JP4976129B2 - Ziegler-Natta catalyst for polyolefin - Google Patents

Description

【００６５】
［式中、Ｒ_１およびＲ_４は、両方とも、ケイ素と結合している第一級、第二級もしくは第三級炭素原子を含有するアルキルもしくはシクロアルキル基であり、Ｒ_１とＲ_４は同じまたは異なってもよく、Ｒ_２およびＲ_３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可能である。Ｒ_１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、Ｒ_２およびＲ_３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、必ずしも同じである必要はなく、そしてＲ_４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。
【００６６】
上述した触媒を用いて生じさせたポリエチレンが示すＭＷＤは少なくとも５．０であり得、約６．０より高い可能性もある。
【００６７】
本発明のポリオレフィンはいろいろな用途で用いるに適し、例えば押出し加工などで用いるに適し、それによって幅広い範囲の製品を生じさせることができる。そのような押出し加工方法には、例えばブローンフィルム押出し加工、キャストフィルム押出し加工、スリットテープ押出し加工、ブロー成形、パイプ押出し加工および発泡シート押出し加工が含まれる。そのような加工には単層押出し加工または多層共押出し加工が含まれ得る。
【００６８】
本発明を利用することができる最終使用用途には、例えばフィルム、繊維、パイプ、織物材料、製造品、おむつ構成要素、女性衛生品、自動車構成要素および医療用材料が含まれ得る。
【００６９】
本明細書で引用する全ての文献（研究論文、米国特許および外国の特許および特許出願の全部を包含）は具体的に引用することによって全体が本明細書に組み入れられる。
１番目の組の実施例
本発明を一般的に記述してきたが、本発明の特定態様を単に説明しかつ本発明の実施および利点を示す目的で以下の実施例を示す。本実施例は説明として示すものであり、決して本明細書の範囲も請求項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。
【００７０】
この系列の触媒で利用する合成スキームは下記の通りである（比率は全部ＢＥＭが基準である）：
（ＢＥＭ＋０．０３ ＴＥＡｌ＋０．６ ＤＩＡＥ）＋２．０９ ２−エチルヘキサノール→Ｍｇ（ＯＲ）_２
Ｍｇ（ＯＲ）_２＋ＣｌＴｉ（ＯＰｒ）_３→溶液Ａ
溶液Ａ＋（２ ＴｉＣｌ_４／Ｔｉ（ＯＢｕ）_４→触媒Ｂ（ＭｇＣｌ_２が基になった担体）
触媒Ｂ＋Ｘ ＴｉＣｌ_４→触媒Ｃ
触媒Ｃ＋０．１５６ ＴＥＡｌ→最終触媒
最適な配合はＸ＝０．５から２であると考えており、触媒ＣにＴＥＡｌによる予活性化を受けさせる前に行う洗浄の回数は０から２回である。チタン化がより有効に起こるように触媒調製に下記の修飾を受けさせた：
触媒Ｂ＋Ｘ ＴｉＣｌ_４→触媒Ｃ
触媒Ｃ＋Ｙ ＴｉＣｌ_４→触媒Ｄ
触媒Ｄ＋０．１５６ ＴＥＡｌ→最終触媒
示すように、ＸおよびＹ＝０．５から１．０の場合、ＴｉＣｌ_４の添加を２段階で完了させる。触媒Ｃに洗浄を一般的には１から２回受けさせる一方、第二世代のチーグラー種として働く可溶なチタン種を除去する目的で、Ｙ後に２回の洗浄を実施する。
【実施例１】
【００７１】
窒素パージボックス内で３Ｌの丸底フラスコにＢＥＭ−１を１４１２．２５ｇ（２．００モル）、ＴＥＡｌ（ヘプタン中２４．８％）を２７．６０ｇ（０．０６０モル）およびＤＩＡＥを１８９．７０ｇ（１．２０モル）加えた。次に、カニューレを用いてその内容物を窒素流下で２０Ｌのビュッキ（Ｂｕｃｈｉ）反応槽に移した。次に、前記フラスコを約４００ｍｌのヘキサンで濯いで、それも前記反応槽に移した。撹拌機を３５０ｒｐｍに設定した。
【００７２】
１Ｌのボトルに２−エチルヘキサノール（５４３．６０ｇ、４．２１モル）を加えて蓋をした。次に、それをヘキサンで全体積が１Ｌになるように希釈した後、前記反応槽に加えた。質量流量制御装置を用いて前記溶液を前記反応槽にカニューレで移した。初期の塔頂温度は２５．３℃でありそしてそれが２９．６℃の最大温度に到達した。前記添加（約２時間）後、前記ボトルを４００ｍｌのヘキサンで濯いで、それも前記反応槽に移した。その反応混合物を０．５バールの窒素圧下で一晩３５０ｒｐｍで撹拌したままにした後、熱交換器のスイッチを切った。
【００７３】
前記熱交換器のスイッチを入れて２５℃に設定した。クロロチタントリイソプロポキサイドを２個の１Ｌボトルに加える（７７４．９９および７７５．０１ｇ、全体で２．００モル）ことで全体で２リットルにした。質量流量制御装置を用いて各ボトルの内容物を前記反応槽にカニューレで移した。初期の塔頂空間部温度は２４．６℃でありそして２番目のボトルの添加を行っている間にそれが２５．９℃の最大温度に到達した。ボトル１および２の添加時間はそれぞれ１４５分および１２５分であった。この添加後、各ボトルを２００ｍｌのヘキサンで濯いで、それも前記反応槽に移した。その反応混合物を０．５バールの窒素圧下で一晩３５０ｒｐｍで撹拌したままにした。熱交換器のスイッチを切った。
ＴｉＣｌ _４ ／Ｔｉ（ＯＢｕ） _４ の調製
標準的なシュレンクライン技術を用いて、四塩化チタン／チタンテトラブトキサド混合物の調製を５リットルの丸底フラスコ内で実施した。１Ｌの加圧ボトルの中で６８０．００ｇ（１．９９モル）のＴｉ（ＯＢｕ）_４をヘキサンで全体積が１Ｌになるように希釈した。次に、この溶液をカニューレで前記反応槽に移した。前記ボトルを２００ｍｌのヘキサンで濯いで、それも前記反応槽に移した。１Ｌのメスシリンダーの中で４４０ｍｌ（〜７６０ｇ、４．００モル）のＴｉＣｌ_４をヘキサンで全体積が１Ｌになるように希釈した。前記５リットルのフラスコに入っている溶液を撹拌しながら、この反応槽にＴｉＣｌ_４溶液をＮ_２圧下でカニューレを用いて滴下して加えた。この滴下が終了した後、その１Ｌのシリンダーを２００ｍｌのヘキサンで濯いで、それも前記反応槽に移した。１時間後の反応混合物をヘキサンで全体積が４Ｌになるまで希釈した後、使用するまで前記フラスコ内に貯蔵した。
【００７４】
熱交換器のスイッチを入れて２５℃に設定した。カニューレおよび質量流量制御装置を用いてＴｉＣｌ_４／Ｔｉ（ＯＢｕ）_４の混合物を２０リットルの反応槽に移した。初期の塔頂空間部温度は２４．７℃でありそして２２５分間の添加中にそれが２６．０℃の最大温度に到達した。この添加後の容器を１リットルのヘキサンで濯いだ後、１時間撹拌した。
【００７５】
撹拌機のスイッチを切って、その溶液を３０分間沈降させた。その反応槽を１バールに加圧し、浸漬管を下げそして取り付けられている透明なプラスチック製ホースを通って固体状触媒が出て行かないことを確保することで、その溶液をデカンテーションした。次に、その触媒を下記の手順で３回洗浄した。加圧容器を用いてこれを秤の上に置き、この容器の中に２．７ｋｇのヘキサンを計量して入れた後、前記反応槽に移した。撹拌機のスイッチを入れて、触媒混合物を１５分間撹拌した。次に、前記撹拌機のスイッチを切って、前記混合物を３０分間沈降させた。この手順を繰り返した。３回目のヘキサン添加を受けさせた後のスラリーを一晩沈降させ、そして熱交換器のスイッチを切った。
【００７６】
その上澄み液をデカンテーションで除去し、そして前記反応槽にヘキサンを２．０ｋｇ加えた。撹拌を３５０ｒｐｍで再開し、そして熱交換器のスイッチを入れて２５℃に設定した。１リットルのメスシリンダーの中に四塩化チタンを４４０ミリリットル（７６０ｇ、４．００モル）加えた。このＴｉＣｌ_４をヘキサンで１リットルになるまで希釈した後、カニューレおよび質量流量制御装置を用いて前記溶液の半分を前記反応槽に移した。初期の塔頂温度は２４．７℃であり、これが前記添加中に０．５℃上昇した。全添加時間は４５分間であった。１時間後に撹拌機のスイッチを切って、固体を３０分間沈降させた。その上澄み液をデカンテーションで除去した後、触媒をこの上に記述した手順に従ってヘキサンで１回洗浄した。この洗浄が完了した後、その反応槽にヘキサンを２．０ｋｇ移して、撹拌を再開した。この２回目のＴｉＣｌ_４滴下を残りの５００ミリリットルの溶液を用いてこの上に記述した様式と同じ様式で完了させた。この滴下後、前記シリンダーを４００ミリリットルのヘキサンで濯いで、それも前記ビュッキに加えた。１時間の反応後に撹拌機のスイッチを切って、固体を３０分間沈降させた。次に、その上澄み液をデカンテーションで除去した後、触媒をヘキサンで３回洗浄した。次に、前記反応槽にヘキサンを２．０ｋｇ移した。
【００７７】
１リットルの加圧ボトルにＴＥＡｌ（ヘキサン中２５．２％）を１４４．８ｇ（３１２ミリモル）加えた。そのボトルに蓋をした後、ヘキサンで１リットルになるまで希釈した。次に、質量流量制御装置を用いて、その溶液を前記反応混合物にカニューレで移した。１２０分間の添加中にスラリーの色が暗褐色に変わった。初期の塔頂温度は２４．５℃であり、これが２５．３℃の最大温度に到達した。この添加後のボトルを４００ミリリットルのヘキサンで濯いで、これも前記反応槽に移した。１時間の反応後、撹拌機のスイッチを切って、触媒を３０分間沈降させた。その上澄み液をデカンテーションで除去した後、その触媒をこの上に記述した手順に従って１回洗浄した。この洗浄後、前記反応槽にヘキサンを２．７ｋｇ加えた。次に、その内容物を３ガロンの加圧容器に移した。前記ビュッキを１．０ｋｇそして０．５ｋｇのヘキサンで濯いだ後、それらも前記加圧容器に加えた。推定触媒収量は３２２ｇであった。
【００７８】
１つの態様における組成（重量パーセントで表す）は下記であった：Ｃｌが５３．４％；Ａｌが２．３％；Ｍｇが１１．８％およびＴｉが７．９％。各元素の実測範囲は下記であった：Ｃｌが４８．６−５５．１％；Ａｌが２．３−２．５％；Ｍｇが１１．８−１４．１％およびＴｉが６．９−８．７％。各元素の範囲は下記であり得る：Ｃｌが４０．０−６５．０％；Ａｌが０．０−６．０％；Ｍｇが６．０−１５．０％およびＴｉが２．０−１４．０％。
【００７９】
表１に、ＴｉＣｌ_４／Ｔｉ（ＯＢｕ）_４添加、３回の洗浄、１回目のＴｉＣｌ_４添加、１回目の洗浄および２回目のＴｉＣｌ_４添加および次の３回目の洗浄後のサンプルに関して測定した［Ｔｉ］を挙げる。上澄み液１−４はＴｉＣｌ_４／Ｔｉ（ＯＢｕ）_４添加後の上澄み液である。上澄み液５および６は１回目のＴｉＣｌ_４添加後の上澄み液である。上澄み液７−１０は２回目のＴｉＣｌ_４添加後の上澄み液である。
【００８０】
【表１】

【００８１】
比較実施例１：
３回目のチタン化を省きそして２回目のチタン化を１／４の量のＴｉＣｌ₄を用いて実施する以外は実施例１の様式と同様な様式で比較実施例１の調製を行った。
実施例２：
２回目および３回目のチタン化を各チタン化段階中に０．５当量のＴｉＣｌ₄を用いて実施する以外は実施例１の様式と同様な様式で実施例２の調製を行った。
比較実施例２：
２回目のチタン化中に用いるＴｉＣｌ₄の量を比較実施例１で用いた量の約４倍にする以外は比較実施例１の様式と同様な様式で比較実施例２の調製を行った。２回目のチタン化後にヘキサンによる洗浄を１回実施した。１つの態様における組成（重量パーセントで表す）は下記であった：Ｃｌが５７．０％；Ａｌが２．０％；Ｍｇが９．５％およびＴｉが１０．０％。各元素の範囲は下記であり得る：Ｃｌが５５．０−５７．０％；Ａｌが２．０−２．６％；Ｍｇが８．９−９．５％およびＴｉが１０．０−１１．０％。
比較実施例３：
２回目のチタン化後にヘキサンによる洗浄を２回実施する以外は比較実施例２の様式と同様な様式で比較実施例３を調製した。１つの態様における組成（重量パーセントで表す）は下記であった：Ｃｌが５３．０％；Ａｌが２．３％；Ｍｇが９．７％およびＴｉが９．５％。各元素の範囲は下記であり得る：Ｃｌが５２．６−５３．０％；Ａｌが２．０−２．３％；Ｍｇが９．７−１０．６％およびＴｉが８．７−９．５％。
【００８２】
表２に、調製した触媒を挙げる。
【００８３】
【表２】

【００８４】
表３に、実施例１および比較実施例１から３を用いて製造した重合体が示したＭＷＤデータを示す。このデータは、触媒／共触媒系が決まっている場合には洗浄回数を多くするか或はＴｉＣｌ₄を用いた３回目のチタン化段階を加えるとより狭いＭＷＤを達成することができることを示している。重合体樹脂が示す固有のＭＷＤは一般に下記の順で高い：
比較実施例１＜実施例２＜比較実施例３＜実施例１＜比較実施例２。
【００８５】
【表３】

【００８６】
表４に示すように、前記触媒は各々が微細物（１２５ミクロン未満の粒子）の濃度が低い粉末をもたらしはしたが、しかしながら、チタン化段階を２回用いて生じさせた本発明の触媒を用いるとかさ密度がより高い綿毛物が一貫してもたらされる。
【００８７】
【表４】

【００８８】
このような特性は、実験室で作成した沈降効率曲線（図１に示す）で示されるように、重合体の沈降効率に実質的な影響を与える。本発明の実施例１の触媒を用いて製造した本発明の重合体では溶液から生じた最初の１０ｍｌの綿毛物が急速に消失することが分かり、このことは、比較実施例３の通常の触媒を用いて製造した重合体のそれらよりも沈降速度が速くかつ重合体の形態が良好であることを意味する。
合成用溶液の粘度制御
触媒合成中の溶液の粘度を変えることでその溶液から沈澱して来る触媒成分の沈澱を修正することができることを見いだした。そのように触媒成分の沈澱を修正することで結果として生じる触媒の粒径および前記触媒を用いて生じさせる重合体の粒径に影響を与えることを見いだした。触媒合成用溶液の粘度は存在させるアルミニウムアルキルの相対量に応じて変わり得る。従って、触媒の粒径および前記触媒を用いて生じさせる重合体の粒径は使用するアルミニウムアルキルの相対量に応じて変わり得る。
【００８９】
合成用溶液に入れるアルミニウムアルキルの量を変えて触媒を調製しそして試験をこれらの触媒を用いて結果として生じさせた重合体綿毛物の試験と一緒に実施した。実施例３に触媒調製で用いた合成を記述しそして表５に結果としてもたらされた触媒および重合体の大きさを示す。
【実施例３】
【００９０】
用いた合成は下記の通りであり、比率は全部ＢＥＭを基準にした比率である：
１． （ＢＥＭ＋Ｘ ＴＥＡｌ＋０．６ ＤＩＡＥ）＋（２＋３Ｘ） ２−エチルヘキサノール→Ｍｇ（Ｏ−２−エチルヘキシル）_２・［Ａｌ（Ｏ−２−エチルヘキシル）_３］
２． Ｍｇ（Ｏ−２−エチルヘキシル）_２・［Ａｌ（Ｏ−２−エチルヘキシル）_３］＋ＣｌＴｉ（ＯＰｒ）_ｘ→「Ａ」
３． 「Ａ」＋２ＴｉＣｌ_４／Ｔｉ（Ｏｂｕ）_４→「Ｂ」（ＭｇＣｌ_２が基になった担体）
４． 「Ｂ」＋Ｙ ＴｉＣｌ_４→「Ｃ」
５． 「Ｃ」＋Ｚ ＴｉＣｌ_４→「Ｄ」
７． 「Ｄ」＋０．１５６ ＴＥＡｌ→触媒
Ｙ＝Ｚ＝１の４種類の触媒を前記一般的合成に従って１リットルのビュッキ反応槽内で調製した。１番目の反応では、ＴＥＡｌの量が結果として触媒の粒径に対して与える影響を研究する目的でそれの量を変えた。いくらか存在する未反応のアルミニウムもしくはマグネシウムアルキル種によってチタン錯体量が減少することがないようにする目的で各触媒合成中に２−エチルヘキサノールの相対量を調整した。以下の表に、合成した触媒、使用したＢＥＭ、ＴＥＡｌおよび２−エチルヘキサノールの相対量、触媒が示した平均粒径および各触媒を用いて生じさせたポリエチレン樹脂が示した平均粒径を挙げる。
【００９１】
以下の表に、各触媒に関して得た粒径分布データを示す。分かるであろうように、平均粒径分布はＴＥＡｌ濃度を高くするにつれて向上する。
【００９２】
【表５】

