titanium agent, but preferably This second halogenation / titanium agent is a stronger halogenation / titanium agent. The stronger second halogenation / titanating agent is preferably titanium halide, more preferably titanium tetrachloride [TiCl_Four].
[0060]
The second halogenation / titanation step is typically performed by placing the solid product “B” in a hydrocarbon solvent and slurrying it to produce a reaction product, ie, catalyst component “C”. carry out. The hydrocarbon solvents mentioned as suitable for use in the first halogenation / titanation step may be used. Generally, the amount of titanium tetrachloride used is generally in the range of about 0.1 to about 5 equivalents, preferably in the range of about 0.15 to about 4 equivalents, and most preferably from about 0.175 to about 2.5. It is a range.
[0061]
Combining catalyst component “C” with organoaluminum, a cocatalyst component (“pre-activator”), produces a pre-activated catalyst suitable for use in olefin polymerization. Cocatalysts used with catalyst component “C” containing transition metals are typically organometallic compounds of Group Ia, IIa and IIIa metals, such as alkylaluminum, alkylaluminum hydride, alkyllithiumaluminum, alkylzinc, alkylmagnesium Etc.
[0062]
Such pre-activators are preferably organoaluminum compounds. The pre-activator organoaluminum is preferably of the formula AlR ^_ThreeWherein R ^ is alkyl or halide having 1-8 carbon atoms, wherein R ^ is the same or different, and at least one R ^ is alkyl. Aluminum. More preferably, the pre-activator organoaluminum is a trialkylaluminum such as trimethylaluminum (TMA), triethylaluminum (TEAl) and triisobutylaluminum (TiBAl). The most preferred preactivator is TEAl. The ratio of Al to titanium is in the range of 0.01: 1 to 2: 1, preferably 0.25: 1 to 1.2: 1.
[0063]
The preactivated catalyst is then heat treated at a temperature in the range of about 90 ° C to about 150 ° C, preferably to a temperature in the range of about 100 ° C to about 125 ° C. The slurry is held at such elevated temperature for a holding time in the range of about 0.5 hours to about 24 hours, preferably in the range of about 1 hour to about 4 hours. Thereafter, the final solid catalyst is recovered and washed with a hydrocarbon solvent.
[0064]
Optionally, an electron donor may be added with the halogenating agent, a mild first halogenating / titanating agent or a stronger second halogenating / titanium agent. Most preferably, an electron donor is used in the second halogenation / titanation step.
[0065]
The electron donors used in the preparation of the polyolefin catalyst are well known, and any suitable electron donor that provides a suitable catalyst can be used in the present invention.
[0066]
An electron donor is an organic compound that contains oxygen, nitrogen, phosphorus or sulfur and can donate an electron pair to the catalyst, also known as a Lewis base.
[0067]
Such electron donors may be monofunctional or polyfunctional compounds, preferably aliphatic or aromatic carboxylic acids and their alkyl esters, aliphatic or cyclic ethers, ketones, vinyl esters, acrylics. Derivatives, in particular acrylic acid or alkyl methacrylate, and silanes are selected. A suitable example of a suitable electron donor is di-n-butyl phthalate. A more preferred example of a suitable electron donor is the general formula RSi (OR ')_Three[Wherein R and R ′ may be the same or different and are alkyl having 1 to 5 carbon atoms], for example, methylsilyltriethoxide [MeSi (OEt_Three]].
[0068]
The support of the catalyst system of the present invention must be an inert solid that is not chemically reactive with any of the components of conventional Ziegler-Natta catalysts. Such a support is preferably a magnesium compound. Examples of magnesium compounds to be used for the purpose of supporting the present catalyst component are magnesium halides, dialkoxymagnesium, alkoxymagnesium halides, and magnesium carboxylates. The preferred magnesium compound is magnesium chloride (MgCl₂).