【００９３】
表５に示すように、触媒の平均粒径および結果としてもたらされる綿毛物の平均粒径は両方ともが最初の触媒合成用溶液で用いるＴＥＡｌ濃度を高くするにつれて大きくなる。アルミニウムアルキルの相対量を変えることで触媒合成溶液の粘度を変えることができる。そのように溶液の粘度を変えることでその溶液から生じさせる触媒成分の沈澱特性を変えることができ、それによって結果としてもたらされる触媒成分の平均粒径およびその触媒を用いて結果として生じさせる重合体の平均粒径に影響を与えることができる。合成用溶液に入れるアルミニウムアルキルの濃度を高くするにつれて触媒成分の平均粒径が大きくなることが分かる。また、合成用溶液に入れるアルミニウムアルキルの濃度を高くするにつれてその触媒を用いて結果として生じさせる重合体樹脂の平均粒径も大きくなることが分かる。
【００９４】
アルミニウムアルキルの量はアルミニウムアルキルとマグネシウムアルキルの比率に換算して測定可能であり、それの範囲を約０．０１：１から約１０：１の範囲にしてもよい。この上に記述した触媒を用いて生じさせたポリエチレンが示すＭＷＤは少なくとも４．０であり得、それを約６．０にまで高くすることも可能である。
【００９５】
表５に示した触媒１０１はこの上に記述した如き実施例１と同じ触媒である。１つの態様における組成（重量パーセントで表す）は下記であった：Ｃｌが５３．４％；Ａｌが２．３％；Ｍｇが１１．８％およびＴｉが７．９％。各元素の範囲は下記であり得る：Ｃｌが４０．０−６５．０％；Ａｌが０．０−６．０％；Ｍｇが６．０−１５．０％およびＴｉが２．０−１４．０％。
【００９６】
表５に示した触媒１０２は１つの態様において下記であった：Ｃｌが４７．０％；Ａｌが３．４％；Ｍｇが１３．１％およびＴｉが４．０％。各元素の範囲は下記であり得る：Ｃｌが４０．０−６５．０％；Ａｌが０．０−６．０％；Ｍｇが６．０−１５．０％およびＴｉが２．０−１４．０％。
【００９７】
表５に示した触媒１０３は１つの態様において下記であった：Ｃｌが５０．０％；Ａｌが２．４％；Ｍｇが１２．１％およびＴｉが３．９％。各元素の範囲は下記であり得る：Ｃｌが４０．０−６５．０％；Ａｌが０．０−６．０％；Ｍｇが６．０−１５．０％およびＴｉが２．０−１４．０％。
【００９８】
表５に示した触媒１０４は１つの態様において下記であった：Ｃｌが５３．０％；Ａｌが３．１％；Ｍｇが１２．８％およびＴｉが４．２％。各元素の範囲は下記であり得る：Ｃｌが４０．０−６５．０％；Ａｌが０．０−６．０％；Ｍｇが６．０−１５．０％およびＴｉが２．０−１４．０％。
【００９９】
本発明のポリオレフィンはいろいろな用途、例えば押出し加工方法などで用いるに適し、それによって幅広い範囲の製品を生じさせるに適する。そのような押出し加工方法には、例えばブローンフィルム押出し加工、キャストフィルム押出し加工、スリットテープ押出し加工、ブロー成形、パイプ押出し加工および発泡シート押出し加工が含まれる。そのような加工には単層押出し加工または多層共押出し加工が含まれ得る。本発明を利用することができる最終使用用途には、例えばフィルム、繊維、パイプ、織物材料、製造品、おむつ構成要素、女性衛生品、自動車構成要素および医療用材料が含まれ得る。
【０１００】
本発明の代替態様に従い、数回の反応を包含する方法を用いてポリオレフィン重合用触媒を生じさせる。最初に、マグネシウムアルキル化合物［即ちＭｇ（Ｒ＊）_２（ここで、Ｒ＊は炭素原子数が約１から２０の同一もしくは異なるアルキル基であり得る）、例えばＢＥＭなど］を下記の反応：
ＢＥＭ＋２ＲＯＨ→Ｍｇ（ＯＲ）_２
（ここで、Ｒはアルキル基、例えば炭素原子を約１から２０個含有するアルキル基である）
に従ってアルコールと反応させることで可溶なマグネシウムアルコキサイド化合物を生じさせる。前記式ＲＯＨで表されるアルコールは分枝しているか或は分枝していなくてもよい。適切なアルコールの例は２−エチルヘキサノールである。ＢＥＭとアルコール反応体をマグネシウムアルコキサイド化合物に転化させるに適した如何なる反応条件も添加順も使用可能である。１つの態様では、前記アルコールをＢＥＭ溶液に添加することで反応混合物を生じさせて、それを周囲の温度および圧力下に維持する。この反応混合物の撹拌を可溶なマグネシウムアルコキサイド化合物が生じるに充分な時間行う。
【０１０１】
その結果として生じたマグネシウムアルコキサイド化合物を穏やかな塩素化剤と混合すると、下記の式：
Ｍｇ（ＯＲ）_２＋ＴｉＣｌ_ｎ（ＯＲ’）_４−ｎ→［Ｔｉ（ＯＲ’）_４−ｎＣｌ_ｎ・Ｍｇ（ＯＲ）_２］_ｍ
［式中、Ｒ’はアルキル、シクロアルキルまたはアリール基であり、ｎは１から３であり、そしてｍは少なくとも１であり、２以上であってもよい］
に従ってマグネシウム−チタン−アルコキサイド付加体が生じる。望ましくは、ｎは１である。反応体にＴｉＣｌ_ｎ（ＯＲ’）_４−ｎ［ここで、Ｒ’＝アルキルまたはアリール、そしてｎは１である］およびまたＴｉ（Ｏ^ｉＰｒ）_３Ｃｌ［ここで、^ｉＰｒはイソプロピルを表す］を含める。この過程では、そのようなマグネシウム−チタン−アルコキサイド付加体を生じさせるに適した如何なる条件も使用可能である。１つの態様では前記過程を周囲の温度および圧力下で実施する。前記反応体の混合をそのようなマグネシウム−チタン−アルコキサイド付加体が生じるに充分な時間行う。前記マグネシウム−チタン−アルコキサイド化合物が立体的に障害を受けていることで前記チタン化合物の塩素原子とマグネシウムアルコキサイド配位子の複分解が起こり難いことからそのような付加体が生じると考えている。本質的に、その付加体は全部ではないが大部分がＭｇＣｌ_２に転化する。
【０１０２】
その後、前記マグネシウム−チタン−アルコキサイド付加体とアルキルクロライド化合物をそれらが担体であるＭｇＣｌ_２に変化するように混合する。この反応は下記の如く進行する：
［Ｔｉ（ＯＲ’）_４−ｎＣｌ_ｎＭｇ（ＯＲ）_２］_ｍ＋Ｒ”Ｃｌ→「ＴｉＭｇＣｌ_２」＋Ｒ”ＯＲ
ここで、Ｒ”はアルキル基、例えば炭素原子を約２から１８個含有するアルキル基であり、そして「ＴｉＭｇＣｌ_２」はチタンが染み込んだ担体であるＭｇＣｌ_２を表す。Ｒ”は分枝しているか或は分枝していなくてもよいが、ある態様では、Ｒ”が分枝していない方が望ましい可能性がある。可能なアルキルクロライド化合物には、塩化ベンゾイル、クロロメチルエチルエーテルおよび塩化ｔ−ブチルが含まれ、特別な態様では塩化ベンゾイルが望ましい。前記マグネシウムアルコキサイド付加体に添加するアルキルクロライドの量はその反応に要する量より多い量であってもよい。この反応混合物に含めるＭｇ（例えばＢＥＭ）の量に対する塩化ベンゾイルの量の比率は約１から２０（即ち約１：１の比率から約２０：１の比率）の範囲であってもよいか、或は約１から１０であってもよく、約４から８の範囲にするのが望ましい可能性がある。この反応は塩化マグネシウムである担体が沈澱するに適した如何なる条件下でも実施可能である。１つの態様では、反応体を担体であるＭｇＣｌ_２が沈澱するに充分な時間還流させる。ｔ−ブチルクロライドを用いる態様では、その反応物を還流中に加熱してもよい。塩化ベンゾイルまたはクロロメチルエチルエーテルを用いる態様では、反応体を還流させている間の温度を室温にしてもよい。この反応ではまた１種以上の副生成物、例えばエーテル（この上に示した反応に示した）なども生じる。ＭｇＣｌ_２を沈澱させている間にＴｉを存在させるとそれが高い活性を示す触媒をもたらす点で主な役割を果たすと考えている。
【０１０３】
ＭｇＣｌ_２である担体を反応混合物から分離した後、その担体を例えばヘキサンなどで洗浄することでいくらか存在する汚染物をそれから除去してもよい。次に、ＭｇＣｌ_２である担体をＴｉＣｌ_４で処理すると下記の式に従って触媒のスラリーが生じる：
「ＭｇＣｌ_２」＋２ ＴｉＣｌ_４→触媒
この処理は触媒スラリーが生じるに適切な如何なる条件下でも実施可能であり、例えば周囲の温度および圧力下で実施可能である。この触媒スラリーを例えばヘキサンなどで洗浄した後、乾燥させる。その結果として得た触媒にアルキルアルミニウム化合物、例えばトリエチルアルミニウム（ＴＥＡｌ）などを用いた予活性化を受けさせることで、その触媒が重合反応槽を腐食しないようにしてもよい。より具体的には、前記触媒に含まれる塩化チタンをアルキルアルミニウム化合物と反応させるとそれはチタンアルキルに転化する。そうしないと、その塩化チタンが水分にさらされると変換を受けてＨＣｌが生じ、その結果として重合反応槽の腐食がもたらされる可能性がある。
２番目の組の実施例
本発明を一般的に記述してきたが、本発明の実施および利点を示す目的で以下の実施例を本発明の特定態様として示す。本実施例は説明として示すものであり、決して本明細書の範囲も請求項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。
【０１０４】
特に明記しない限り、標準的なシュレンク技術を用いて、あらゆる実験実施例を不活性な雰囲気下で実施した。本発明の方法に従って数種の触媒（サンプルＣ−Ｍ）を調製した。加うるに、サンプルＡおよびサンプルＢと呼ぶ２種類の通常触媒も調製したが、サンプルＢは、他の触媒サンプルと比較する目的で、米国特許第５，５６３，２２５号に従って調製したサンプルである。本実施例に必要な化合物の多く、即ち２−エチルヘキサノール、塩化ベンゾイル、塩化ｎ−ブチル、塩化ｔ−ブチル、クロロメチルエチルエーテル、ＣｌＴｉ（Ｏ^ｉＰｒ）_３およびＴｉＣｌ_４をＡｌｄｒｉｃｈ Ｃｈｅｍｉｃａｌ Ｃｏｍｐａｎｙから購入して、受け取ったまま用いた。ＢＥＭ含有量が１５．６重量％でＡｌ含有量が０．０４重量％のヘプタン溶液をＡｋｚｏ Ｎｏｂｅｌから購入した。触媒サンプル全部が示す触媒粒径分布（平均粒径Ｄ_５０を包含）の測定をＭａｌｖｅｒｎ Ｍａｓｔｅｒｓｉｚｅｒを用いて行い、そして本明細書に示す粒径分布値は全部体積平均を基に計算した値である。
【０１０５】
ヘキサンをPhillipsから購入して、３Ａモレキュラーシーブのカラム、Ｆ２００アルミナのカラムそしてＢＡＳＦ Ｒ３−１１銅触媒が充填されているカラムに１２ｍＬ／分の流量で通すことで精製を行った。エチレンを触媒サンプル各々の存在下で重合させる目的でAutoclave Engineer反応槽を用いた。この反応槽の容量は４リットルであり、これには向かい合う２個のピッチプロペラが備わっている混合用邪魔板が４個取り付けられている。ドーム装備背圧調節装置を用いて反応圧力を維持しかつ蒸気と冷水を用いて反応温度を維持しながらエチレンおよび水素を前記反応槽に導入した。ヘキサンを希釈剤として前記反応槽に導入した。特に明記しない限り、重合を表３Ａに挙げる条件下で実施した。結果として生じたポリエチレンが示す綿毛物粒径分布（質量を基準）をＣＳＣ Scientific Sieve Shakerを用いたふるい分け分析で得た。微細物のパーセントを１２５ミクロンより小さい綿毛物粒子の重量パーセントとして定義する。
参考例
ＢＥＭ含有量が１５．６重量％のヘプタン溶液（７０．８３ｇ、１００ミリモル）を１リットルの反応槽に仕込むことを通して、本発明触媒サンプルＡの調製を行った。次に、前記ＢＥＭ含有溶液に２−エチルヘキサノールを２６．４５ｇ（２０３ミリモル）ゆっくり加えた。この反応混合物を周囲温度で１時間撹拌した。次に、前記混合物にＣｌＴｉ（ＯⁱＰｒ）₃が１．０Ｍのヘキサン溶液７７．５０ｇ（１００ミリモル）をゆっくり加えた。この反応混合物を周囲温度で１時間撹拌することで［Ｍｇ（Ｏ−２−エチルヘキシル）２ＣｌＴｉ（ＯｉＰｒ）３］付加体を生じさせた。その後、その結果として生じた溶液にＴＮＢＴ（３４．０４ｇ、１００モル）とＴｉＣｌ₄（３７．８４ｇ、２００ミリモル）の混合物が入っているヘキサン溶液（２５０ｍＬ）を加えた。この反応混合物を周囲温度で１時間撹拌すると白色沈澱物が生じた。この沈澱物を沈降させた後、その上澄み液をデカンテーションで除去した。前記沈澱物を約２００ｍＬのヘキサンで３回洗浄した。その固体を約１５０ｍＬのヘキサンに入れることで再びスラリー状にした後、ＴｉＣｌ₄（１８．９７ｇ、１００ミリモル）が入っているヘキサン溶液を５０ｍＬ加えた。そのスラリーを周囲温度で１時間撹拌した。固体を沈降させた後、その上澄み液をデカンテーションで除去した。その固体を２００ｍＬのヘキサンで１回洗浄した。次に、その沈澱物にヘキサンを約１５０ｍＬ加えた。この触媒を再びＴｉＣｌ₄（１８．９７ｇ、１００ミリモル）が入っている５０ｍＬのヘキサン溶液で処理した。そのスラリーを周囲温度で１時間撹拌した。固体を沈降させた後、その上澄み液をデカンテーションで除去した。その触媒を２００ｍＬのヘキサンで２回洗浄した。次に、その沈澱物にヘキサンを約１５０ｍＬ加えた。それをＴＥＡｌが２５重量％入っているヘプタン溶液７．１６ｇ（１５．６ミリモル）と周囲温度で１時間反応させることで最終的な触媒を得た。
比較実施例１Ａ
１リットルのフラスコにジブチルマグネシウムが１５重量％入っているヘプタン溶液を３３０ｍｌ、テトライソブチルアルミノキサンが２０重量％入っているペンタン溶液を１３．３ｍＬ、ジイソアミルエーテルを３ｍｌおよびヘキサンを１５３ｍｌ導入することを通して、比較触媒サンプルＢの調製を行った。その混合物を５０℃で１０時間撹拌した。次に、０．２ｍｌのＴｉＣｌ₄およびｔ−ブチルクロライド（９６．４ｍＬ）とＤＩＡＥ（２７．７ｍＬ）の混合物を加えた。この混合物を５０℃で３時間撹拌した。沈澱物を沈降させた後、その上澄み液をデカンテーションで除去した。その固体を室温のヘキサン（１００ｍＬ）で３回洗浄した。その固体を１００ｍＬのヘキサンに入れることで再びスラリー状にした。この反応混合物に無水ＨＣｌを２０分間導入した。固体を濾過した後、１００ｍＬのヘキサンで２回洗浄した。その固体を再びヘキサンに入れて懸濁させた。このスラリーに高純度のＴｉＣｌ₄を５０ｍＬ加えた後、その混合物を８０℃で２時間撹拌した。上澄み液をデカンテーションで除去した後、その触媒を１００ｍＬのヘキサンで１０回洗浄した。この触媒をＮ₂流下５０℃で乾燥させた。
比較実施例２Ａ
本発明に従う触媒サンプルＣの調製を下記の如く行った：滴下漏斗と隔膜と凝縮器を取り付けておいた２５０ｍＬの３つ口丸底フラスコにＢＥＭ含有量が１５．６重量％のヘプタン溶液（１７．７１ｇ、２５ミリモル）を仕込んだ。次に、前記ＢＥＭ含有溶液に２−エチルヘキサノール６．６１ｇ（５１ミリモル）をゆっくり加えた後、この反応混合物を周囲温度で１時間撹拌した。次に、その溶液にＣｌＴｉ（ＯⁱＰｒ）₃（ヘキサン中１Ｍ）を１９．３８ｇ（２５ミリモル）加えた。この反応混合物を周囲温度で１時間撹拌することで［Ｍｇ（Ｏ−２−エチルヘキシル）₂ＣｌＴｉ（ＯⁱＰｒ）₃］付加体を生じさせた。次に、その結果として生じた溶液に塩化ｔ−ブチルを塩化ｔ−ブチルのＢＥＭに対するモル比が約８：１になるように１８．５１ｇ（２００ミリモル）加えた。この反応混合物を還流温度、即ち約８０℃で２４時間加熱することでＭｇＣｌ₂沈澱物（即ち次に触媒担体になる）を生じさせた。その白色沈澱物を沈降させた後、黄色がかった上澄み液をデカンテーションで除去した。その沈澱物を約１００ｍＬのヘキサンで３回洗浄した。次に、この沈澱物に約１００ｍＬのヘキサンを加えた後、その結果として生じた溶液にＴｉＣｌ₄（９．４８５ｇ、５０ミリモル）をゆっくり添加した。そのスラリーを周囲温度で１時間撹拌した。固体を沈降させた後、その上澄み液をデカンテーションで除去した。この触媒を５０ｍＬのヘキサンで４回洗浄した。
比較実施例３Ａ
前記フラスコに塩化ｔ−ブチルをより多い量で添加して反応速度を速める以外は比較実施例２Ａの手順に従うことで触媒サンプルＤを生じさせた。詳細には、前記フラスコに入っている溶液に塩化ｔ−ブチルを３７．０２ｇ（４００ミリモル）加えた後、その溶液を５５℃で２４時間加熱した。従って、その溶液には塩化ｔ−ブチル／ＢＥＭが約１６：１のモル比で入っていた（ＢＥＭに対して１６当量）。期待したように、比較実施例３Ａの方が比較実施例２Ａよりも収率が高いことを観察した。
【０１０６】
以下の表１Ａに、比較実施例１Ａおよび２Ａそして実施例１Ａおよび２Ａで生じさせた触媒の組成を示す。
【０１０７】
【表６】