[0069]
In some cases, such Ziegler-Natta catalysts may be pre-polymerized. The prepolymerization step is generally performed by contacting the catalyst after contacting the cocatalyst with a small amount of monomer. The prepolymerization process is described in US Pat. Nos. 5,106,804, 5,153,158, and 5,594,071, which are incorporated herein by reference.
[0070]
This catalyst can be used by any known method for homopolymerization or copolymerization of any kind of α-olefin. The catalyst is useful for catalyzing, for example, ethylene, propylene, butylene, pentene, hexene, 4-methylpentene, and other α-alkenes having at least 2 carbon atoms, and also mixtures thereof. The catalyst of the present invention is preferably used to produce polyethylene by polymerizing ethylene.
[0071]
The resulting catalyst of the present invention exhibits very high activity, which depends at least in part on the olefin polymerization conditions. The activity of the catalyst is generally at least 6,000 g of PE per gram of catalyst, but may also show catalytic activity in excess of 100,000 g of PE per gram of catalyst.
[0072]
The resulting catalyst of the present invention additionally provides a polymer having an excellent fluff morphology. Thus, the catalyst of the present invention provides large polymer particles that exhibit a uniform size distribution, with very small fines (less than about 125 microns) present, even if present. Since the catalyst of the present invention contains a large powder having a high powder bulk density and can be easily transferred, this is suitable for the polymerization production process.
[0073]
The polymerization process may be a bulk, slurry or gas phase polymerization. The catalyst of the present invention is preferably used in slurry phase polymerization. The polymerization conditions (eg temperature and pressure) depend not only on the type of equipment used but also on the type of polymerization process used, which are well known in the art. The temperature is for example in the range of about 50-200 ° C. and the pressure is in the range of about 10-800 psi.
[0074]
The olefin monomer can be introduced into the polymerization reaction zone in a diluent (which is a liquid non-reactive heat transfer agent under the reaction conditions). Examples of such diluents are hexane and isobutane. When ethylene is copolymerized with another alpha-olefin, such as butene or hexene, the second alpha-olefin is present in an amount of 0.01-20 mole percent, preferably 0.02-10 mole percent. Can be made.
[0075]
In the present polymerization method, an internal electron donor is included in the synthesis of the catalyst, and an external electron donor or a stereoselective control agent (SCA) for the purpose of activating the catalyst during the polymerization. It may be preferred to include An internal electron donor can be used during the chlorination step or chlorination / titanation step during the production reaction of the catalyst. Compounds suitable for use as internal electron donors to produce conventional supported Ziegler-Natta catalyst components include ethers, diethers, ketones, lactones, electrons having N, P and / or S atoms. Donor compounds and certain types of esters are included. In particular phthalates such as diisobutyl phthalate, dioctyl, diphenyl and benzylbutyl, malonates such as diisobutyl and diethyl malonate, alkyl and aryl pivalates, alkyl maleates, cycloalkyl and aryl, alkyl and aryl carbonates Suitable are succinic esters such as diisobutyl, ethylphenyl and diphenyl carbonate, such as mono- and diethyl succinate.
[0076]
External donors that can be used when producing the catalyst according to the present invention include organosilane compounds, such as the general formula SiR_m(OR ’)_4-mWherein R is selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, and a vinyl group, R ′ is an alkyl group, and m is 0-3, where R is R ′ And when m is 0, 1 or 2, the R ′ groups may be the same or different, and when m is 2 or 3, the R groups may be the same or different.] The alkoxysilanes represented are included.