【０１０８】
サンプルＣおよびＤにおけるＭｇおよびＣｌの量はサンプルＡにおけるそれらの量と同様であった。サンプルＣおよびＤにおけるＴｉの量はサンプルＡにおけるＴｉの量とＢにおけるＴｉの量の中間であった。
【０１０９】
実施例２Ａおよび３Ａでは、Ｔｉ（ＯⁱＰｒ）₃ＣｌＭｇ（ＯＲ）₂］_nと塩化ｔ−ブチルを反応させた時の副生成物をプロトン核磁気共鳴（¹Ｈ ＮＭＲ）およびガスクロ質量分光（ＧＣＭＳ）分析で測定した。主副生成物は予測したｔ−ブチル２−エチルヘキシルエーテルでもｔ−ブチル−２−イソプロピルエーテルでもなく２−エチルヘキサノールであることを確認した。この結果を基にして、前記混合物の中である種の還元反応が起こったことで恐らくはイソブテンが生じたと仮定し、それを反応から除去する。図１ＡにサンプルＡ−Ｄが示した粒径分布を示す。サンプルＡおよびＢの触媒は両方ともが狭い粒子分布を示す。サンプルＢの触媒が示した平均粒径の方がサンプルＡのそれよりも若干大きい。塩化ｔ−ブチルを用いて生じさせた触媒サンプルＣおよびＤはより幅広い二頂分布を示す。
比較実施例４Ａ
塩化ｔ−ブチルの代わりに第一級塩化物である塩化ｎ−ブチルをフラスコに加えて塩化ｎ−ブチル／ＢＥＭのモル比が約１６：１（ＢＥＭに対して１６当量）の溶液を生じさせる以外は比較実施例２Ａの手順に従った。不幸なことに、塩化ｎ−ブチルを用いると５０℃に２４時間加熱した後でも［Ｔｉ（ＯⁱＰｒ）₃ＣｌＭｇ（ＯＲ）₂］_nの沈澱を起こさせることができなかった。このような観察は塩素置換機構に安定なカルボカチオン種が必要な解離除去（dissociative elimination）（Ｅ１）段階が関与することを示唆すると仮定する。
比較実施例５Ａ
触媒サンプルＫの調製を下記の如く行った：滴下漏斗と隔膜と凝縮器を取り付けておいた５００ｍＬの３つ口丸底フラスコにＢＥＭ含有量が１５．６重量％のヘプタン溶液（８．８５ｇ、１２．５ミリモル）およびヘキサン１００ｍＬを仕込んだ。次に、前記ＢＥＭ含有溶液に２−エチルヘキサノール３．３１ｇ（２５ミリモル）をゆっくり加えた後、この反応混合物を周囲温度で１時間撹拌した。次に、前記混合物にＣｌＴｉ（ＯⁱＰｒ）₃９．６９ｇ（１２．５ミリモル）をゆっくり加えた後、この反応混合物を周囲温度で１時間撹拌した。次に、前記溶液に塩化ベンゾイル（ＰｈＣＯＣｌ）をＰｈＣＯＣｌのＢＥＭに対するモル比が約１０：１（ＢＥＭに対して１０当量）になるように１７．６ｇ（１２５ミリモル）加えた。この反応混合物を周囲温度で２時間撹拌することでＭｇＣｌ₂沈澱物を生じさせた。この白色沈澱物を沈降させた後、その上澄み液をデカンテーションで除去した。その沈澱物を１００ｍＬのヘキサンで３回洗浄した。その後、この沈澱物にヘキサンを１００ｍＬ加えた後、その溶液にＴｉＣｌ₄（４．２５ｇ、２５ミリモル）をゆっくり添加した。その結果として生じたスラリーを室温で１時間撹拌した。黄色がかった固体を沈降させた後、黄色の上澄み液をデカンテーションで除去した。この触媒を５０ｍＬのヘキサンで３回洗浄した。
【０１１０】
注目すべきは、ＰｈＣＯＣｌを用いて担体であるＭｇＣｌ₂を生じさせる反応では、塩化ｔ−ブチルとの反応の場合のような加熱を行う必要がなかった。また、図３に示すように、ＰｈＣＯＣｌを用いて生じさせた触媒サンプルＫが示した粒径分布も触媒サンプルＡおよびＢが示した粒径分布に匹敵していた。
比較実施例６Ａ−１１Ａ
各場合ともＰｈＣＯＣｌの量をＢＥＭに対するモル当量が１．２から７．２の範囲になるように変える以外は実施例４Ａの手順に従うことで更に６種類のサンプル（サンプルＥ−Ｊ）を調製した。
【０１１１】
図４に、比較実施例５Ａ−１１Ａの場合の触媒の収率をＰｈＣＯＣｌ使用量の関数として示す。触媒の収率はＰｈＣＯＣｌ濃度を高くするにつれて最初は高くなった後、約７．０の当量の時に一定になり、約１．７ｇの最大収率に到達した。以下の表２Ａに、比較実施例５Ａ−１１Ａで生じさせた触媒の組成を示す。
【０１１２】
【表７】

【０１１３】
表２Ａに示すように、チタン含有量はＰｈＣＯＣｌ濃度が６．０当量になるまではそれの濃度を高くするにつれて低下しそして当量をより高くしても一定のままであった。触媒サンプルＨ−ＫのＴｉ含有量は触媒サンプルＢのそれと同様であったが、触媒サンプルＡのそれよりも低かった。このようなチタン量低下の可能な説明は、ベンゾイルエステル生成物または未反応のＰｈＣＯＣｌが関与している可能性があると言った説明である。ＮＭＲおよびＧＣＭＳ分析で塩素化反応の主副生成物は安息香酸２−エチルヘキシルおよび安息香酸イソプロピルであることを確認した。そのようなエステルおよび未反応のＰｈＣＯＣｌは全部ルイス塩基であり、これらは電子不足のチタンもしくはマグネシウムと錯体を形成し得る。そのような錯体の形成によってチタンが担体からより多い量で抽出されるであろうと考えている。また、担体であるＭｇＣｌ_２との錯体形成によって次のチタン化でＴｉＣｌ_４が起こすエピタキシャル置換が邪魔されるであろうとも考えている。ＰｈＣＯＣｌの当量が７当量を超えるとチタン濃度が一定になることは興味の持たれることである。この値はＣｌＴｉ（Ｏ^ｉＰｒ）_３およびＭｇ（ＯＲ）_２の全部が塩素化されたことに相当する。ＰｈＣＯＣｌの量がそのような量を超えると、また、エステルの量も一定になり、このことは、そのエステルが最終触媒中のチタン量を決める点で重要な役割を果たしていることを示唆している。
【０１１４】
ＰｈＣＯＣｌをいろいろな濃度で用いて生じさせた触媒サンプルＥ−ＨおよびＩ−Ｋが示した粒径分布をそれぞれ図５および６に示す。ＰｈＣＯＣｌの濃度を最も低くして（ＢＥＭに対して１．２当量にして）生じさせたサンプルＥは幅広い二頂分布を示した。ＰｈＣＯＣｌの濃度を高くするとより狭い一頂分布を示す触媒がもたらされ、従って触媒の形態が向上した。その上、図７に示すように、ＰｈＣＯＣｌの濃度を高くすると平均粒径（Ｄ₅₀）も若干小さくなった。ＰｈＣＯＣｌとエステル生成物の両方ともが生じさせる担体であるＭｇＣｌ₂上の飽和状態ではないマグネシウム部位と錯体を形成し得ると仮定する。この上に記述したように、そのようなルイス塩基は生じさせる担体からチタンが抽出されるのを補助する可能性がある。このように、チタン錯体が存在しないようにすることで担体形成の原動力を修正することができると考えている。
比較実施例１２Ａ
触媒サンプルＬの調製を下記の如く行った：滴下漏斗と隔膜と凝縮器を取り付けておいた２５０ｍＬの３つ口丸底フラスコにＢＥＭ含有量が１５．６重量％のヘプタン溶液（４．４３ｇ、６．２５ミリモル）およびヘキサンを３０ｍＬ仕込んだ（３０ｍＬ）。次に、前記ＢＥＭ含有溶液に２−エチルヘキサノール１．６６ｇ（１２．５ミリモル）をゆっくり加えた後、この反応混合物を周囲温度で１時間撹拌した。その後、前記混合物にＣｌＴｉ（ＯⁱＰｒ）₃溶液（ヘキサン中１Ｍ、４．８５ｇ、６．２５ミリモル）をゆっくり加えた後、この反応混合物を周囲温度で１時間撹拌した。次に、前記溶液にクロロメチルエチルエーテル（ＣＭＥＥ）（９．４５ｇ、１００ミリモル）が入っているヘキサン溶液（２５ｍＬ）をＣＭＥＥのＢＥＭに対するモル比が約８：１（ＢＥＭに対して８当量）になるように加えた。この反応混合物を周囲温度で１時間撹拌すると結果としてＭｇＣｌ₂沈澱物が生じた。この白色沈澱物を沈降させた後、その上澄み液をデカンテーションで除去した。その沈澱物を５０ｍＬのヘキサンで３回洗浄した。次に、この沈澱物にヘキサンを３０ｍＬ加えた後、その溶液にＴｉＣｌ₄（２．１３ｇ、１２５ミリモル）のヘキサン溶液（３０ｍＬ）をゆっくり添加した。その結果として生じたスラリーを周囲温度で１時間撹拌した。黄色がかった固体を沈降させた後、黄色の上澄み液をデカンテーションで除去した。その後、この触媒を５０ｍＬのヘキサンで３回洗浄した。
【０１１５】
図９に、ＣＭＥＥが基になった触媒サンプルＬ、ＰｈＣＯＣｌが基になった触媒サンプルＫおよび触媒サンプルＡおよびＢが示した粒径分布を示す。前記ＣＭＥＥが基になった触媒サンプルが示した粒径分布の方がサンプルＡ、サンプルＢおよびＰｈＣＯＣｌが基になった触媒サンプルＫが示したそれよりも若干広い。前記ＣＭＥＥが基になった触媒が示した粒径分布には約７ミクロンの所にショルダーが存在する。
比較実施例１２Ａ
触媒サンプルＡおよびＴＥＡｌ共触媒の存在下でエチレンを表３Ａに挙げた条件下で重合させた。
比較実施例１３Ａ
触媒サンプルＢおよびＴＥＡｌ共触媒の存在下でエチレンを表３Ａに挙げた条件下で重合させた。
比較実施例１４Ａ
塩化ｔ−ブチルを用いて生じさせた触媒サンプルＣおよびＤを用いてエチレンを表３Ａに挙げる条件下で重合させた。図９に、比較実施例１４Ａそして実施例２Ａおよび比較実施例１３Ａで生じさせた重合体が示した綿毛物粒径分布を示す。触媒サンプルＣおよびＤを用いた時に得た粒径分布は非常に広い。それとは対照的に、触媒サンプルＡおよびＢを用いた時に得た分布は相対的に狭い。サンプルＣおよびＤを用いた時に得た綿毛物に含まれる微細物の方がサンプルＡおよびＢを用いた時に得た綿毛物に含まれるそれよりも多かった。また、サンプルＣおよびＤを用いた時に得た綿毛物が示したかさ密度も相対的に低かった。
【０１１６】
【表８】

【０１１７】
以下の表４Ａに、触媒サンプルＡ、Ｂ、ＣおよびＤを用いて生じさせた重合体樹脂が示した特性を示す。
【０１１８】
【表９】

【０１１９】
各触媒サンプルが示した活性（マグネシウムが基準）の測定では、最初に当該触媒およびそれを用いて生じさせた重合体を酸に溶解させて残存するＭｇを抽出することで測定を実施した。残存Ｍｇ含有量を基にして触媒活性を決定した。表４Ａに示すように、触媒サンプルＣが示したＭｇ基準活性の方が触媒サンプルＡが示したそれよりも若干低くかつ触媒サンプルＢが示したそれよりも高かった。触媒サンプルＤが示した活性の方が触媒サンプルＡおよびＢが示した活性よりも高かった。これらの触媒サンプルを用いて生じさせた重合体が示すせん断反応（shear response）の計算では、高荷重のメルト
インデックス（ＨＬＭＩ）のメルトインデックスに対する比率を確認することで計算を行った。触媒サンプルＣおよびＤを用いて生じさせた重合体が示したせん断反応はサンプルＢを用いて生じさせた重合体が示したせん断反応に類似していたが、サンプルＡを用いて生じさせた重合体が示したせん断反応よりも若干低かった。生じたワックスの量は全ての重合体で匹敵していた。
比較実施例１５Ａ
塩化ベンゾイルを用いて生じさせた触媒サンプルＥ−Ｋを用いてエチレンを表３Ａに挙げる条件下で重合させた。図１０Ａに、この実施例（サンプルＧ−Ｋ）で生じさせた重合体が示した綿毛物粒径分布を示す。ＰｈＰＯＣｌが基になった樹脂が示した平均粒径（Ｄ₅₀）はサンプルＡおよびサンプルＢの樹脂が示したそれに比べて大きかった。
【０１２０】
以下の表５Ａに、ＰｈＰＯＣｌ触媒サンプルの形態とこのＰｈＰＯＣｌ触媒サンプルを用いて生じさせた重合体が示した形態の比較を示す。
【０１２１】
【表１０】

【０１２２】
複製理論を基にして、重合体の形態は触媒の形態と関連している可能性がある。しかしながら、サンプルＦ−Ｋの場合には重合体の形態が触媒の形態に対応しない（即ち比例しない）と思われる一方、サンプルＡおよびＢの場合には対応するように思われる。
【０１２３】
以下の表６Ａに、ＰｈＰＯＣｌ触媒サンプル（サンプルＥ−Ｋ）および触媒サンプルＡおよびＢを用いて生じさせた重合体が示した特性を示す。
【０１２４】
【表１１】

【０１２５】
サンプルＥ−Ｋが示したＭｇ基準活性の方がサンプルＡおよびＢが示した活性よりも高い。活性はサンプルＫ（ＰｈＰＯＣｌの当量は１０である）を除いて一般にＰｈＰＯＣｌの当量を高くするにつれて低下した。サンプルＥ−Ｋの重合体の密度はサンプルＡおよびＢの重合体の密度と同様であった。サンプルＥ−Ｋの重合体およびサンプルＡの重合体が示したメルトフロー率（即ちメルトインデックス）の方がサンプルＢの重合体が示したそれよりも高かった。サンプルＥ−Ｋの重合体が示したせん断反応はサンプルＢの重合体が示したそれと同様であったが、サンプルＡの重合体が示したそれよりも若干低かった。生じたワックスの量は全ての重合体で匹敵していた。
比較実施例１６Ａ
この上に記述したように、ＭｇＣｌ₂沈澱物をヘキサンで洗浄することで、ＰｈＣＯＣｌが基になった触媒サンプルＩ（本明細書では以降「サンプルＩ₁」と識別）を調製した。この実施例では、サンプルＩ₁から洗浄段階を省いて同じ様式で生じさせた別の触媒サンプルＩ₂と触媒サンプルＩ₁を比較する。そのように洗浄段階をなくすと触媒製造における時間が有意に短縮されかつ費用も低くなる可能性があると考えている。以下の表７Ａに、サンプルＩ₁とサンプルＩ₂の触媒組成を示す。
【０１２６】
【表１２】

【０１２７】
洗浄段階をなくすと結果としてチタン濃度が約３０％低くなった。洗浄した触媒サンプルＩ_１の外観の色は明黄色であった。また、洗浄していない触媒サンプルＩ_２でもＴｉＣｌ_４を添加している間の色は黄色であることは明らかであった。しかしながら、ＴｉＣｌ_４を母液と接触させると直ちに無色になった。エステルとＴｉＣｌ_４の錯体は黄色をもたらし得るがＴｉＣｌ_４がＰｈＣＯＣｌと反応すると無色の化合物が生じ得ると仮定する。このような観察は、チタンの濃度がＰｈＣＯＣｌの量に依存すると言ったこの上で行った考察を裏付けている。余分なＰｈＣＯＣｌおよびエステルを除去しておかないとそれらはＴｉＣｌ_２および担体表面の両方と一緒に錯体を形成することでチタンが担体表面に付着しなくなると考えている。
【０１２８】
図１１に示すように、サンプルＩ_１およびサンプルＩ_２が示した粒径分布はほとんど同じであった。従って、触媒の粒径分布は洗浄段階の影響を受けなかった。このような観察はあまり驚くべきことではない、と言うのは、洗浄段階を実施したのは担体であるＭｇＣｌ_２を生じさせた後であったからである。サンプルＩ_１およびサンプルＩ_２の両方を用いてエチレンを重合させた。以下の表８Ａに、サンプルＩ_１およびサンプルＩ_２の触媒形態および重合体形態を示す。
【０１２９】
【表１３】

【０１３０】
表８Ａは、更に、粒径分布が洗浄段階の影響を受けないと言った結論を裏付けている。洗浄段階をなくすと重合体に含まれる生じた微細物の数が有意に多くなった。このように微細物が多くなった理由は生産性が低くなったことによる可能性がある。触媒サンプルＩ_１およびサンプルＩ_２を用いて生じさせた重合体の特性を以下の表９Ａに示す。
【０１３１】
【表１４】

【０１３２】
表９Ａに示すように、洗浄を受けさせなかった触媒が示した重合活性は洗浄を受けさせた触媒が示したそれのほぼ半分であった。２種類の重合体が示した密度はほとんど同じであった。しかしながら、せん断反応データは、洗浄を受けさせなかった触媒を用いた時の分子量分布の方が洗浄を受けさせた触媒のそれよりも狭いことを示している。触媒の中にＰｈＣＯＣｌおよびエステルが存在しているとその触媒の中の活性部位の分布に影響が生じると考えている。
比較実施例１７Ａ
また、ＢＥＭ濃度が触媒の特性に対して示す影響も研究した。１００ｍＬのヘキサンで希釈しておいたＢＥＭ溶液を用いてＰｈＣＯＣｌが基になった１番目の触媒サンプル（サンプルＬ）を調製した。比較の目的で、２０ｍＬのヘキサンで希釈しておいたＢＥＭ溶液を用いてＰｈＣＯＣｌが基になった２番目の触媒サンプル（サンプルＭ）を調製した。図１２に、触媒サンプルＬおよびＭが示した触媒粒径分布を示す。両方の触媒とも分布は非常に類似している。触媒サンプルＬおよびＭそしてそれらを用いて生じさせた重合体の組成および特性をそれぞれ以下の表１０Ａおよび１１Ａに示す。
【０１３３】
【表１５】

【０１３４】
【表１６】

【０１３５】
表１０Ａおよび１１Ａは、触媒の組成および重合体の特性はＢＥＭの濃度の影響を本質的に受けないことを示している。
【０１３６】
結論として、アルキルクロライド、例えば塩化ｎ−ブチル、塩化ｔ−ブチルおよびクロロメチルエチルエーテルなどを用いて新規な触媒を合成した。塩化ベンゾイルおよびクロロメチルエチルエーテルを用いると満足される粒径分布を示す触媒が生じる一方、塩化ｔ−ブチルを用いると結果として二頂分布がもたらされ、そして塩化ｎ−ブチルを用いるとＭｇＣｌ_２を生じさせることができなかった。マグネシウムアルコキサイド付加体に添加する塩化ベンゾイルの量を変えることで触媒調製を最適にした。期待したように、触媒の収率は塩化ベンゾイルの量を多くするにつれて高くなりそしてＢＥＭを基準にした塩化ベンゾイルの当量がほぼ７当量になった時点で飽和状態になった。触媒の粒径分布は塩化ベンゾイルの量を多くするにつれて狭くなった。
【０１３７】
また、担体を生じさせた後に行う洗浄段階をなくした時の影響を観察する実験も実施した。洗浄を受けさせなかった触媒サンプルは洗浄を受けさせたサンプルに比べて示した活性が低くかつせん断反応も低かった。また、ＢＥＭ濃度が触媒特性に対して示す影響も調査した。粒径分布も触媒組成も重合体特性もＢＥＭの濃度の影響を受けなかった。
【０１３８】
本発明の態様を示しかつ説明してきたが、本分野の技術者は本発明の精神および教示から逸脱しない限りそれの修飾を行うことができる。本明細書に記述した態様は単に例示であり、限定を意図したものでない。化学的機構または理論を開示する場合、それは情報および考えを基に示すものであり、必ずしもそれによって範囲を限定することを意図するものでない。本明細書に開示した発明のいろいろな変形および修飾が可能であり、それらも本発明の範囲内である。従って、保護の範囲をこの上に挙げた説明で限定するものでなく、限定するのは本請求の範囲のみであるが、その範囲には本請求の範囲の主題事項のあらゆる均当物が含まれる。
【図面の簡単な説明】
【０１３９】
【図１】図１に、本発明の触媒（実施例１）を用いて生じさせた重合体および通常の触媒（比較実施例４）を用いて生じさせた重合体が示した沈降効率曲線（ｓｅｔｔｌｉｎｇ ｅｆｆｉｃｉｅｎｃｙ）を示す。
【図２】図２に、比較実施例１Ａ−２Ａおよび実施例１Ａ−２Ａに記述した触媒が示した粒径分布を示す。
【図３】図３に、比較実施例１Ａ−２Ａおよび実施例４Ａに記述した触媒が示した粒径分布を示す。
【図４】図４に、実施例４Ａ−１０Ａの場合の触媒の収率をＰｈＣＯＣｌ使用量の関数として示す。
【図５】図５に、実施例４Ａ−１０Ａで生じさせた触媒が示した粒径分布を示す。
【図６】図６に、実施例４Ａ−１０Ａで生じさせた触媒が示した粒径分布を示す。
【図７】図７に、実施例４Ａ−１０Ａの場合の平均触媒粒径（Ｄ_５０）をＰｈＣＯＣｌ使用量の関数として示す。
【図８】図８に、比較実施例１Ａ−２Ａおよび実施例４Ａおよび１１Ａに記述した触媒が示した粒径分布を示す。
【図９】図９に、比較実施例３Ａ−４Ａおよび実施例１２Ａに記述した重合体樹脂が示した綿毛物粒径分布を示す。
【図１０】図１０に、比較実施例３Ａ−４Ａおよび実施例１３Ａに記述した重合体樹脂が示した綿毛物粒径分布を示す。
【図１１】図１１に、実施例１４Ａに記述した触媒が示した粒径分布を示す。
【図１２】図１２に、実施例１５Ａに記述した触媒が示した粒径分布を示す。[Cross-reference of related applications]
[0001]
  This application is filed on Jan. 28, 1997 under the title “Ziegler-Natta Catalysts for Olefin Polymerization”, U.S. Patent Application Serial No. 08 / 789,862, dated Jan. 16, 2001, U.S. Pat. No. 174,971, which was issued as a continuation-in-part of US Patent No. 174,971, which is hereby incorporated by reference), entitled "Ziegler-Natta Catalyst For Narrow To". US Patent Application Serial No. 09 / 687,5 of “Broad MWD of Polyolefins, Method of Making, Method of Using, And Polyolefins Made Thewith” 0 (which is also incorporated herein by reference) which is a continuation-in-part application of.
【Technical field】
[0002]
  The present invention generally 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. More particularly, the present invention relates to polyolefin catalysts and Ziegler-Natta catalysts, methods for making the catalysts, methods for using the catalysts, polymerization of polyolefins and polyolefins.
[Background]
[0003]
  Olefin (also called alkene) is an unsaturated hydrocarbon containing one or more pairs of carbon atoms in which the molecules are linked together by double bonds. By subjecting olefins to a polymerization step, they can be converted to polyolefins such as polyethylene and polypropylene. One commonly used polymerization method involves contacting an olefin monomer with a Ziegler-Natta type catalyst system. Various Ziegler-Natta type polyolefin catalysts, their general preparation and subsequent use are well known in the polymerization art. Such systems typically contain a Ziegler-Natta type polymerization catalyst component, a cocatalyst and an electron donor compound. The Ziegler-Natta type polymerization catalyst component can be a complex derived from a transition metal, for example a halide such as titanium, chromium or vanadium and a metal hydride and / or metal alkyl (typically an organoaluminum compound). . Such a catalyst component is generally composed of a titanium halide supported on a magnesium compound and forming a complex with an alkylaluminum. There are numerous issued patents relating to catalysts and catalyst systems designed primarily for the polymerization of propylene and ethylene, which are known to those skilled in the art. Examples of such catalyst systems are given in US Pat.
[0004]
  A typical Ziegler-Natta catalyst has the formula MR_x[Wherein M is a transition metal compound, R is halogen or hydrocarboxyl, and x is the valence of the transition metal]. M is typically selected from Group IV to Group VII metals such as titanium, chromium or vanadium, and R is a chlorine, bromine or alkoxy group. Common transition metal compounds are TiCl₄, TiBr₄, Ti (OC₂H₅)₃Cl, Ti (OC₃H₇)₂Cl₂, Ti (OC₆H₁₃)₂Cl₂, Ti (OC₂H₅)₂Br₂And Ti (OC₁₂H₂₅) Cl₃It is. Such transition metal compounds are typically supported on an inert solid such as magnesium chloride.
[0005]
  The Ziegler-Natta catalyst is generally supported on a support, that is, deposited on a solid crystalline support. Such a support can be an inert solid that does not chemically react with any of the components contained in a conventional Ziegler-Natta catalyst. Such carriers are often magnesium compounds. Examples of magnesium compounds that can be used for the purpose of providing a carrier source for the catalyst component are magnesium halides, dialkoxymagnesium, alkoxymagnesium halides, magnesium oxyhalides, dialkylmagnesium, magnesium oxide, magnesium hydroxide and magnesium carboxylic acids Salt.
[0006]
  The properties of the polymer produced using such a polymerization catalyst can be influenced by the properties of the catalyst. For example, the polymer morphology typically depends on the catalyst morphology. Good polymer morphology includes uniformity of particle size and shape and satisfaction of bulk density. In addition, minimizing the number of very small polymer particles (ie fines) is desirable for a variety of reasons, such as avoiding clogging of the transfer or recirculation lines. Also, very large particles should be minimized so that lumps and threads do not form in the polymerization reactor.
[0007]
  Another polymer property that is affected by the type of catalyst used is molecular weight distribution (MWD), which refers to the range of variation in the length of the molecules contained in a given polymer resin. For example, in the case of polyethylene, tight toughness, i.e. perforation, tension and impact performance can be improved with a narrow MWD. On the other hand, if the MWD is wide, processing can be facilitated and the melt strength can be improved.
[0008]
  Various things are known about Ziegler-Natta catalysts, but research continues to improve the polymer yields, catalyst life, catalyst activity and ability to produce polyolefins with specific properties Has been done.
[Patent Document 1]
US Pat. No. 4,107,413
[Patent Document 2]
U.S. Pat. No. 4,294,721
[Patent Document 3]
U.S. Pat. No. 4,439,540
[Patent Document 4]
U.S. Pat. No. 4,114,319
[Patent Document 5]
U.S. Pat. No. 4,220,554
[Patent Document 6]
U.S. Pat. No. 4,460,701
[Patent Document 7]
U.S. Pat. No. 4,562,173
[Patent Document 8]
US Pat. No. 5,066,738
[Patent Document 9]
US Pat. No. 6,174,971
DISCLOSURE OF THE INVENTION
[Means for Solving the Problems]
[0009]
  In one aspect of the present invention, a method for producing a catalyst is provided, the method comprising: a) contacting a magnesium dialkoxide compound with a halogenating agent to produce reaction product A; b) reaction product A. Is brought into contact with the first halogenation / titanium agent to give reaction product B, and c) reaction product B is brought into contact with the second halogenation / titanium agent to give reaction product C. And d) contacting reaction product C with a third halogenation / titanating agent to form reaction product D. Titanium tetrachloride may be included in the second and third halogenation / titanium agents. The ratio of titanium to magnesium included in each of the second and third halogenation / titanation stages may range from about 0.1 to 5. Each of the reaction products A, B and C may be washed with a hydrocarbon solvent before being subjected to the next halogenation / titanation step. Reaction product D may be washed with a hydrocarbon solvent until the titanium species [Ti] content is less than about 100 mmol / L.
[0010]
  In another aspect of the present invention, there is provided a catalyst for polyolefins produced by a process generally comprising contacting the catalyst component of the present invention with an organometallic agent. The catalyst component is a catalyst component produced by a method as described above. The catalyst of the present invention can have a fluff morphology suitable for the polymerization production process, which can be used to produce polyethylene having a molecular weight distribution of at least 5.0 and less than about 125 microns. A uniform particle size distribution with a low concentration of particles can result. The activity of the catalyst depends on the polymerization conditions. The activity exhibited by the catalyst is generally an activity that yields at least 5,000 g PE per gram of catalyst, but also an activity that yields more than 50,000 g PE per gram catalyst or 100,000 g PE per gram catalyst. It is also possible to make it higher.
[0011]
  In yet another embodiment of the invention, the method comprises a) contacting one or more olefin monomers together in the presence of the catalyst of the invention under polymerization conditions and b) extracting the polyolefin polymer. A polyolefin polymer produced by the method is provided. The monomer is generally an ethylene monomer and the polymer is polyethylene.
[0012]
  In yet another aspect of the present invention there is provided a film, fiber, pipe, textile material or article of manufacture comprising the polymer produced by the present invention. Such an article may be a film containing at least one layer comprising a polymer formed in a process including the catalyst of the present invention.
[0013]
  In another aspect of the present invention, when the catalyst component is precipitated from the catalyst synthesis solution, an aluminum alkyl is added to control the viscosity of the catalyst synthesis solution so that the average particle size of the catalyst component is within the synthesis solution. There is provided a process for preparing a catalyst comprising modifying a precipitate to increase as the concentration of aluminum alkyl increases. In this method, further, the catalyst component is an organometallic organic activator so that the average particle size of the catalyst increases as the concentration of aluminum alkyl in the synthesis solution increases as the catalyst is formed. contacting with a preactivating agent) may also be included.
[0014]
  In another embodiment of the present invention, a) contacting the magnesium dialkoxide compound with a halogenating agent yields reaction product A, and b) contacting the reaction product A with the first halogenating / titanating agent. To produce reaction product B, c) contacting reaction product B with a second halogenation / titanating agent to yield reaction product C, and d) reacting product C to the third. A catalyst comprising contacting reaction product D with a halogenated / titanating agent and e) forming a catalyst by contacting reaction product D with a pre-activator that is an organometallic. A manufacturing method is provided. The magnesium dialkoxide compound has a general formula MgRR ′ [wherein R and R ′ are alkyl groups having 1 to 10 carbon atoms, which may be the same or different] and a general formula A linear or branched alcohol represented by the formula R ″ OH [wherein R ″ is an alkyl group having 2 to 20 carbon atoms] and a formula AlR ″ ′₃Wherein at least one R ″ ′ is an alkyl or alkoxide or halide having 1 to 8 carbon atoms, and each R ″ ′ may be the same or different. Is a reaction product of the reaction. The average particle size of the catalyst increases as the ratio of aluminum alkyl to magnesium alkyl increases.
[0015]
  Titanium tetrachloride may be included in the second and third halogenation / titanium agents. The ratio of titanium to magnesium included in each of the second and third halogenation / titanium stages may be in the range of about 0.1 to 5. Each of reaction products A, B and C may be washed with a hydrocarbon solvent prior to being subjected to the next halogenation / titanation step. Reaction product D is washed with a hydrocarbon solvent until the titanium species [Ti] content is less than about 100 mmol / L.
[0016]
  In yet another embodiment of the present invention, the method comprises a) contacting one or more olefin monomers together under polymerization conditions in the presence of the catalyst of the present invention and b) extracting the polyolefin polymer. A polyolefin polymer produced by the method is provided. The average particle size of the polymer increases as the ratio of aluminum alkyl to magnesium alkyl used in the preparation of the catalyst increases. The monomer is generally an ethylene monomer and the polymer is polyethylene.
[0017]
  In yet another aspect of the present invention, there is provided a film, fiber, pipe, textile material or article of manufacture comprising a polymer produced using the present invention. This article may be a film containing at least one layer comprising a polymer prepared using the present invention.
[0018]
  Another embodiment includes a method for producing a catalyst suitable for use in the polymerization of olefins. This method is magnesium chloride by reacting a chlorinating agent with a magnesium alkoxide compound to form a magnesium-titanium-alkoxide adduct and reacting the magnesium-titanium-alkoxide adduct with an alkyl chloride compound. Producing a carrier. Next, the carrier is titanium tetrachloride (TiCl₄To give a highly active catalyst useful in the production of polyolefins.
[0019]
  In one embodiment of the invention, an alcohol generally represented by butylethylmagnesium (BEM) and the formula ROH, wherein R is an alkyl group, such as an alkyl group containing about 1 to 20 carbon atoms. To form a magnesium alkoxide compound first. The magnesium alkoxide compound is then represented by the formula:
                      TiCl_n(OR ’)_4-n
Wherein R 'is an alkyl, cycloalkyl or aryl group, and n is 1 to 3.
Combined with a chlorinating agent generally represented by Mixing the magnesium alkoxide compound and the chlorinating agent results in a magnesium-titanium-alkoxide adduct.
[0020]
  When an alkyl chloride compound is reacted with the magnesium-titanium-alkoxide adduct, magnesium chloride (MgCl₂) And one or more by-products such as ethers and / or alcohols. Next, the MgCl₂TiCl₄MgCl after treatment with₂The Ziegler-Natta catalyst supported on the catalyst is produced. Polyolefins produced using this catalyst exhibit a narrow molecular weight distribution and can therefore be formed into end-use products such as barrier films, fibers and pipes.
BEST MODE FOR CARRYING OUT THE INVENTION
[0021]
  In general, a method for producing a catalyst component according to one embodiment of the present invention includes generating a reaction product by generating a metal dialkoxide from a metal dialkyl and an alcohol, and subjecting the metal dialkoxide to halogenation. After the product is brought into contact with one or more halogenation / titanium agents in three or more stages to form a catalyst component, the catalyst component is treated with a preactivator, such as organoaluminum. Includes stages.
[0022]
  One aspect of the present invention may generally be as follows:
1. MRR ′ + 2R ″ OH → M (OR ″)₂
2. M (OR ")₂+ ClAR ”’_x→ "A"
3. "A" + TiCl₄/ Ti (OR "")₄→ "B"
4). “B” + TiCl₄→ "C"
5). “C” + TiCl₄→ "D"
6). “D” + preactivator → catalyst
  M in the above formula can be any suitable metal, usually a Group IIA metal, typically Mg. Wherein R, R ′, R ″, R ″ ′ and R ″ ″ are each independently a hydrocarbyl or substituted hydrocarbyl moiety, wherein R and R ′ have 1 to 20 carbon atoms, Generally, it has 1 to 10 carbon atoms, typically 2 to 6 carbon atoms, but may have 2 to 4 carbon atoms. R ″ generally has 3 to 20 carbon atoms, R ″ ′ typically has 2-6 carbon atoms, and R ″ ″ typically has 2-6 carbon atoms, which is typically Is butyl. Any combination of two or more of R, R ′, R ″, R ″ ′ and R ″ ″ can also be used and may be the same or the combination of R groups may be different from each other .
[0023]
  Said embodiment is of the formula ClAR "'_xA is a non-reducing oxyphilic compound capable of exchanging one chloride for one alkoxide, R ″ ′ is hydrocarbyl or substituted hydrocarbyl; And x is 1 minus the valence of A. Examples of A include titanium, silicon, aluminum, carbon, tin and germanium, which is typically titanium or silicon, where x is 3 Examples of R ″ ′ include methyl, ethyl, propyl, isopropyl and analogs having 2-6 carbon atoms. Non-limiting examples of chlorinating agents that can be used in the present invention include ClTi (OⁱPr)₃And ClSi (Me)₃It is.
[0024]
  The metal dialkoxide of the embodiment shown above is subjected to chlorination to produce the reaction product “A”. The exact composition of product “A” is unknown, but it is believed that it contains some chlorinated metal compound, an example of which could be ClMg (OR ″).
[0025]
  The reaction product “A” is then converted into one or more halogenation / titanating agents such as TiCl₄And Ti (OBu)₄The reaction product “B” is produced by contacting with a combination of the above. The reaction product “B” is probably a complex of a chlorinated and partially chlorinated metal and titanium compound. Reaction product “B” is a carrier MgCl impregnated with titanium₂For example, (MCl₂)_y(TiCl_x(OR)_4-x)_zIt can be represented by a compound such as Reaction product “B” can be precipitated as a solid from the catalyst slurry.
[0026]
  The reaction product produced in the second halogenation / titanium stage, ie the catalyst component “C”, is also probably a complex of halogenated and partially halogenated metal and titanium compounds, Unlike "B"₂)_y(TiCl_{x '}(OR)_{4-x '})_{z '}It can be expressed as It is expected that the degree of halogenation of “C” will be higher than that of product “B”. With such a higher degree of halogenation, the resulting complex of compounds can vary.
[0027]
  The reaction product produced in the third halogenation / titanation stage, ie the catalyst component “D”, is also likely a complex of a halogenated and partially halogenated metal and titanium compound. Unlike "B" and "C", perhaps (MCl₂)_y(TiCl_{x ”}(OR)_{4-x "})_{z ”}It can be expressed as It is expected that the degree of halogenation of “D” will be higher than that of product “C”. With such a higher degree of halogenation, the resulting complex of compounds will be different. While the description of such reaction products provides an explanation of the most probable chemistry at the present time, the invention as set forth in the claims is not limited by such a theoretical mechanism.
[0028]
  Metal dialkyls suitable for use in the present invention and reactant metal dialkoxides can include any that can be used in the present invention for the purpose of producing suitable polyolefin catalysts. Such metal dialkoxides and dialkyls may include group IIA metal dialkoxides and dialkyls. Such metal dialkoxides or dialkyls may be magnesium dialkoxides or dialkyls. Non-limiting examples of suitable magnesium dialkyl include diethyl magnesium, dipropyl magnesium, dibutyl magnesium, butyl ethyl magnesium, and the like. Butylethylmagnesium (BEM) is one suitable magnesium dialkyl.
[0029]
  The metal dialkoxide used in the practice of the present invention has the general formula Mg (OR ")₂[Wherein R ″ is a hydrocarbyl having 1 to 20 carbon atoms or a substituted hydrocarbyl].
[0030]
  Such metal dialkoxides are soluble and are typically non-reducing. A non-reducing compound is not an insoluble species that can result from the reduction of a compound such as MgRR ', which can result in a catalyst exhibiting a broad particle size distribution.₂Has the advantage of producing. In addition, Mg (OR ")₂[This shows lower reactivity than MgRR 'when used in reactions involving the next halogenation / titanation step followed by chlorination with a mild chlorinating agent] For example, the control and distribution of catalyst particle size may be better.
[0031]
  Non-limiting examples of metal dialkoxide species that can be used are magnesium butoxado, magnesium pentoxide, magnesium hexoxide, magnesium di (2-ethylhexoxide) and suitable for solubilizing the system Any alkoxide is included.
[0032]
  As a non-limiting example, an alkylmagnesium compound (MgRR ') and an alcohol (ROH) can be reacted as shown below to produce magnesium dialkoxide, such as magnesium di (2-ethylhexoxide):
        MgRR ′ + 2R ″ OH → Mg (OR ″)₂+ RH + R'H
  This reaction can be carried out at room temperature and these reactants form a solution. R and R ′ may be any alkyl group having 1 to 10 carbon atoms, and may be the same or different. Suitable MgRR 'compounds include, for example, diethyl magnesium, dipropyl magnesium, dibutyl magnesium and butyl ethyl magnesium. The MgRR 'compound may be BEM, where RH and R'H are butane and ethane, respectively.
[0033]
  In practicing the present invention, any alcohol that provides the desired metal dialkoxide can be used. The alcohol used is generally of the general formula R ″ OH, wherein R ″ is an alkyl group having 2-20 carbon atoms, the number of carbon atoms being at least 3, at least 4, at least 5, at least carbon atoms. Any alcohol represented by the formula (6) may be used. Non-limiting examples of suitable alcohols include ethanol, propanol, isopropanol, butanol, isobutanol, 2-methyl-pentanol, 2-ethylhexanol, and the like. Although it is believed that almost all linear or branched alcohols can be used, alcohols having a higher degree of branching, such as 2-ethyl-1-hexanol, may be used.
[0034]
  The amount of alcohol added may vary, for example, but not exclusively, may be in the range of 0 to 10 equivalents, generally from about 0.5 equivalents to about 6 equivalents (equivalents throughout Equivalents based on magnesium or metal compound) and may be in the range of about 1 to about 3 equivalents.
[0035]
  The use of alkyl metal compounds can result in high molecular weight species that exhibit very high viscosity in solution. The addition of aluminum alkyls, such as triethylaluminum (TEAl), to the reaction can break the bonds between individual alkyl metal molecules, thereby reducing such high viscosity. Such alkyl aluminum to metal ratios may typically be in the range of 0.001: 1 to 1: 1, 0.01 to 0.5: 1, and also 0.03: It may be in the range of 1 to 0.2: 1. In addition, it is possible to use an electron donor such as an ether such as diisoamyl ether (DIAE) for the purpose of further reducing the viscosity of such an alkyl metal. The ratio of such electron donor to metal is typically in the range of 0: 1 to 10: 1, but may be in the range of 0.1: 1 to 1: 1.
[0036]
  Agents useful in the step of subjecting the metal alkoxide to halogenation include any halogenating agent that will result in a suitable polyolefin catalyst when used in the present invention. Such a halogenation step can be a chlorination step in which the halogenating agent contains a chloride (ie is a chlorinating agent).
[0037]
  Halogenation of such metal alkoxide compounds 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. 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, may be in the range of about 3: 1 to about 1: 2, and about 2: It may range from 1 to about 1: 2 and may also be about 1: 1.
[0038]
  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 may be 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 hour to about 4 hours.
[0039]
  After performing the halogenation step, the metal alkoxide may be subjected to halogenation, and then the product “A” which is the halide may be subjected to halogenation / titanium treatment twice or more.
[0040]
  The halogenated / titanium agent used is two types of tetra-substituted titanium compounds [all four substituents are the same and the substituents are halides or alkoxides or phenoxides having 2 to 10 carbon atoms] A mixture of, for example, TiCl₄Or Ti (OR "")₄A mixture of these may be used. The halogenation / titanium agent used may be a chlorination / titanium agent.
[0041]
  The halogenating / titanating agent may be a single compound or a combination of compounds. The process of the present invention provides a catalyst that is active even after the initial halogenation / titanation, however, desirably, a total of at least three halogenation / titanation steps are performed.
[0042]
  The first halogenating / titanating agent is typically a mild titanating agent, which may be a mixture of titanium halide and organic titanate. The first halogenation / titanium agent is TiCl₄/ Ti (OBu)₄TiCl in the range of 0.5: 1 to 6: 1₄And Ti (OBu)₄The ratio may be 2: 1 to 3: 1. Such a mixture of titanium halide and organic titanate reacts with a titanium alkoxy halide, ie Ti (OR)._aX_b[Wherein OR and X are alkoxide and halide, respectively, and a + b is the valence of titanium, typically 4].
[0043]
  Alternatively, such first halogenation / titanating agent may be a single compound. The first halogenated / titanating agent example is Ti (OC₂H₅)₃Cl, Ti (OC₂H₅)₂Cl₂, Ti (OC₃H₇)₂Cl₂, Ti (OC₃H₇)₃Cl, Ti (OC₄H₉) Cl₃, Ti (OC₆H₁₃)₂Cl₂, Ti (OC₂H₅)₂Br₂And Ti (OC₁₂H₂₅) Cl₃It is.
[0044]
  Such a first halogenation / titanation step is generally carried out through first slurrying the halogenated product “A” in a room temperature / ambient temperature hydrocarbon solvent. Non-limiting examples of suitable hydrocarbon solvents include heptane, hexane, toluene, octane and the like. Product “A” may be at least partially soluble in such hydrocarbon solvents.
[0045]
  When the halogenated / titanating agent is added to the soluble product “A”, the solid product “B” precipitates at room temperature. The amount of halogenating / titanating agent used must be sufficient to precipitate the solid product from solution. In general, the amount of halogenating / titanating agent used is generally in the range of about 0.5 to about 5, typically in the range of about 1 to about 4, based on the ratio of titanium to metal. , About 1.5 to about 2.5.
[0046]
  Next, after recovering the solid product “B” precipitated in the first halogenation / titanation step by any suitable recovery technique, room temperature / ambient temperature using a solvent such as hexane Wash with. Generally, the solid product “B” is washed until [Ti] is less than about 100 mmol / L. Within the scope of the present invention, [Ti] represents any titanium species that can act as a second generation Ziegler catalyst, including titanium species that are not part of the reaction product as described herein. It will consist of The resulting product “B” is then subjected to a second and third halogenation / titanation step to yield products “C” and “D”. The solid product produced after each halogenation / titanation step is washed until [Ti] is less than the desired amount, such as less than about 100 mmol / L, less than about 50 mmol / L, or less than about 10 mmol / L. May be. After the final halogenation / titanation step, the product has a [Ti] less than the desired amount, such as less than about 20 mmol / L, less than about 10 mmol / L, or less than about 1.0 mmol / L. You may wash until it becomes. It is believed that the lower the [Ti], the less titanium that can serve as the second generation Ziegler species, resulting in an improved catalyst. We believe that reducing [Ti] can result in an improved catalyst, for example, a factor that narrows the MWD.
[0047]
  The second halogenation / titanation stage is typically through the solid product recovered in the first titanation stage, ie, the solid product “B” is slurried in a hydrocarbon solvent. carry out. The hydrocarbon solvents mentioned as suitable for use in the first halogenation / titanium stage can be used. The compound or combination of compounds used in the second and third halogenation / titanation stages may be different from that used in the first halogenation / titanation stage. Although not necessary, the same agent used in the first halogenation / titanium stage may be used at a higher concentration in the second and third halogenation / titanium stages. The second and third halogenating / titanating agents are titanium halides such as titanium tetrachloride (TiCl₄Or the like. This halogenating / titanating agent is added to the slurry. This addition can be performed at ambient temperature / room temperature, but can also be performed under temperatures and pressures other than ambient temperature and pressure.
[0048]
  The second and third halogenation / titanium agents generally include titanium tetrachloride. The ratio of titanium to magnesium included in each of the second and third halogenation / titanation stages is typically in the range of about 0.1 to 5, although a ratio of about 2.0 is also used. A ratio of about 1.0 can be used. This third halogenation / titanation step is generally carried out in a room temperature slurry, but can also be carried out at temperatures and pressures other than ambient and pressure.
[0049]
  The amount of titanium tetrachloride used or the amount of alternative halogenating / titanating agent is also expressed in equivalents, but the equivalents shown here are the amounts of titanium based on magnesium or metal compounds. The amount of titanium in each of the second and third halogenation / titanation stages is generally in the range of about 0.1 to about 5.0 equivalents, but in the range of about 0.25 to about 4 equivalents. It may typically be desirable to be in the range of about 0.3 to about 3 equivalents and in the range of about 0.4 to about 2.0 equivalents. In one particular embodiment, the amount of titanium tetrachloride used in each of the second and third halogenation / titanation stages is in the range of about 0.45 to about 1.5 equivalents.
[0050]
  Combining the catalyst component “D” produced in the manner described above with an organometallic catalyst component (“preactivator”) produces a preactivated catalyst system suitable for olefin polymerization. Pre-activators used with the transition metal-containing catalyst component “D” are typically organometallic compounds such as aluminum alkyls, aluminum hydrides, lithium aluminum alkyls, zinc alkyls, magnesium alkyls, and the like.
[0051]
  This preactivator is generally an organoaluminum compound. This organoaluminum preactivator is typically of the formula AlR₃[Wherein at least one R is an alkyl or halide having 1 to 8 carbon atoms, and each R may be the same or different]. The organoaluminum preactivator may be a trialkylaluminum, such as trimethylaluminum (TMA), triethylaluminum (TEAl), and triisobutylaluminum (TiBAl). The ratio of Al to titanium may be in the range of 0.1: 1 to 2: 1, typically 0.25: 1 to 1.2: 1.
[0052]
  In some cases, such Ziegler-Natta catalysts may be pre-polymerized. Generally, such a prepolymerization step is carried out by contacting the catalyst with a cocatalyst and then contacting the catalyst 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.
[0053]
  The catalyst of the present invention can be used in any method for causing homopolymerization or copolymerization of all types of α-olefins. For example, the catalyst can be used to catalyze ethylene, propylene, butylene, pentene, hexene, 4-methylpentene and other α-alkenes having at least 2 carbon atoms and also mixtures thereof. Such copolymers may provide desirable results, for example, a wide range of MWD and multi-peak distributions, such as bimodal and trimodal characteristics. The catalyst of the present invention can be used in a polymerization that produces polyethylene from ethylene.
[0054]
  In the present invention, various polymerization methods can be used. For example, a single loop and / or multiple loop method, a batch method, or a continuous method without a loop reactor can be used. An example of a multi-loop process in which the present invention can be utilized is that the MW exhibited by the polyolefin resulting from the polymerization reaction occurring in the first loop is that of the polyolefin resulting from the polymerization reaction occurring in the second loop. Lowering it results in a double loop system that results in a resin that exhibits a broad molecular weight distribution and / or bimodal properties. Alternatively, another example of a multi-loop process in which the present invention can be utilized is polymerization where the MW exhibited by the polyolefin resulting from the polymerization reaction that occurs in the first loop is caused in the second loop. A double loop system that results in a resin that exhibits a broad molecular weight distribution and / or bimodal properties by being higher than that of the resulting polyolefin in the reaction.
[0055]
  Such polymerization methods can be, for example, bulk, slurry or gas phase methods. The catalyst of the present invention can be used in slurry phase polymerization. The polymerization conditions (eg temperature and pressure) depend not only on the type of equipment used in the polymerization process but also on the type of polymerization process used and these are well known in the art. Generally, the temperature is in the range of about 50-110 ° C. and the pressure is in the range of about 10-800 psi.
[0056]
  The activity exhibited by the catalyst resulting from the embodiments of the present invention depends, at least in part, on the polymerization method and conditions, such as the equipment used and the reaction temperature. For example, the activity exhibited by the catalyst in a polymerization mode that produces polyethylene from ethylene is generally an activity that yields at least 5,000 g of PE per gram of catalyst, but an activity that yields more than 50,000 g of PE per gram of catalyst. And can be activated to yield 100,000 g or more of PE per gram of catalyst.
[0057]
  In addition, the catalyst resulting from the present invention can result in a polymer having improved fluff morphology. Thus, using the catalyst of the present invention can yield large polymer particles that exhibit a uniform size distribution, with the concentration of fine particles present (less than about 125 microns) being low, eg, less than 2% or 1 Less than%. Since the catalyst of the present invention contains a large powder having a high powder bulk density, it can be easily transferred and is suitable for a polymerization production process. The use of the catalyst of the present invention generally results in a polymer with a lower amount of fines and a higher bulk density (BD). D. The value can be about 0.31 g / cc or more, about 0.33 g / cc or more, even about 0.35 g / cc or more.
[0058]
  When the olefin monomer is introduced into the polymerization reaction zone, it may be introduced in a diluent that is a non-reactive heat transfer agent that is liquid 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 may be present at 0.01-20 mole percent and is about 0.02-10 moles. It may be present in a percentage range.
[0059]
  Optionally, an electron donor may be added together with the halogenating agent, the first halogenating / titanium agent or one or more of the following halogenating / titanium agents. It may be desirable to use an electron donor in the second halogenation / titanation step. Electron donors suitable for use in generating polyolefin catalysts are well known and any suitable electron donor that will provide a suitable catalyst can be used in the present invention. An electron donor (also known as a Lewis base) is an organic compound that contains oxygen, nitrogen, phosphorus or sulfur and can donate an electron pair to the catalyst.
[0060]
  Such electron donors may be monofunctional or polyfunctional compounds, such as aliphatic or aromatic carboxylic acids and their alkyl esters, aliphatic or cyclic ethers, ketones, vinyl esters, acrylic derivatives, especially alkyl acrylates. Alternatively, it can be selected from alkyl methacrylate and silane. An example of a suitable electron donor is di n-butyl phthalate. A general example of a suitable electron donor is the general formula RSi (OR ')₃Alkylsilyl alkoxides represented by, for example, methylsilyltriethoxide [MeSi (OEt₃Wherein R and R 'are alkyl having 1-5 carbon atoms and may be the same or different.
[0061]
  In the polymerization step, an internal electron donor may be used when synthesizing the catalyst, and an external electron donor or a stereoselectivity control agent (SCA) is used for the purpose of activating the catalyst during the polymerization. May be. An internal electron donor can be used during the halogenation or halogenation / titanation step when conducting the reaction that produces the catalyst. Compounds suitable for use as internal electron donors when generating conventional supported Ziegler-Natta catalyst components include electron donor compounds having ether, diether, ketone, lactone, N, P and / or S atoms and certain species Of esters. Especially esters of phthalic acid such as diisobutyl phthalate, dioctyl, diphenyl and benzylbutyl, esters of malonic acid such as diisobutyl and diethyl malonate, alkyl and aryl pivalates, alkyl maleates, cycloalkyl and aryl, alkyl and aryl Suitable are carbonates such as diisobutyl, ethyl-phenyl and diphenyl carbonate, such as succinic esters such as mono and diethyl succinate.
[0062]
  External donors that can be used when producing the catalyst according to the 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, but m is 0, 1 or 2 And R ′ and R may be the same, 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.] included.
[0063]
  The external donor of the present invention has the following formula:
[0064]
[Chemical 1]