[0077]
The external donor of the present invention preferably has the following formula:
[0078]
[Chemical 1]

[0079]
Wherein R 1 and R 4 are both alkyl or cycloalkyl groups containing primary, secondary or tertiary carbon atoms bonded to silicon, wherein R 1 and R 4 may be the same or different. Well, R2 and R3 are alkyl or aryl groups]
It selects from the silane compound represented by these. R1 may be methyl, isopropyl, cyclopentyl, cyclohexyl or t-butyl, R2 and R3 may be methyl, ethyl, propyl or butyl groups and are not necessarily identical, and R4 is also It may be methyl, isopropyl, cyclopentyl, cyclohexyl or t-butyl. Specific external donors are cyclohexylmethyldimethoxysilane (CMDS), diisopropyldimethoxysilane (DIDS), cyclohexylisopropyldimethoxysilane (CIDS), dicyclopentyldimethoxysilane (CPDS) or di-t-butyldimethoxysilane (DTDS). .
[0080]
The polyethylene produced using the catalyst described above has an MWD (MW / MD) of at least 4.0, preferably at least 5.0, more preferably at least 6.0, and even more preferably at least 7.0. Will show.
[0081]
【Example】
Although the present invention has been generally described, the following examples are given solely for the purpose of illustrating specific embodiments of the invention. It should be understood that the examples are given by way of illustration and are not intended to limit the specification or the claims in any way.
Catalyst preparation
In this example, a controlled-morphology polyethylene catalyst is described, and when this catalyst is used, the intrinsic molecular weight distribution (MWD) of the polymer obtained using this catalyst is finely tuned (fine tuning). be able to. By adjusting the MWD in this way, polymers of various qualities can be obtained using a single catalyst system, that is, from an injection molding polymer (narrow MWD) to an inflation film polymer (wide range). Various quality polymers used in applications in the range of (MWD) can be obtained.
[0082]
The catalyst was prepared as follows:
Process 1
Soluble intermediate A is produced by BuEtMg / DIAE / TEAl (1: 0.6: 0.03) + 2-ethylhexanol (2.09).
Process 2
Intermediate +1.0 ClTi (OPr)_ThreeTo produce soluble intermediate B.
Process 3
Intermediate B + Ti (OBu)_Four/ TiCl_Four(2.0: 1.0) produces a solid pre-catalyst.
Process 4
Pre-catalyst + TiCl_FourThe final catalyst is produced by (0.25) + TEAl.
Process 5
Next, the final catalyst is heat-treated at 90 ° C. for the time shown in Table 1 below.
polymerization
The reactor used for the polymerization of ethylene (Engineer autoclave) has a capacity of 4 liters, which is fitted with four baffle plates for mixing with two opposing pitch mixing propellers. Yes. Ethylene and hydrogen are introduced into the reaction vessel via the Teledyne-Hastings Raydist mass flow controller, and during this time, the internal reaction pressure is kept constant by a dome-loaded back-pressure regulator. The temperature of the reaction is maintained with steam and cold water (reactor jacket) using a Kammer Valve connected to a Barber-Coleman Controller. Hexane was used as a diluent.
Experimental variables:
80 ℃
Reaction time 60 minutes
Pressure 125 psi
0.2 cc of catalyst slurry (about 10 mg of catalyst)
Cocatalyst TEAl 0.25 mmol / L
Flow rate H₂/ C₂0.25
[0083]
[Table 1]

[0084]
Sampling of the catalyst solution was performed at 2, 4, 6 and 24 hours. The heat treatment at this stage significantly widens the intrinsic MWD of the catalyst as shown by the SR5 and GPC data in Table 1 and FIG. Here, it can be seen that the MWD increases steadily with the first 6 hours of heating. At that point, the degree of widening is leveled out (levels out). Such data further indicates that the molecular weight distribution of the catalyst can possibly be fine-tuned to the desired value based on the polymer application. Finally, it can be seen that even when the catalyst is heat-treated, the high activity and excellent fluff form exhibited by the catalyst are not lost.
[0085]
Although illustrative embodiments of the present invention have been described in detail, it is understood that various other modifications that do not depart from the spirit and scope of the present invention will be apparent to and readily made by those skilled in the art. It will be. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions provided herein, but rather that the claims be given the patent attributable to the invention. Should be construed as encompassing all of the novel features that may be obtained, such features include all of the features that would be treated as equivalent to those skilled in the art to which the present invention pertains. included.