[0065]
[Wherein R₁And R₄Are both alkyl or cycloalkyl groups containing primary, secondary or tertiary carbon atoms bonded to silicon, and R₁And R₄May be the same or different and R₂And R₃Is an alkyl or aryl group]. R₁May be methyl, isopropyl, cyclopentyl, cyclohexyl or t-butyl, R₂And R₃May be methyl, ethyl, propyl or butyl groups and need not be the same and R₄May also 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). .
[0066]
  The MWD exhibited by the polyethylene produced using the catalyst described above can be at least 5.0 and can be higher than about 6.0.
[0067]
  The polyolefins of the present invention are suitable for use in a variety of applications, for example in extrusion processes, thereby producing a wide range of products. Such extrusion processes include, for example, blown film extrusion, cast film extrusion, slit tape extrusion, blow molding, pipe extrusion and foam sheet extrusion. Such processing can include single layer extrusion or multilayer coextrusion.
[0068]
  End use applications that can utilize the present invention may include, for example, films, fibers, pipes, textile materials, manufactured articles, diaper components, feminine hygiene products, automotive components and medical materials.
[0069]
  All references cited herein (including all research articles, US patents and foreign patents and patent applications) are hereby incorporated by reference in their entirety.
First set of examples
  Having generally described the invention, the following examples are presented merely for the purpose of illustrating certain embodiments of the invention and illustrating the practice and advantages of the invention. It should be understood that the examples are given by way of illustration and are in no way intended to limit the scope of the specification or the claims.
[0070]
  The synthesis scheme utilized with this series of catalysts is as follows (all ratios are based on BEM):
(BEM + 0.03 TEAl + 0.6 DIAE) +2.09 2-ethylhexanol → Mg (OR)₂
Mg (OR)₂+ ClTi (OPr)₃→ Solution A
Solution A + (2 TiCl₄/ Ti (OBu)₄→ Catalyst B (MgCl₂Based carrier)
Catalyst B + X TiCl₄→ Catalyst C
Catalyst C + 0.156 TEAl → Final catalyst
  The optimum formulation is considered to be X = 0.5 to 2, and the number of washings performed before the catalyst C is preactivated with TEAl is 0 to 2 times. The catalyst preparation was subjected to the following modifications so that titanation occurred more effectively:
Catalyst B + X TiCl₄→ Catalyst C
Catalyst C + Y TiCl₄→ Catalyst D
Catalyst D + 0.156 TEAl → Final catalyst
  As shown, when X and Y = 0.5 to 1.0, TiCl₄Is completed in two stages. While the catalyst C is typically washed once or twice, it is washed twice after Y for the purpose of removing soluble titanium species that act as second generation Ziegler species.
[Example 1]
[0071]
  In a 3 L round bottom flask in a nitrogen purge box, 1412.25 g (2.00 mol) of BEM-1, 27.60 g (0.060 mol) of TEAl (24.8% in heptane) and 189.70 g of DIAE (1.20 mol) was added. The contents were then transferred using a cannula to a 20 L Buchi reactor under a stream of nitrogen. The flask was then rinsed with about 400 ml of hexane, which was also transferred to the reaction vessel. The stirrer was set at 350 rpm.
[0072]
  To a 1 L bottle, 2-ethylhexanol (543.60 g, 4.21 mol) was added and capped. Next, it was diluted with hexane so that the total volume became 1 L, and then added to the reaction vessel. The solution was cannulated into the reaction vessel using a mass flow controller. The initial top temperature was 25.3 ° C and it reached a maximum temperature of 29.6 ° C. After the addition (about 2 hours), the bottle was rinsed with 400 ml of hexane and it was also transferred to the reactor. The reaction mixture was left stirring at 350 rpm overnight under 0.5 bar nitrogen pressure and then the heat exchanger was switched off.
[0073]
  The heat exchanger was switched on and set to 25 ° C. Chlorotitanium triisopropoxide was added to two 1 L bottles (774.99 and 775.01 g, 2.00 moles total) to give a total of 2 liters. The contents of each bottle were cannulated into the reaction vessel using a mass flow controller. The initial headspace temperature was 24.6 ° C and it reached a maximum temperature of 25.9 ° C during the addition of the second bottle. The addition times for bottles 1 and 2 were 145 minutes and 125 minutes, respectively. After this addition, each bottle was rinsed with 200 ml of hexane, which was also transferred to the reactor. The reaction mixture was left stirring at 350 rpm overnight under a nitrogen pressure of 0.5 bar. The heat exchanger was switched off.
TiCl ₄ / Ti (OBu) ₄ Preparation of
  Preparation of the titanium tetrachloride / titanium tetrabutoxide mixture was performed in a 5 liter round bottom flask using standard Schlenk line techniques. 680.00 g (1.99 mol) Ti (OBu) in a 1 L pressurized bottle₄Was diluted with hexane to a total volume of 1L. This solution was then cannula transferred to the reaction vessel. The bottle was rinsed with 200 ml of hexane and it was also transferred to the reactor. 440 ml (~ 760 g, 4.00 mol) TiCl in a 1 L graduated cylinder₄Was diluted with hexane to a total volume of 1L. While stirring the solution in the 5 liter flask, the reaction vessel was charged with TiCl.₄N solution₂Added dropwise using a cannula under pressure. After the addition was complete, the 1 L cylinder was rinsed with 200 ml of hexane, which was also transferred to the reactor. The reaction mixture after 1 hour was diluted with hexane to a total volume of 4 L, and then stored in the flask until used.
[0074]
  The heat exchanger was turned on and set to 25 ° C. TiCl using cannula and mass flow controller₄/ Ti (OBu)₄Was transferred to a 20 liter reaction vessel. The initial headspace temperature was 24.7 ° C and it reached a maximum temperature of 26.0 ° C during the 225 minute addition. The container after this addition was rinsed with 1 liter of hexane and stirred for 1 hour.
[0075]
  The stirrer was switched off and the solution was allowed to settle for 30 minutes. The solution was decanted by pressurizing the reactor to 1 bar, lowering the dip tube and ensuring that no solid catalyst exited through the attached transparent plastic hose. The catalyst was then washed 3 times according to the following procedure. This was placed on a balance using a pressure vessel, and 2.7 kg of hexane was weighed into the vessel and then transferred to the reaction vessel. The agitator was turned on and the catalyst mixture was stirred for 15 minutes. The stirrer was then turned off and the mixture was allowed to settle for 30 minutes. This procedure was repeated. The slurry after the third hexane addition was allowed to settle overnight and the heat exchanger was switched off.
[0076]
  The supernatant was removed by decantation and 2.0 kg of hexane was added to the reaction vessel. Agitation was resumed at 350 rpm and the heat exchanger was switched on and set to 25 ° C. In a 1 liter graduated cylinder, 440 milliliters (760 g, 4.00 mole) of titanium tetrachloride was added. This TiCl₄Was diluted to 1 liter with hexane and then half of the solution was transferred to the reactor using a cannula and mass flow controller. The initial top temperature was 24.7 ° C., which rose by 0.5 ° C. during the addition. Total addition time was 45 minutes. The stirrer was switched off after 1 hour and the solid was allowed to settle for 30 minutes. After removing the supernatant by decantation, the catalyst was washed once with hexane according to the procedure described above. After this washing was completed, 2.0 kg of hexane was transferred to the reaction vessel and stirring was resumed. This second TiCl₄The dripping was completed in the same manner as described above with the remaining 500 milliliters of solution. After this addition, the cylinder was rinsed with 400 milliliters of hexane, which was also added to the bucchi. The stirrer was switched off after 1 hour of reaction and the solids were allowed to settle for 30 minutes. Next, after removing the supernatant by decantation, the catalyst was washed three times with hexane. Next, 2.0 kg of hexane was transferred to the reaction vessel.
[0077]
  To a 1 liter pressurized bottle was added 144.8 g (312 mmol) of TEAl (25.2% in hexane). The bottle was capped and diluted to 1 liter with hexane. The solution was then cannulated into the reaction mixture using a mass flow controller. During the 120 minute addition, the color of the slurry turned dark brown. The initial top temperature was 24.5 ° C., which reached a maximum temperature of 25.3 ° C. The bottle after the addition was rinsed with 400 milliliters of hexane and transferred to the reactor as well. After 1 hour of reaction, the stirrer was switched off and the catalyst was allowed to settle for 30 minutes. After removing the supernatant by decantation, the catalyst was washed once according to the procedure described above. After this washing, 2.7 kg of hexane was added to the reaction vessel. The contents were then transferred to a 3 gallon pressurized container. After rinsing the bucchi with 1.0 kg and 0.5 kg hexane, they were also added to the pressure vessel. The estimated catalyst yield was 322 g.
[0078]
  The composition (expressed in weight percent) in one embodiment was: Cl 53.4%; Al 2.3%; Mg 11.8% and Ti 7.9%. The actual measurement range of each element was as follows: Cl was 48.6-55.1%; Al was 2.3-2.5%; Mg was 11.8-14.1% and Ti was 6.9- 8.7%. The range of each element can be: Cl 40.0-65.0%; Al 0.0-6.0%; Mg 6.0-15.0% and Ti 2.0-14 0.0%.
[0079]
  Table 1 shows TiCl₄/ Ti (OBu)₄Addition, 3 washes, 1st TiCl₄Addition, first wash and second TiCl₄List the [Ti] measured for the sample after addition and the next third wash. The supernatant liquid 1-4 is TiCl₄/ Ti (OBu)₄It is a supernatant after addition. The supernatants 5 and 6 are the first TiCl₄It is a supernatant after addition. Supernatant 7-10 is the second TiCl₄It is a supernatant after addition.
[0080]
[Table 1]

[0081]
Comparative Example 1:
  The third titanization is omitted and the second titanation is 1/4 of the amount of TiCl_FourComparative Example 1 was prepared in a manner similar to that of Example 1 except that
Example 2:
  The second and third titanation is 0.5 equivalent of TiCl during each titanation stage._FourThe same style as in Example 1 except thatRealExample 2 was prepared.
Comparative Example 2:
  TiCl used during the second titanation_FourComparative Example in a manner similar to that of Comparative Example 1 except that the amount of is about 4 times the amount used in Comparative Example 12Was prepared. After the second titanation, washing with hexane was performed once. The composition (expressed in weight percent) in one embodiment was: Cl 57.0%; Al 2.0%; Mg 9.5% and Ti 10.0%. The range of each element may be: Cl 55.0-57.0%; Al 2.0-2.6%; Mg 8.9-9.5% and Ti 10.0-11 0.0%.
Comparative Example 3:
  Comparative Example except that hexane was washed twice after the second titanation2Comparative examples in the same manner as3Was prepared. In one embodiment, the composition (expressed in weight percent) was: Cl 53.0%; Al 2.3%; Mg 9.7% and Ti 9.5%. The range of each element may be: Cl 52.6-53.0%; Al 2.0-2.3%; Mg 9.7-10.6% and Ti 8.7-9 .5%.
[0082]
  Table 2 lists the prepared catalysts.
[0083]
[Table 2]

[0084]
  In Table 3, from Example 1 and Comparative Example 13The MWD data which the polymer manufactured using this showed. This data shows that if the catalyst / cocatalyst system is determined, the number of washes is increased or TiCl_FourIt has been shown that a narrower MWD can be achieved by adding a third titanation step using. The inherent MWD exhibited by the polymer resin is generally higher in the following order:
Comparative Example 1 <Example2 <comparative example3<Example 1> Comparative Example2.
[0085]
[Table 3]

[0086]
  As shown in Table 4, each of the catalysts resulted in a powder with a low concentration of fines (particles less than 125 microns), however, the catalyst of the present invention produced by using the titanization stage twice. When used, consistently results in fluff with higher bulk density.
[0087]
[Table 4]

[0088]
  Such characteristics have a substantial effect on the sedimentation efficiency of the polymer as shown by the sedimentation efficiency curve (shown in FIG. 1) prepared in the laboratory. It can be seen that the first 10 ml of fluff produced from the solution rapidly disappears in the polymer of the present invention prepared using the catalyst of Example 1 of the present invention, which is a comparative example.3This means that the settling rate is higher than those of the polymers produced using the conventional catalysts, and the polymer morphology is good.
Viscosity control of synthesis solution
  It has been found that by changing the viscosity of the solution during catalyst synthesis, the precipitation of the catalyst components that precipitate from the solution can be corrected. It has been found that modifying the catalyst component precipitation in this way affects the resulting catalyst particle size and the polymer particle size produced using the catalyst. The viscosity of the catalyst synthesis solution can vary depending on the relative amount of aluminum alkyl present. Accordingly, the catalyst particle size and the polymer particle size produced using the catalyst can vary depending on the relative amount of aluminum alkyl used.
[0089]
  Catalysts were prepared with varying amounts of aluminum alkyl in the synthesis solution and the tests were performed along with tests of the resulting polymer fluff with these catalysts. Example3Describes the synthesis used in the catalyst preparation and Table 5 shows the resulting catalyst and polymer sizes.
[Example 3]
[0090]
  The synthesis used is as follows, and the ratios are all based on BEM:
1. (BEM + X TEAl + 0.6 DIAE) + (2 + 3X) 2-ethylhexanol → Mg (O-2-ethylhexyl)₂・ [Al (O-2-ethylhexyl)₃]
2. Mg (O-2-ethylhexyl)₂・ [Al (O-2-ethylhexyl)₃] + ClTi (OPr)_x→ "A"
3. “A” + 2TiCl₄/ Ti (Obu)₄→ "B" (MgCl₂Based carrier)
4). “B” + Y TiCl₄→ "C"
5). “C” + Z TiCl₄→ "D"
7). “D” +0.156 TEAl → catalyst
  Four catalysts with Y = Z = 1 were prepared in a 1 liter Bucchi reactor according to the general synthesis. In the first reaction, the amount of TEAl was varied to study the effect of the resulting amount on the catalyst particle size. The relative amount of 2-ethylhexanol was adjusted during each catalyst synthesis in order to prevent the titanium complex amount from being reduced by any unreacted aluminum or magnesium alkyl species. The following table lists the synthesized catalyst, the relative amounts of BEM, TEAl and 2-ethylhexanol used, the average particle size indicated by the catalyst and the average particle size indicated by the polyethylene resin produced using each catalyst.
[0091]
  The following table shows the particle size distribution data obtained for each catalyst. As can be seen, the average particle size distribution improves with increasing TEAl concentration.
[0092]
[Table 5]

[0093]
  As shown in Table 5, both the average particle size of the catalyst and the resulting average particle size of the fluff increase with increasing TEAl concentration used in the initial catalyst synthesis solution. Viscosity of the catalyst synthesis solution can be changed by changing the relative amount of aluminum alkyl. By so changing the viscosity of the solution, the precipitation characteristics of the catalyst component produced from the solution can be altered, and the resulting average particle size of the catalyst component and the resulting polymer using the catalyst. Can affect the average particle size. It can be seen that the average particle diameter of the catalyst component increases as the concentration of aluminum alkyl in the synthesis solution increases. It can also be seen that the average particle size of the resulting polymer resin using the catalyst increases with increasing concentration of aluminum alkyl in the synthesis solution.
[0094]
  The amount of aluminum alkyl can be measured in terms of the ratio of aluminum alkyl to magnesium alkyl, and may range from about 0.01: 1 to about 10: 1. The MWD exhibited by polyethylene produced using the catalysts described above can be at least 4.0, and it can be as high as about 6.0.
[0095]
  The catalyst 101 shown in Table 5 is the same catalyst as Example 1 as described above. The composition (expressed in weight percent) in one embodiment was: Cl 53.4%; Al 2.3%; Mg 11.8% and Ti 7.9%. The range of each element can be: Cl 40.0-65.0%; Al 0.0-6.0%; Mg 6.0-15.0% and Ti 2.0-14 0.0%.
[0096]
  The catalyst 102 shown in Table 5 was in one embodiment: Cl 47.0%; Al 3.4%; Mg 13.1% and Ti 4.0%. The range of each element can be: Cl 40.0-65.0%; Al 0.0-6.0%; Mg 6.0-15.0% and Ti 2.0-14 0.0%.
[0097]
  The catalyst 103 shown in Table 5 was in one embodiment: Cl 50.0%; Al 2.4%; Mg 12.1% and Ti 3.9%. The range of each element can be: Cl 40.0-65.0%; Al 0.0-6.0%; Mg 6.0-15.0% and Ti 2.0-14 0.0%.
[0098]
  The catalyst 104 shown in Table 5 was in one embodiment: Cl 53.0%; Al 3.1%; Mg 12.8% and Ti 4.2%. The range of each element can be: Cl 40.0-65.0%; Al 0.0-6.0%; Mg 6.0-15.0% and Ti 2.0-14 0.0%.
[0099]
  The polyolefins of the present invention are suitable for use in a variety of applications, such as extrusion processes, thereby producing a wide range of products. Such extrusion processes include, for example, blown film extrusion, cast film extrusion, slit tape extrusion, blow molding, pipe extrusion and foam sheet extrusion. Such processing can include single layer extrusion or multilayer coextrusion. End use applications that can utilize the present invention may include, for example, films, fibers, pipes, textile materials, manufactured articles, diaper components, feminine hygiene products, automotive components and medical materials.
[0100]
  In accordance with an alternative embodiment of the present invention, a polyolefin polymerization catalyst is produced using a process involving several reactions. First, a magnesium alkyl compound [ie, Mg (R *)₂(Wherein R * may be the same or different alkyl group having about 1 to 20 carbon atoms), such as BEM, etc.]
                    BEM + 2ROH → Mg (OR)₂
Where R is an alkyl group, for example an alkyl group containing about 1 to 20 carbon atoms.
To produce a soluble magnesium alkoxide compound. The alcohol represented by the formula ROH may be branched or unbranched. An example of a suitable alcohol is 2-ethylhexanol. Any reaction conditions and order of addition suitable for converting the BEM and alcohol reactant to the magnesium alkoxide compound can be used. In one embodiment, the alcohol is added to the BEM solution to form a reaction mixture that is maintained under ambient temperature and pressure. The reaction mixture is stirred for a time sufficient to produce a soluble magnesium alkoxide compound.
[0101]
  When the resulting magnesium alkoxide compound is mixed with a mild chlorinating agent, the following formula:
Mg (OR)₂+ TiCl_n(OR ’)_4-n→ [Ti (OR ’)_4-nCl_n・ Mg (OR)₂]_m
Wherein R 'is an alkyl, cycloalkyl or aryl group, n is 1 to 3, and m is at least 1 and may be 2 or more.
To produce a magnesium-titanium-alkoxide adduct. Desirably, n is 1. Reactant is TiCl_n(OR ’)_4-n[Where R ′ = alkyl or aryl and n is 1] and also Ti (OⁱPr)₃Cl [where:ⁱPr represents isopropyl]. Any conditions suitable for producing such a magnesium-titanium-alkoxide adduct can be used in this process. In one embodiment, the process is performed at ambient temperature and pressure. The reactants are mixed for a time sufficient to produce such a magnesium-titanium-alkoxide adduct. The magnesium-titanium-alkoxide compound is sterically hindered so that it is difficult for metathesis of the chlorine atom and magnesium alkoxide ligand of the titanium compound to occur. . In essence, the adduct is mostly but not all MgCl.₂Convert to.
[0102]
  Thereafter, the magnesium-titanium-alkoxide adduct and the alkyl chloride compound are converted to MgCl, which is a carrier.₂Mix to change. This reaction proceeds as follows:
[Ti (OR ’)_4-nCl_nMg (OR)₂]_m+ R "Cl →" TiMgCl₂"+ R" OR
Where R ″ is an alkyl group, for example an alkyl group containing about 2 to 18 carbon atoms, and “TiMgCl₂"MgCl is a carrier impregnated with titanium"₂Represents. R ″ may be branched or unbranched, but in certain embodiments it may be desirable that R ″ is not branched. Possible alkyl chloride compounds include benzoyl chloride, chloromethyl ethyl ether and t-butyl chloride, with benzoyl chloride being preferred in a particular embodiment. The amount of alkyl chloride added to the magnesium alkoxide adduct may be larger than the amount required for the reaction. The ratio of the amount of benzoyl chloride to the amount of Mg (eg, BEM) included in the reaction mixture may range from about 1 to 20 (ie, a ratio of about 1: 1 to about 20: 1), or May be about 1 to 10, and may be desirable in the range of about 4 to 8. This reaction can be carried out under any conditions suitable for the precipitation of the magnesium chloride support. In one embodiment, the reactant is MgCl as a support.₂Reflux for a time sufficient to precipitate. In embodiments using t-butyl chloride, the reaction may be heated during reflux. In embodiments using benzoyl chloride or chloromethyl ethyl ether, the temperature while the reactants are refluxed may be at room temperature. This reaction also produces one or more by-products, such as ether (shown in the reaction shown above). MgCl₂The presence of Ti while precipitating is believed to play a major role in that it provides a highly active catalyst.
[0103]
  MgCl₂After separating the carrier from the reaction mixture, some of the contaminants may be removed therefrom by washing the carrier with, for example, hexane. Next, MgCl₂The carrier which is TiCl₄Treatment produces a catalyst slurry according to the following formula:
                  "MgCl₂+2 TiCl₄→ Catalyst
  This treatment can be carried out under any conditions suitable to produce a catalyst slurry, for example under ambient temperature and pressure. The catalyst slurry is washed with, for example, hexane and then dried. The resulting catalyst may be preactivated with an alkylaluminum compound such as triethylaluminum (TEAl) so that the catalyst does not corrode the polymerization reactor. More specifically, when titanium chloride contained in the catalyst is reacted with an alkylaluminum compound, it is converted to titanium alkyl. Otherwise, when the titanium chloride is exposed to moisture, it undergoes conversion to produce HCl, which can result in corrosion of the polymerization reactor.
Second set of examples
  Having generally described the invention, the following examples are presented as specific embodiments of the invention for the purpose of illustrating the practice and advantages of the invention. It should be understood that the examples are given by way of illustration and are in no way intended to limit the scope of the specification or the claims.
[0104]
  Unless otherwise stated, all experimental examples were conducted under an inert atmosphere using standard Schlenk techniques. Several catalysts (Samples CM) were prepared according to the method of the present invention. In addition, two conventional catalysts called Sample A and Sample B were also prepared, but Sample B is a sample prepared according to US Pat. No. 5,563,225 for purposes of comparison with other catalyst samples. . Many of the compounds required for this example: 2-ethylhexanol, benzoyl chloride, n-butyl chloride, t-butyl chloride, chloromethyl ethyl ether, ClTi (OⁱPr)₃And TiCl₄Was purchased from Aldrich Chemical Company and used as received. A heptane solution having a BEM content of 15.6 wt% and an Al content of 0.04 wt% was purchased from Akzo Nobel. Catalyst particle size distribution (average particle size D) shown by all catalyst samples₅₀Measurement is performed using a Malvern Mastersizer, and the particle size distribution values shown in this specification are all calculated based on the volume average.
[0105]
  Hexane was purchased from Phillips and purified by passing it through a 3A molecular sieve column, F200 alumina column and a column packed with BASF R3-11 copper catalyst at a flow rate of 12 mL / min. An Autoclave Engineer reactor was used for the purpose of polymerizing ethylene in the presence of each catalyst sample. The capacity of this reaction tank is 4 liters, and four mixing baffles equipped with two pitch propellers facing each other are attached thereto. Ethylene and hydrogen were introduced into the reaction vessel while maintaining the reaction pressure using a dome-equipped back pressure regulator and maintaining the reaction temperature using steam and cold water. Hexane was introduced into the reactor as a diluent. Unless otherwise stated, the polymerization was carried out under the conditions listed in Table 3A. The resulting fluff particle size distribution (based on mass) of the resulting polyethylene was obtained by sieving analysis using a CSC Scientific Sieve Shaker. The percent fines is defined as the weight percent of fluff particles smaller than 125 microns.
Reference example
  The catalyst sample A of the present invention was prepared by charging a 1 liter reaction vessel with a heptane solution (70.83 g, 100 mmol) having a BEM content of 15.6 wt%. Next, 26.45 g (203 mmol) of 2-ethylhexanol was slowly added to the BEM-containing solution. The reaction mixture was stirred at ambient temperature for 1 hour. Next, ClTi (OⁱPr)_ThreeWas slowly added 77.50 g (100 mmol) of 1.0 M hexane solution. The reaction mixture was stirred at ambient temperature for 1 hour to give the [Mg (O-2-ethylhexyl) 2ClTi (OiPr) 3] adduct. The resulting solution was then added to TNBT (34.04 g, 100 mol) and TiCl._FourA hexane solution (250 mL) containing a mixture of (37.84 g, 200 mmol) was added. The reaction mixture was stirred at ambient temperature for 1 hour resulting in a white precipitate. The precipitate was allowed to settle, and the supernatant was removed by decantation. The precipitate was washed 3 times with about 200 mL of hexane. The solid was slurried again in about 150 mL of hexane and then TiCl._Four50 mL of a hexane solution containing (18.97 g, 100 mmol) was added. The slurry was stirred at ambient temperature for 1 hour. After the solid was allowed to settle, the supernatant was removed by decantation. The solid was washed once with 200 mL of hexane. Next, about 150 mL of hexane was added to the precipitate. The catalyst is again TiCl_FourTreated with 50 mL of hexane solution containing (18.97 g, 100 mmol). The slurry was stirred at ambient temperature for 1 hour. After the solid was allowed to settle, the supernatant was removed by decantation. The catalyst was washed twice with 200 mL hexane. Next, about 150 mL of hexane was added to the precipitate. It was reacted with 7.16 g (15.6 mmol) of a heptane solution containing 25% by weight of TEAl at ambient temperature for 1 hour to obtain the final catalyst.
Comparative Example 1A
  Through introduction of 330 ml of heptane solution containing 15% by weight of dibutylmagnesium, 13.3 ml of pentane solution containing 20% by weight of tetraisobutylaluminoxane, 3 ml of diisoamyl ether and 153 ml of hexane into a 1 liter flask, Comparative catalyst sample B was prepared. The mixture was stirred at 50 ° C. for 10 hours. Next, 0.2 ml of TiCl_FourAnd a mixture of t-butyl chloride (96.4 mL) and DIAE (27.7 mL) was added. The mixture was stirred at 50 ° C. for 3 hours. After the precipitate was allowed to settle, the supernatant was removed by decantation. The solid was washed 3 times with hexane (100 mL) at room temperature. The solid was slurried again in 100 mL of hexane. Anhydrous HCl was introduced into the reaction mixture for 20 minutes. The solid was filtered and then washed twice with 100 mL of hexane. The solid was again suspended in hexane. To this slurry, high purity TiCl_FourWas added, and the mixture was stirred at 80 ° C. for 2 hours. After removing the supernatant by decantation, the catalyst was washed 10 times with 100 mL of hexane. N₂Dried at 50 ° C. under flow.
Comparative Example 2A
  Catalyst sample C according to the present invention was prepared as follows: A 250 mL three-necked round bottom flask equipped with a dropping funnel, a diaphragm and a condenser was charged with a heptane solution (17% BEM content) (17 .71 g, 25 mmol) was charged. Next, 6.61 g (51 mmol) of 2-ethylhexanol was slowly added to the BEM-containing solution, and the reaction mixture was stirred at ambient temperature for 1 hour. Next, ClTi (OⁱPr)_Three19.38 g (25 mmol) of (1M in hexane) was added. The reaction mixture was stirred at ambient temperature for 1 hour to give [Mg (O-2-ethylhexyl)₂ClTi (OⁱPr)_Three] An adduct was formed. Next, 18.51 g (200 mmol) of t-butyl chloride was added to the resulting solution so that the molar ratio of t-butyl chloride to BEM was about 8: 1. The reaction mixture is heated at reflux temperature, ie about 80 ° C., for 24 hours to produce MgCl₂A precipitate (i.e., subsequently becomes the catalyst support) was formed. The white precipitate was allowed to settle and the yellowish supernatant was removed by decantation. The precipitate was washed 3 times with about 100 mL of hexane. Next, about 100 mL of hexane was added to the precipitate and the resulting solution was added to TiCl._Four(9.485 g, 50 mmol) was added slowly. The slurry was stirred at ambient temperature for 1 hour. After the solid was allowed to settle, the supernatant was removed by decantation. The catalyst was washed 4 times with 50 mL of hexane.
Comparative Example 3A
  Catalyst sample D was generated by following the procedure of Comparative Example 2A, except that the reaction rate was increased by adding a larger amount of t-butyl chloride to the flask. Specifically, after adding 37.02 g (400 mmol) of t-butyl chloride to the solution in the flask, the solution was heated at 55 ° C. for 24 hours. Therefore, the solution contained t-butyl chloride / BEM in a molar ratio of about 16: 1 (16 equivalents relative to BEM). As expected, it was observed that Comparative Example 3A had a higher yield than Comparative Example 2A.
[0106]
  Table 1A below shows the composition of the catalysts produced in Comparative Examples 1A and 2A and Examples 1A and 2A.
[0107]
[Table 6]