[0086]
The features and aspects of the present invention are as follows.
[0087]
1.
a) General formula Mg (OR ")₂[Wherein R ″ is a hydrocarbyl having 1 to 20 carbon atoms or a substituted hydrocarbyl] The soluble magnesium dialkoxide compound represented by the following formula can be used to exchange one halogen for one alkoxide: Contact with the agent to produce reaction product A,
b) contacting reaction product A with a first halogenation / titanating agent to form reaction product B;
c) contacting reaction product B with a stronger second halogenation / titanating agent to form reaction product C;
d) contacting the reaction product C with organoaluminum as a pre-activator to produce a pre-activated catalyst; and
e) heating the preactivated catalyst to a temperature in the range of about 90 ° C. to about 150 ° C. for a time in the range of about 30 minutes to about 24 hours;
A polyolefin catalyst produced by a process comprising:
[0088]
2. The soluble magnesium dialkoxide compound is an alkylmagnesium represented by the general formula MgRR ′ [wherein R and R ′ may be the same or different and are alkyl groups having 1 to 10 carbon atoms]. A reaction product of a reaction comprising a compound and a linear or branched alcohol represented by the general formula R ″ OH [wherein R ″ is an alkyl group having 4 to 20 carbon atoms] The catalyst according to claim 1.
[0089]
3. The catalyst according to claim 2, wherein the soluble magnesium compound is magnesium di (2-ethylhexoxide).
[0090]
4). The catalyst according to claim 2, wherein the alkylmagnesium compound is diethylmagnesium, dipropylmagnesium, dibutylmagnesium or butylethylmagnesium.
[0091]
5. The catalyst according to claim 2, wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol or 2-ethylhexanol.
[0092]
6). The catalyst of claim 2 wherein the reaction further comprises an alkylaluminum.
[0093]
7. The catalyst according to claim 6, wherein the alkylaluminum is triethylaluminum.
[0094]
8). The catalyst according to claim 7, wherein the ratio of alkyl aluminum to magnesium is 0.001: 1 to 1: 1.
[0095]
9. The catalyst of claim 1 wherein the catalyst has a fluff morphology compatible with the polymerization process and exhibits a uniform particle size distribution, as well as a low level of particles below about 125 microns.
[0096]
10. The catalyst of claim 2 wherein the reaction further comprises an electron donor.
[0097]
11. The catalyst of claim 10, wherein the ratio of said electron donor to magnesium ranges from about 0: 1 to about 10: 1.
[0098]
12 The catalyst according to claim 11, wherein the electron donor is an ether.
[0099]
13. The halogenating agent has the general formula ClAR "'_x[Wherein A is a non-reducing non-oxygenous compound, and R ″ ′_xIs a hydrocarbyl moiety having about 2 to 6 carbon atoms, and x is a value obtained by subtracting 1 from the valence of A].
[0100]
14 The mild first chlorinating / titanating agent is a blend of two tetrasubstituted titanium compounds, where all four substituents are identical and these substituents are halides or carbon atoms The catalyst according to claim 1, which is 2 to 10 alkoxide or phenoxide.
[0101]
15. 15. The catalyst of claim 14, wherein the mild first chlorination / titanating agent is a blend of titanium halide and an organic titanate.
[0102]
16. The mild first chlorination / titanating agent is TiCl_Four/ Ti (OBu)_FourTiCl in the range 0.5: 1 to 6: 1_FourAnd Ti (OBu)_FourThe catalyst according to claim 15, which is a blend of
[0103]
17. Step b) further comprises the general formula RSi (OR ')_ThreeThe catalyst according to claim 1, which also comprises an electron donor represented by the formula: wherein R and R 'may be the same or different and each is alkyl having 1 to 5 carbon atoms.