[0108]
The amounts of Mg and Cl in Samples C and D were similar to those in Sample A. The amount of Ti in samples C and D was intermediate between the amount of Ti in sample A and the amount of Ti in B.
[0109]
  Example2A and3In A, Ti (OⁱPr)_ThreeClMg (OR)₂]_nBy-products produced by the reaction of t-butyl chloride with proton nuclear magnetic resonance (¹1 H NMR) and gas chromatography mass spectroscopy (GCMS) analysis. The main by-product was confirmed to be 2-ethylhexanol rather than the predicted t-butyl 2-ethylhexyl ether or t-butyl-2-isopropyl ether. Based on this result, it is assumed that a certain reduction reaction has occurred in the mixture, possibly resulting in isobutene, which is removed from the reaction. FIG. 1A shows the particle size distribution shown by Sample AD. Both samples A and B show a narrow particle distribution. The average particle size exhibited by the sample B catalyst is slightly larger than that of sample A. Catalyst samples C and D produced with t-butyl chloride show a broader bimodal distribution.
Comparative Example 4A
  N-Butyl chloride, the primary chloride, is added to the flask instead of t-butyl chloride to produce a solution having a n-butyl chloride / BEM molar ratio of about 16: 1 (16 equivalents to BEM). exceptComparisonExample2The procedure of A was followed. Unfortunately, when n-butyl chloride is used, [Ti (OⁱPr)_ThreeClMg (OR)₂]_nIt was not possible to cause precipitation. It is hypothesized that such observations suggest that the chlorine substitution mechanism involves a dissociative elimination (E1) step that requires a stable carbocation species.
Comparative Example 5A
  Catalyst sample K was prepared as follows: In a 500 mL three-necked round bottom flask fitted with a dropping funnel, diaphragm and condenser, a 15.6 wt% heptane solution (8.85 g, 12.5 mmol) and 100 mL of hexane. Next, 3.31 g (25 mmol) of 2-ethylhexanol was slowly added to the BEM-containing solution, and the reaction mixture was stirred at ambient temperature for 1 hour. Next, ClTi (OⁱPr)_ThreeAfter slowly adding 9.69 g (12.5 mmol), the reaction mixture was stirred for 1 h at ambient temperature. Next, 17.6 g (125 mmol) of benzoyl chloride (PhCOCl) was added to the solution so that the molar ratio of PhCOCl to BEM was about 10: 1 (10 equivalents to BEM). The reaction mixture is stirred at ambient temperature for 2 hours to give MgCl₂A precipitate was formed. The white precipitate was allowed to settle, and the supernatant was removed by decantation. The precipitate was washed 3 times with 100 mL of hexane. Thereafter, 100 mL of hexane was added to the precipitate, and then TiCl was added to the solution._Four(4.25 g, 25 mmol) was added slowly. The resulting slurry was stirred at room temperature for 1 hour. After the yellowish solid was allowed to settle, the yellow supernatant was removed by decantation. The catalyst was washed 3 times with 50 mL of hexane.
[0110]
  It should be noted that MgCl is a carrier using PhCOCl.₂It was not necessary to carry out the heating in the reaction for generating the same as in the reaction with t-butyl chloride. In addition, as shown in FIG. 3, the particle size distribution exhibited by catalyst sample K produced using PhCOCl was comparable to the particle size distribution exhibited by catalyst samples A and B.
Comparative Example 6A-11A
  In each case, six more samples (samples EJ) were prepared by following the procedure of Example 4A, except that the amount of PhCOCl was changed so that the molar equivalent to BEM was in the range of 1.2 to 7.2. .
[0111]
  In FIG.ComparisonExample5A-11The catalyst yield for A is shown as a function of PhCOCl usage. The catalyst yield initially increased with increasing PhCOCl concentration and then remained constant at an equivalent weight of about 7.0, reaching a maximum yield of about 1.7 g. In Table 2A below,ComparisonExample5A-11The composition of the catalyst produced in A is shown.
[0112]
[Table 7]

[0113]
  As shown in Table 2A, the titanium content decreased with increasing concentration until the PhCOCl concentration reached 6.0 equivalents and remained constant at higher equivalents. The Ti content of catalyst sample H-K was similar to that of catalyst sample B, but lower than that of catalyst sample A. A possible explanation for this reduction in titanium content is that a benzoyl ester product or unreacted PhCOCl may be involved. NMR and GCMS analysis confirmed that the main by-products of the chlorination reaction were 2-ethylhexyl benzoate and isopropyl benzoate. Such esters and unreacted PhCOCl are all Lewis bases, which can form complexes with electron deficient titanium or magnesium. It is believed that the formation of such a complex will extract more titanium from the support. In addition, the carrier MgCl₂The next titanation by complex formation with TiCl₄We believe that the epitaxial substitution caused by this will be disturbed. It is interesting that the titanium concentration becomes constant when the equivalent of PhCOCl exceeds 7 equivalents. This value is ClTi (OⁱPr)₃And Mg (OR)₂This is equivalent to chlorination of all of the above. When the amount of PhCOCl exceeds such an amount, the amount of ester also becomes constant, suggesting that the ester plays an important role in determining the amount of titanium in the final catalyst. Yes.
[0114]
  The particle size distributions shown by catalyst samples EH and IK produced using various concentrations of PhCOCl are shown in FIGS. 5 and 6, respectively. Sample E produced with the lowest concentration of PhCOCl (1.2 equivalents to BEM) showed a broad bimodal distribution. Increasing the concentration of PhCOCl resulted in a catalyst with a narrower peak distribution and thus improved catalyst morphology. Moreover, as shown in FIG. 7, when the concentration of PhCOCl is increased, the average particle diameter (D₅₀) Is also slightly smaller. MgCl, the carrier that both PhCOCl and the ester product produce₂Suppose that it can form a complex with the upper non-saturated magnesium moiety. As described above, such Lewis bases can assist in the extraction of titanium from the resulting support. Thus, it is thought that the driving force of carrier formation can be corrected by making the titanium complex not present.
Comparative Example 12A
  Catalyst sample L was prepared as follows: a 250 mL three-necked round bottom flask fitted with a dropping funnel, a diaphragm and a condenser with a 15.6 wt% heptane solution (4.43 g, 6.25 mmol) and 30 mL of hexane were charged (30 mL). Next, 1.66 g (12.5 mmol) of 2-ethylhexanol was slowly added to the BEM-containing solution, and the reaction mixture was stirred at ambient temperature for 1 hour. Thereafter, ClTi (OⁱPr)_ThreeAfter the solution (1M in hexanes, 4.85 g, 6.25 mmol) was added slowly, the reaction mixture was stirred at ambient temperature for 1 hour. Next, a hexane solution (25 mL) containing chloromethyl ethyl ether (CMEE) (9.45 g, 100 mmol) in the solution has a molar ratio of CMEE to BEM of about 8: 1 (8 equivalents to BEM). It was added to become. The reaction mixture was stirred at ambient temperature for 1 hour resulting in MgCl₂A precipitate formed. The white precipitate was allowed to settle, and the supernatant was removed by decantation. The precipitate was washed 3 times with 50 mL of hexane. Next, 30 mL of hexane was added to the precipitate, and TiCl was added to the solution._FourA hexane solution (30 mL) of (2.13 g, 125 mmol) was added slowly. The resulting slurry was stirred for 1 hour at ambient temperature. After the yellowish solid was allowed to settle, the yellow supernatant was removed by decantation. The catalyst was then washed 3 times with 50 mL of hexane.
[0115]
  FIG. 9 shows the particle size distribution of catalyst sample L based on CMEE, catalyst sample K based on PhCOCl, and catalyst samples A and B. The particle size distribution of the catalyst sample based on CMEE is slightly wider than that of sample A, sample B and catalyst sample K based on PhCOCl. The particle size distribution exhibited by the catalyst based on CMEE has a shoulder at about 7 microns.
Comparative Example 12A
  Ethylene was polymerized under the conditions listed in Table 3A in the presence of Catalyst Sample A and TEAl cocatalyst.
Comparative Example 13A
  Ethylene was polymerized under the conditions listed in Table 3A in the presence of catalyst sample B and TEAl cocatalyst.
Comparative Example 14A
  Ethylene was polymerized under the conditions listed in Table 3A using catalyst samples C and D produced using t-butyl chloride. In FIG.ComparisonExample14A andFruitExamples2A andComparative Example 13The fluff particle size distribution exhibited by the polymer produced in A is shown. The particle size distribution obtained when using catalyst samples C and D is very broad. In contrast, the distribution obtained when using catalyst samples A and B is relatively narrow. The fines contained in the fluff obtained when using Samples C and D were more than those contained in the fluff obtained when using Samples A and B. Further, the bulk density obtained by using the samples C and D was relatively low.
[0116]
[Table 8]

[0117]
  Table 4A below shows the properties exhibited by the polymer resins produced using catalyst samples A, B, C and D.
[0118]
[Table 9]

[0119]
  In the measurement of the activity (magnesium is based) exhibited by each catalyst sample, the measurement was performed by first dissolving the catalyst and a polymer produced using the catalyst in an acid and extracting the remaining Mg. The catalyst activity was determined based on the residual Mg content. As shown in Table 4A, the Mg reference activity exhibited by catalyst sample C was slightly lower than that shown by catalyst sample A and higher than that shown by catalyst sample B. The activity exhibited by catalyst sample D was higher than that exhibited by catalyst samples A and B. The calculation of the shear response exhibited by the polymer produced using these catalyst samples shows a high load of melt.
The calculation was performed by checking the ratio of the index (HLMI) to the melt index. The shear reaction exhibited by the polymer produced using catalyst samples C and D was similar to the shear reaction exhibited by the polymer produced using sample B, but the shear reaction produced using sample A was similar. It was slightly lower than the shearing reaction exhibited by coalescence. The amount of wax produced was comparable for all polymers.
Comparative Example 15A
  Ethylene was polymerized under the conditions listed in Table 3A using catalyst sample EK produced with benzoyl chloride. FIG. 10A shows the fluff particle size distribution exhibited by the polymer produced in this example (sample G-K). Average particle size (D) of the resin based on PhPOCl₅₀) Was larger than that shown for the samples A and B.
[0120]
  Table 5A below shows a comparison between the morphology of the PhPOCl catalyst sample and the morphology exhibited by the polymer produced using this PhPOCl catalyst sample.
[0121]
[Table 10]

[0122]
  Based on replication theory, the polymer morphology may be related to the catalyst morphology. However, in the case of sample F-K, the polymer form does not seem to correspond to (i.e. not proportional to) the catalyst form, whereas in the case of samples A and B, it appears to correspond.
[0123]
  Table 6A below shows the properties exhibited by the polymers produced using the PhPOCl catalyst sample (sample EK) and catalyst samples A and B.
[0124]
[Table 11]

[0125]
  The Mg reference activity shown by samples EK is higher than the activity shown by samples A and B. The activity generally decreased with increasing PhPOCl equivalent, except for Sample K (PhPOCl equivalent is 10). The density of the polymer of sample EK was similar to that of samples A and B. The melt flow rate (i.e., melt index) exhibited by the sample EK polymer and the sample A polymer was higher than that exhibited by the sample B polymer. The shear reaction exhibited by the polymer of sample EK was similar to that exhibited by the polymer of sample B, but was slightly lower than that exhibited by the polymer of sample A. The amount of wax produced was comparable for all polymers.
Comparative Example 16A
  As described above, MgCl₂By washing the precipitate with hexane, the catalyst sample I based on PhCOCl (hereinafter referred to as “Sample I₁") Was prepared. In this example, sample I₁Another catalyst sample I produced in the same manner without the washing step₂And catalyst sample I₁Compare It is believed that eliminating such a washing step can significantly reduce the time for catalyst production and lower costs. Table 7A below shows Sample I₁And sample I₂The catalyst composition of is shown.
[0126]
[Table 12]