[0104]
18. The catalyst according to claim 17, wherein the electron donor is methylsilyltriethoxide.
[0105]
19. The catalyst of claim 1 wherein the stronger second chlorination / titanium agent is a titanium halide.
[0106]
20. 20. The catalyst of claim 19, wherein the stronger second chlorination / titanium agent is titanium tetrachloride and the titanium and magnesium range is from 0: 1 to 2: 1.
[0107]
21. The pre-activator organoaluminum is of the formula AlR ^_Three[Wherein R ^ is the same or different and is alkyl or halide having 1 to 8 carbon atoms, and at least one R ^ is alkyl]. catalyst.
[0108]
22. The catalyst according to claim 21, wherein the pre-activator organoaluminum is a trialkylaluminum.
[0109]
23. 24. The catalyst of claim 22, wherein the ratio of aluminum to titanium is in the range of 0.1: 1 to 2: 1.
[0110]
24.
a) i) General formula Mg (OR ")₂[Wherein R ″ is a hydrocarbyl having 1 to 20 carbon atoms or a substituted hydrocarbyl] A soluble magnesium dialkoxide compound represented by the following formula: halogenation capable of exchanging one halogen for one alkoxide Contact with the agent to produce reaction product A,
ii) contacting reaction product A with a first halogenation / titanating agent to form reaction product B;
iii) contacting reaction product B with a stronger second halogenation / titanating agent to form reaction product C;
iv) contacting reaction product C with organoaluminum as a pre-activator to produce a pre-activated catalyst; and
v) heating the preactivated catalyst to a temperature in the range of about 90 ° C. to about 150 ° C. for a time in the range of about 30 minutes to about 24 hours;
Contacting one or more α-olefin monomers together under polymerization conditions in the presence of a catalyst prepared by
A polymer produced by a process comprising:
[0111]
25. 25. The polymer of claim 24, wherein the monomer is an ethylene monomer and the polymer is polyethylene.
[0112]
26. 26. The polymer of claim 25, wherein the polyethylene exhibits a molecular weight distribution greater than about 4.0.
[0113]
27. 25. The polymer according to item 24, wherein the polymerization is a bulk, slurry or gas phase polymerization.
[0114]
28. The soluble magnesium dialkoxide compound is an alkylmagnesium represented by the general formula MgRR ′ [wherein R and R ′ may be the same or different and are alkyl groups having 1 to 10 carbon atoms]. A reaction product of a reaction comprising a compound and a linear or branched alcohol represented by the general formula R ″ OH [wherein R ″ is an alkyl group having 4 to 20 carbon atoms] The polymer according to 24.
[0115]
29. The soluble magnesium compound is magnesium di (2-ethylhexoxide), the alkyl magnesium compound is selected from the group consisting of diethyl magnesium, dipropyl magnesium, dibutyl magnesium and butyl ethyl magnesium, and the alcohol is ethanol, propanol 25. The polymer of claim 24, selected from the group consisting of: isopropanol, butanol, isobutanol and 2-ethylhexanol.
[0116]
30. 26. The polymer of claim 25, wherein the reaction further comprises alkylaluminum and the ratio of alkylaluminum to magnesium is 0.001: 1 to 1: 1.
[0117]
31. The polymer of claim 25, wherein any one of steps i) -v) further comprises an electron donor and the ratio of said electron donor to magnesium ranges from about 0: 1 to about 10: 1. .
[0118]
32. 32. The polymer according to item 31, wherein the electron donor is an ether.
[0119]
33. The halogenating agent has the general formula ClAR "'_x[Wherein A is a non-reducing non-oxygenous compound, and R ″ ′_xIs a hydrocarbyl moiety having from about 2 to 6 carbon atoms, and x is a value obtained by subtracting 1 from the valence of A].
[0120]
34. The mild first chlorination / titanating agent is TiCl_Four/ Ti (OBu)_FourTiCl in the range 0.5: 1 to 6: 1_FourAnd Ti (OBu)_Four25. The polymer according to item 24, which is a blend of
[0121]
35. 25. The polymer of claim 24, wherein the more potent second chlorination / titanating agent is titanium tetrachloride and the range of titanium and magnesium is from 0: 1 to 2: 1.
[0122]
36. The pre-activator organoaluminum is of the formula AlR ^_ThreeWherein R ^ is the same or different, is an alkyl or halide having 1-8 carbon atoms, and at least one R ^ is alkyl; and Al and titanium 25. The polymer of claim 24, wherein the ratio is in the range of 0.1: 1 to 2: 1.
[0123]
37.
a) General formula Mg (OR ")₂[Wherein R ″ is a hydrocarbyl having 1 to 20 carbon atoms or a substituted hydrocarbyl] A soluble magnesium dialkoxide compound represented by the following formula: halogenation capable of exchanging one halogen for one alkoxide Contact with the agent to produce reaction product A,
b) contacting reaction product A with a first halogenation / titanating agent to form reaction product B;
c) contacting reaction product B with a stronger second halogenation / titanating agent to form reaction product C;
d) contacting the reaction product C with organoaluminum as a pre-activator to produce a pre-activated catalyst; and
e) heating the preactivated catalyst to a temperature in the range of about 90 ° C. to about 150 ° C. for a time in the range of about 30 minutes to about 24 hours;
A process for producing a catalyst comprising:
[0124]
38. The soluble magnesium dialkoxide compound is an alkylmagnesium represented by the general formula MgRR ′ [wherein R and R ′ may be the same or different and are alkyl groups having 1 to 10 carbon atoms]. A reaction product of a reaction comprising a compound and a linear or branched alcohol represented by the general formula R ″ OH [wherein R ″ is an alkyl group having 4 to 20 carbon atoms] 38. The method according to 37.
[0125]
39. 40. The method of claim 37, wherein the soluble magnesium compound is magnesium di (2-ethylhexoxide).
[0126]
40. 40. The method of claim 38, wherein the alkylmagnesium compound is diethylmagnesium, dipropylmagnesium, dibutylmagnesium or butylethylmagnesium.
[0127]
41. 40. The method of paragraph 38, wherein the alcohol is ethanol, propanol, isopropanol, butanol, isobutanol or 2-ethylhexanol.
[0128]
42. 40. The method of claim 38, wherein the reaction further comprises an alkylaluminum.
[0129]
43. 43. The method of claim 42, wherein the alkylaluminum is triethylaluminum.
[0130]
44. 44. The method of claim 43, wherein the ratio of alkyl aluminum to magnesium is 0.001: 1 to 1: 1.
[0131]
45. 38. The method of claim 37, wherein the catalyst has a fluff morphology compatible with the polymerization process and exhibits a uniform particle size distribution, as well as a low level of particles below about 125 microns.
[0132]
46. 40. The method of claim 38, wherein the reaction further comprises an electron donor.
[0133]
47. 47. The method of claim 46, wherein the ratio of the electron donor to magnesium ranges from about 0: 1 to about 10: 1.
[0134]
48. The halogenating agent has the general formula ClAR "'_x[Wherein A is a non-reducing non-oxygenous compound, and R ″ ′_xIs a hydrocarbyl moiety having from about 2 to 6 carbon atoms, and x is a value obtained by subtracting 1 from the valence of A].
[0135]
49. The halogenating agent is ClTi (OⁱPr)_Three49. The method of paragraph 48, wherein
[0136]
50. 50. The method of claim 49, wherein the ratio of titanium to magnesium ranges from about 0.5 to about 5.0.
[0137]
51. The mild first chlorinating / titanating agent is a blend of two tetrasubstituted titanium compounds, where all four substituents are identical and these substituents are halides or carbon atoms 38. The method of paragraph 37, which is 2 to 10 alkoxides or phenoxides.
[0138]
52. 52. The method of claim 51, wherein the mild first chlorination / titanating agent is a blend of titanium halide and an organic titanate.