[0127]
  The elimination of the cleaning step resulted in a titanium concentration that was about 30% lower. Washed catalyst sample I₁The appearance color was bright yellow. Also, unwashed catalyst sample I₂But TiCl₄It was clear that the color was yellow during the addition of. However, TiCl₄Became colorless immediately upon contact with the mother liquor. Esters and TiCl₄The complex of can yield yellow but TiCl₄Assume that can react with PhCOCl to yield a colorless compound. Such observations support the observations made above that the concentration of titanium depends on the amount of PhCOCl. If excess PhCOCl and esters are not removed, they will be TiCl₂It is thought that titanium does not adhere to the support surface by forming a complex with both the support surface and the support surface.
[0128]
  As shown in FIG.₁And sample I₂Showed almost the same particle size distribution. Therefore, the particle size distribution of the catalyst was not affected by the washing step. Such an observation is not very surprising, because the washing step was performed on the support MgCl₂It was because it was after producing. Sample I₁And sample I₂Both were used to polymerize ethylene. Table 8A below shows Sample I₁And sample I₂The catalyst form and polymer form of are shown.
[0129]
[Table 13]

[0130]
  Table 8A further supports the conclusion that the particle size distribution is not affected by the washing step. The elimination of the washing step significantly increased the number of fines produced in the polymer. The reason for the increased amount of fines may be due to the lower productivity. Catalyst sample I₁And sample I₂The properties of the polymer produced using are shown in Table 9A below.
[0131]
[Table 14]

[0132]
  As shown in Table 9A, the polymerization activity exhibited by the unwashed catalyst was approximately half that exhibited by the washed catalyst. The densities exhibited by the two polymers were almost the same. However, the shear reaction data show that the molecular weight distribution when using a non-washed catalyst is narrower than that of the washed catalyst. The presence of PhCOCl and esters in the catalyst is believed to affect the distribution of active sites in the catalyst.
Comparative Example 17A
  We also studied the effect of BEM concentration on catalyst properties. A first catalyst sample (Sample L) based on PhCOCl was prepared using a BEM solution diluted with 100 mL of hexane. For comparison purposes, a second catalyst sample (Sample M) based on PhCOCl was prepared using a BEM solution diluted with 20 mL of hexane. FIG. 12 shows the catalyst particle size distribution shown by the catalyst samples L and M. Both catalysts have a very similar distribution. The compositions and properties of catalyst samples L and M and the polymers produced using them are shown in Tables 10A and 11A below, respectively.
[0133]
[Table 15]

[0134]
[Table 16]

[0135]
Tables 10A and 11A show that catalyst composition and polymer properties are essentially unaffected by the concentration of BEM.
[0136]
  In conclusion, novel catalysts were synthesized using alkyl chlorides such as n-butyl chloride, t-butyl chloride and chloromethyl ethyl ether. The use of benzoyl chloride and chloromethyl ethyl ether results in a catalyst that exhibits a satisfactory particle size distribution, while t-butyl chloride results in a bimodal distribution and n-butyl chloride produces MgCl.₂Could not be produced. The catalyst preparation was optimized by changing the amount of benzoyl chloride added to the magnesium alkoxide adduct. As expected, the catalyst yield increased with increasing amounts of benzoyl chloride and became saturated when the equivalent of benzoyl chloride based on BEM was approximately 7 equivalents. The particle size distribution of the catalyst narrowed with increasing amount of benzoyl chloride.
[0137]
  Experiments were also conducted to observe the effect of eliminating the washing step performed after the carrier was formed. Catalyst samples that were not washed had lower activity and lower shear response than the washed samples. The effect of BEM concentration on the catalyst properties was also investigated. Neither the particle size distribution, the catalyst composition nor the polymer properties were affected by the BEM concentration.
[0138]
  While embodiments of the invention have been illustrated and described, those skilled in the art can make modifications without departing from the spirit and teachings of the invention. The embodiments described herein are merely exemplary and are not intended to be limiting. Where a chemical mechanism or theory is disclosed, it is presented on the basis of information and ideas and is not necessarily intended to limit the scope thereby. Various variations and modifications of the invention disclosed herein are possible and are within the scope of the invention. Accordingly, the scope of protection is not limited by the above description, but is limited only by the scope of the claims, which includes all equivalents of the subject matter of the claims. It is.
[Brief description of the drawings]
[0139]
FIG. 1 is a sedimentation efficiency curve (FIG. 1) showing a polymer produced using a catalyst of the present invention (Example 1) and a polymer produced using a conventional catalyst (Comparative Example 4). settling efficiency).
FIG. 2 shows the particle size distribution exhibited by the catalysts described in Comparative Examples 1A-2A and Examples 1A-2A.
FIG. 3 shows the particle size distribution exhibited by the catalysts described in Comparative Examples 1A-2A and Example 4A.
FIG. 4 shows the catalyst yield for Examples 4A-10A as a function of PhCOCl usage.
FIG. 5 shows the particle size distribution exhibited by the catalyst produced in Examples 4A-10A.
FIG. 6 shows the particle size distribution exhibited by the catalyst produced in Examples 4A-10A.
FIG. 7 shows the average catalyst particle size (D) in Examples 4A-10A.₅₀) As a function of PhCOCl usage.
FIG. 8 shows the particle size distribution exhibited by the catalysts described in Comparative Examples 1A-2A and Examples 4A and 11A.
FIG. 9 shows the fluff particle size distribution exhibited by the polymer resins described in Comparative Examples 3A-4A and Example 12A.
FIG. 10 shows the fluff particle size distribution exhibited by the polymer resins described in Comparative Examples 3A-4A and Example 13A.
FIG. 11 shows the particle size distribution exhibited by the catalyst described in Example 14A.
FIG. 12 shows the particle size distribution exhibited by the catalyst described in Example 15A.

Claims (41)

A method for producing a catalyst component D for producing a polyolefin, comprising the following steps (a) to (d):
(A) A magnesium dialkoxide compound is represented by the general formula: ClTiR ′ ″ _x , wherein R ′ ″ is a hydrocarbyl moiety having 2 to 6 carbon atoms, and x is a valence of Ti−1. To make a reaction product A by contacting with a halogenating agent represented by
(B) Reaction product A is converted into two types of tetrasubstituted titanium compounds [all four substituents are the same and the substituents are halides or alkoxides or phenoxides having 2 to 10 carbon atoms] A reaction product B by contacting with a first halogenation / titanating agent comprising a mixture of or a mixture of titanium halide and organic titanate,
(C) the reaction product B with a second make C reaction product is contacted with a halogenating / titanation agent comprising titanium tetrachloride,
(D) The reaction product C is brought into contact with a third halogenating / titanating agent containing titanium tetrachloride to form catalyst component D. The method of claim 1, wherein the halogenating agent is ClTi (O ⁱ Pr) ₃ . The first halogenating / titanating agent is a mixture of TiCl ₄ and Ti (OBu) ₄ with TiCl ₄ / Ti (OBu) _{4 in} the range of 0.5: 1 to 6: 1. Method.   The process of claim 1 wherein the ratio of titanium tetrachloride to magnesium included in each of steps (c) and (d) is in the range of 0.1 to 5.   The process of claim 1 wherein the reaction products A, B and C are washed with a hydrocarbon solvent prior to being subjected to the next halogenation / titanation step.   6. Reaction products A, B and C are washed with a hydrocarbon solvent until the content of titanium species [Ti] prior to undergoing the next halogenation / titanation step is less than 100 mmol / L. the method of.   The process according to claim 1, wherein the reaction product D is washed with a hydrocarbon solvent until the titanium species [Ti] content is less than 20 mmol / L.   An electron donor is present in any one or more of steps (a), (b), (c) or (d) and the ratio of electron donor to metal is from 0: 1 to 10: 1. The method of claim 1, wherein the method is within range.   The method of claim 1, further comprising disposing the catalyst component on an inert support.   The method according to claim 9, wherein the inert carrier is a magnesium compound.   The method of claim 1, further comprising the step (e) of contacting catalyst component D with a pre-activator of an organometallic to form a pre-activated catalyst system. A catalyst for producing a polyolefin produced by a process comprising the step (a) of contacting a catalyst component D produced by a process comprising the following steps (i) to (iv) with an organometallic preactivator:
(I) A magnesium dialkoxide compound is represented by the general formula: ClTiR ′ ″ _x , wherein R ′ ″ is a hydrocarbyl moiety having 2 to 6 carbon atoms, and x is Ti valence of −1. To produce a reaction product A by contacting with a halogenating agent represented by
(Ii) Reaction product A is converted into two types of tetra-substituted titanium compounds [all four substituents are the same and the substituents are halides or alkoxides or phenoxides having 2 to 10 carbon atoms] A reaction product B by contacting with a first halogenation / titanating agent comprising a mixture of or a mixture of titanium halide and organic titanate,
(Iii) the reaction product B with a second make C reaction product is contacted with a halogenating / titanation agent comprising titanium tetrachloride,
(Iv) The reaction product C is brought into contact with a third halogenating / titanating agent containing titanium tetrachloride to form catalyst component D. The organometallic preactivator is an aluminum alkyl represented by the formula AlR ₃ , wherein R is an alkyl or halide having 1 to 8 carbon atoms, each R may be the same or different. 12. The catalyst according to 12.   14. The catalyst of claim 13 wherein the organometallic preactivator is trialkylaluminum.   The catalyst of claim 13 wherein the ratio of aluminum to titanium is in the range of 0.1: 1 to 2: 1.   13. A catalyst according to claim 12, wherein the reaction products A, B and C have been washed with a hydrocarbon solvent before being subjected to the next halogenation / titanation step.   The catalyst according to claim 12, wherein the catalyst component D is washed with a hydrocarbon solvent until the content of titanium species [Ti] is less than 20 mmol / L. Olefin polymerization method comprising the following steps (a) and (b):
(A) contacting one or more olefin monomers under polymerization conditions in the presence of a catalyst component made by a process comprising the following steps (i) to (iv):
(I) A magnesium dialkoxide compound is represented by the general formula: ClTiR ′ ″ _x , wherein R ′ ″ is a hydrocarbyl moiety having 2 to 6 carbon atoms, and x is Ti valence of −1. To produce a reaction product A by contacting with a halogenating agent represented by
(Ii) Reaction product A is converted into two types of tetra-substituted titanium compounds [all four substituents are the same and the substituents are halides or alkoxides or phenoxides having 2 to 10 carbon atoms] A reaction product B by contacting with a first halogenation / titanating agent comprising a mixture of or a mixture of titanium halide and organic titanate,
(Iii) the reaction product B with a second make C reaction product is contacted with a halogenating / titanation agent comprising titanium tetrachloride,
(Iv) contacting the reaction product C with a third halogenating / titanating agent comprising titanium tetrachloride to form the catalyst component,
(However, at least one of the reaction products A, B, and C is washed with a hydrocarbon solvent before being subjected to the next halogenation / titanation step, and the reaction product D is added to the hydrocarbon solvent. Is washed until the titanium species [Ti] content is less than 100 mmol / L)
(B) Take out the polyolefin polymer.   The method of claim 18, wherein the polymer exhibits a molecular weight distribution of at least 4.0.   The method of claim 18, wherein the bulk density exhibited by the polymer is at least 0.31 g / cc. A method for producing a catalyst for producing a polyolefin, comprising the following steps (a) to (e):
(A) A magnesium dialkoxide compound is represented by the general formula: ClTiR ′ ″ _x , wherein R ′ ″ is a hydrocarbyl moiety having 2 to 6 carbon atoms, and x is a valence of Ti−1. To make a reaction product A by contacting with a halogenating agent represented by
(B) Reaction product A is converted into two types of tetrasubstituted titanium compounds [all four substituents are the same and the substituents are halides or alkoxides or phenoxides having 2 to 10 carbon atoms] A reaction product B by contacting with a first halogenation / titanating agent comprising a mixture of or a mixture of titanium halide and organic titanate,
(C) the reaction product B with a second make C reaction product is contacted with a halogenating / titanation agent comprising titanium tetrachloride,
(D) contacting reaction product C with a third halogenating / titanium agent comprising titanium tetrachloride to form reaction product D;
(E) contacting the reaction product D with an organometallic preactivator to make a catalyst;
Wherein the magnesium dialkoxide compound is represented by the general formula: MgRR ′ (wherein R and R ′ are alkyl groups having 1 to 10 carbon atoms, which may be the same or different). An alkyl compound, a linear or branched alcohol represented by a general formula: R ″ OH [wherein R ″ is an alkyl group having 2 to 20 carbon atoms], and a formula: AlR ′ ″. _{3 wherein} at least one R ′ ″ is an alkyl, alkoxide or halide having 1 to 8 carbon atoms, and each R ′ ″ may be the same or different; The average particle size of the catalyst increases as the ratio of aluminum alkyl to magnesium alkyl increases.]   The method of claim 21, wherein the ratio of aluminum alkyl to magnesium alkyl is in the range of 0.01: 1 to 10: 1.   24. The step of claim 21, wherein each of steps (c) and (d) includes titanium tetrachloride as a halogenating / titanating agent and the ratio of titanium tetrachloride to magnesium is in the range of 0.1 to 5. Method described.   The method according to claim 21, wherein the magnesium dialkoxide compound is magnesium di (2-ethylhexoxide).   The method according to claim 21, wherein the alkylmagnesium compound is diethylmagnesium, dipropylmagnesium, dibutylmagnesium or butylethylmagnesium.   The method of claim 21, wherein the alcohol is selected from the group consisting of ethanol, propanol, isopropanol, butanol, isobutanol, 2-methyl-pentanol, and 2-ethylhexanol.   The method of claim 21, wherein the organometallic preactivator comprises aluminum alkyl. The first halogenation / titanation agent is TiCl ₄ / Ti (OBu) ₄ is 0.5: 1 to 6: claim 21 which is a TiCl ₄ and Ti (OBu) ₄ mixture in the first range the method of.   The method of claim 21, further comprising an electron donor in the reaction of steps (a), (b) and (c).   The method of claim 21, wherein the ratio of electron donor to magnesium is in the range of 0: 1 to 10: 1.   30. The method of claim 29, wherein the electron donor is an ether. The method according to claim 21, wherein the halogenating agent is ClTi (O ⁱ Pr) ₃ .   The process according to claim 21, wherein at least one of the reaction products A, B, C and D is washed with a hydrocarbon solvent until the titanium species [Ti] content is less than 100 mmol / L.   An electron donor is present in any one or more of steps (a), (b), (c) or (d) and the ratio of electron donor to metal is in the range of 0: 1 to 10: 1. The method of claim 21.   The method of claim 21, further comprising disposing the catalyst on an inert support. 36. The method of claim 35 , wherein the inert carrier is a magnesium compound. A catalyst for producing a polyolefin produced by a process comprising the step (a) of contacting a catalyst component D produced by a process comprising the following steps (i) to (iv) with an organometallic preactivator:
(I) A magnesium dialkoxide compound represented by the general formula: ClTiR ″, represented by the general formula: Mg (OR ″) ₂ , wherein R ″ is a hydrocarbyl having 1 to 20 carbon atoms or a substituted hydrocarbyl. 1 halogen of 1 halogenating agent represented by ' _x [wherein R ″ is a hydrocarbyl moiety having 2 to 6 carbon atoms, and x is a valence of Ti-1] To make a reaction product A by contacting with a halogenating agent capable of exchanging with alkoxide of
(Ii) Reaction product A is converted into two types of tetra-substituted titanium compounds [all four substituents are the same and the substituents are halides or alkoxides or phenoxides having 2 to 10 carbon atoms] A reaction product B by contacting with a first halogenation / titanating agent comprising a mixture of or a mixture of titanium halide and organic titanate,
(Iii) the reaction product B with a second make C reaction product is contacted with a halogenating / titanation agent comprising titanium tetrachloride,
(Iv) contacting the reaction product C with a third halogenating / titanium agent containing titanium tetrachloride to form a catalyst component D [wherein the magnesium dialkoxide compound is represented by the general formula: MgRR ′ (wherein , R and R ′ are alkyl groups having 1 to 10 carbon atoms, which may be the same or different, and a general formula: R ″ OH [wherein R ″ is A linear or branched alcohol represented by the formula: AlR ′ ″ ₃ , wherein at least one R ′ ″ has 1 carbon atom. An alkyl or alkoxide or halide of ˜8, each R ′ ″ may be the same or different), and the average particle size of the catalyst relative to magnesium alkyl Armini Increases as to increase the ratio of Muarukiru] The organometallic preactivator is an aluminum alkyl represented by the formula AlR ₃ , wherein R is an alkyl or halide having 1 to 8 carbon atoms, and each R may be the same or different. 38. The catalyst according to claim 37.   38. The catalyst of claim 37, wherein the organometallic preactivator is trialkylaluminum.   38. The catalyst of claim 37, wherein the ratio of aluminum to titanium is in the range of 0.1: 1 to 2: 1. A method for adjusting the particle size of a polyolefin polymer comprising the following steps (a) and (b):
(A) contacting one or more olefin monomers under polymerization conditions in the presence of a catalyst made by a process comprising the steps of (i) to (vi) below:
(I) a magnesium alkyl compound represented by the general formula: MgRR ′ (wherein R and R ′ are alkyl groups having 1 to 10 carbon atoms, which may be the same or different), and a general formula: R A linear or branched alcohol represented by '' OH (wherein R '' is an alkyl group having 2 to 20 carbon atoms) and a formula: AlR ''' ₃ (wherein at least one R ″ ′ is alkyl having 1 to 8 carbon atoms, alkoxide or halide, and each R ′ ″ may be the same or different. (OR ″) ₂ (wherein R ″ is a hydrocarbyl having 1 to 20 carbon atoms or a substituted hydrocarbyl), and a magnesium dialkoxide represented by
(Ii) The magnesium dialkoxide compound represented by the general formula: ClTiR ′ ″ _x , wherein R ′ ″ is a hydrocarbyl moiety having 2 to 6 carbon atoms, and x is the valence of A−1. To form a reaction product A by contacting with a halogenating agent represented by
(Iii) Reaction product A is converted into two types of tetrasubstituted titanium compounds [all four substituents are the same and the substituents are halides, alkoxides or phenoxides having 2 to 10 carbon atoms] A reaction product B by contacting with a first halogenation / titanating agent comprising a mixture of or a mixture of titanium halide and organic titanate,
(Iv) the reaction product B with a second make C reaction product is contacted with a halogenating / titanation agent comprising titanium tetrachloride,
(V) contacting the reaction product C with a third halogenating / titanating agent containing titanium tetrachloride to form a catalyst component;
(Vi) contacting the catalyst component with an organoaluminum agent;
(B) Take out the polyolefin polymer.
(Here, the average particle size of the polyolefin increases as the ratio of aluminum alkyl to magnesium alkyl used in step (i) increases)

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