[0139]
53. The mild first chlorination / titanating agent is TiCl_Four/ Ti (OBu)_FourTiCl in the range 0.5: 1 to 6: 1_FourAnd Ti (OBu)_Four52. The method of claim 51, which is a blend of
[0140]
54. 40. The method of claim 37, wherein the reaction further comprises an electron donor.
[0141]
55. 38. The method of claim 37, wherein the more potent second chlorination / titanium agent is a titanium halide.
[0142]
56. 56. The method of claim 55, wherein the more potent second chlorination / titanium agent is titanium tetrachloride and the titanium and magnesium range is from 0: 1 to 2: 1.
[0143]
57. 57. The method of claim 56, wherein the titanium tetrachloride is present in the range of about 0.1 to about 5.0 equivalents.
[0144]
58. The pre-activator organoaluminum is of the formula AlR ^_Three38. An alkylaluminum represented by the formula: wherein R ^ is the same or different, and is alkyl or halide having 1 to 8 carbon atoms, and at least one R ^ is alkyl. Method.
[0145]
59. 59. The method of claim 58, wherein the pre-activator organoaluminum is a trialkylaluminum.
[0146]
60. 60. The method of claim 59, wherein the ratio of aluminum to titanium is in the range of 0.1: 1 to 2: 1.
[0147]
61. 61. The method of claim 60, wherein the pre-activator organoaluminum is TEAl.
[0148]
62. 38. The electron donor is present in any one of steps a), b), c) or d) and the ratio of electron donor to metal ranges from about 0: 1 to about 10: 1. the method of.
[0149]
63. 38. The method of claim 37, wherein the catalyst is useful in the production of polyethylene exhibiting a desired molecular weight distribution.
[0150]
64.
a) i) General formula Mg (OR ")₂[Wherein R ″ is a hydrocarbyl having 1 to 20 carbon atoms or a substituted hydrocarbyl] A soluble magnesium dialkoxide compound represented by the following formula: halogenation capable of exchanging one halogen for one alkoxide Contact with the agent to produce reaction product A,
ii) contacting reaction product A with a first halogenation / titanating agent to form reaction product B;
iii) contacting reaction product B with a stronger second halogenation / titanating agent to form reaction product C;
iv) contacting reaction product C with organoaluminum as a pre-activator to produce a pre-activated catalyst; and
v) heating the preactivated catalyst to a temperature in the range of about 90 ° C. to about 150 ° C. for a time in the range of about 30 minutes to about 24 hours;
Contacting one or more α-olefin monomers together under polymerization conditions in the presence of a catalyst prepared by
A process for polymerizing α-olefins.
[0151]
65. More
b) extracting a polyolefin polymer;
65. The method of paragraph 64, comprising:
[0152]
66. 65. The method of paragraph 64, wherein the monomer is an ethylene monomer and the polymer is polyethylene.
[0153]
67. 68. The method of claim 66, wherein the polyethylene exhibits a molecular weight distribution of at least about 4.0.
[0154]
68. 65. The method of paragraph 64, wherein the polymerization is a bulk, slurry or gas phase polymerization.
[0155]
69. The halogenating agent has the general formula ClAR "'_x[Wherein A is a non-reducing non-oxygenous compound, and R ″ ′_xIs a hydrocarbyl moiety having from about 2 to 6 carbon atoms].
[0156]
70. The halogenating agent is ClTi (OiPr)_Three70. The method of paragraph 69, wherein
[0157]
71. The first halogenating / titanating agent is a blend of two tetrasubstituted titanium compounds, which has the general formula TiCl_Four/ Ti (OR "")_Four[Where R ""_FourIs a hydrocarbyl moiety having from 2 to 6 carbon atoms].
[0158]
72. The first halogenating / titanium agent is TiCl_FourAnd Ti (OBu)_FourAnd a TiCl_FourAnd Ti (OBu)_Four72. The method of clause 71, wherein the ratio is from about 0.5: 1 to about 6: 1.
[0159]
73. 75. The method of paragraph 72, wherein the ratio of titanium to magnesium present in step (ii) ranges from about 0.5 to about 5.0.
[0160]
74. The more powerful second halogenating / titanating agent is TiCl_Four65. The method of paragraph 64, wherein
[0161]
75. TiCl_Four75. The method of paragraph 74, wherein is present in the range of about 0.1 to about 5.0 equivalents.
[0162]
76. 65. The method according to item 64, wherein the pre-activator organoaluminum is TEAl.
[0163]
77. 65. The method of paragraph 64, wherein the electron donor is present in any one of steps i-iv and the ratio of electron donor to metal ranges from about 0: 1 to about 10: 1.
[Brief description of the drawings]
FIG. 1 is a bar graph showing the effect of heat treatment on the intrinsic MWD of a catalyst.

Claims (3)

a) A soluble magnesium dialkoxide compound represented by the general formula MgTi (OR ") ₂ [wherein R" is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms] ''') ₃ wherein, R''' are carbon atoms and is a hydrocarbyl unit content of 2 to 6] to produce a reaction product a is contacted with a halogenating agent represented by the
b) The reaction product A is converted into a first halogenation / titanium agent which is a blend of titanium tetraalkoxide with 2 to 10 carbon atoms and titanium tetrachloride (Ti (OR) ₄ / TiCl ₄ ). Contacting to produce reaction product B;
c) contacting reaction product B with titanium tetrachloride to form reaction product C;
d) contacting the reaction product C with organoaluminum as a pre-activator to produce a pre-activated catalyst, and e) bringing the pre-activated catalyst to a temperature in the range of 90 ° C. to 150 ° C. Heating for a time ranging from 30 minutes to 24 hours,
A polyolefin catalyst produced by a process comprising: a) A soluble magnesium dialkoxide compound represented by the general formula MgTi (OR ") ₂ [wherein R" is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms] ''') ₃ wherein, R''' are carbon atoms and is a hydrocarbyl moiety of 2 to 6] to produce a reaction product a is contacted with a halogenating agent represented by the
b) Reaction product A is converted into a first halogenation / titanium agent which is a blend of tetraalkoxide of titanium having 2 to 10 carbon atoms and titanium tetrachloride (Ti (OR) ₄ / TiCl ₄ ). Contacting to produce reaction product B;
c) contacting reaction product B with titanium tetrachloride to form reaction product C;
d) contacting the reaction product C with organoaluminum as a pre-activator to produce a pre-activated catalyst, and e) bringing the pre-activated catalyst to a temperature in the range of 90 ° C. to 150 ° C. Heating for a time ranging from 30 minutes to 24 hours,
A process for producing a catalyst comprising: a) A soluble magnesium dialkoxide compound represented by the general formula MgTi (OR ") ₂ [wherein R" is a hydrocarbyl or substituted hydrocarbyl having 1 to 20 carbon atoms] ''') ₃ wherein, R''' are carbon atoms and is a hydrocarbyl moiety of 2 to 6] to produce a reaction product a is contacted with a halogenating agent represented by the
b) Reaction product A is converted into a first halogenation / titanium agent which is a blend of tetraalkoxide of titanium having 2 to 10 carbon atoms and titanium tetrachloride (Ti (OR) ₄ / TiCl ₄ ). Contacting to produce reaction product B;
c) contacting reaction product B with titanium tetrachloride to form reaction product C;
d) contacting the reaction product C with organoaluminum as a pre-activator to produce a pre-activated catalyst, and e) bringing the pre-activated catalyst to a temperature in the range of 90 ° C. to 150 ° C. Heating for a time ranging from 30 minutes to 24 hours,
Contacting one or more α-olefin monomers together under polymerization conditions in the presence of a catalyst prepared by
A process for polymerizing α-olefins.

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