JP2013516542A - チーグラー・ナッタ触媒系及びそれから生成するポリマー - Google Patents
チーグラー・ナッタ触媒系及びそれから生成するポリマー Download PDFInfo
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- JP2013516542A JP2013516542A JP2012548223A JP2012548223A JP2013516542A JP 2013516542 A JP2013516542 A JP 2013516542A JP 2012548223 A JP2012548223 A JP 2012548223A JP 2012548223 A JP2012548223 A JP 2012548223A JP 2013516542 A JP2013516542 A JP 2013516542A
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
-
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Abstract
Description
本発明の態様は、一般的にチーグラー・ナッタ型触媒組成物の調製方法に関する。
チーグラー・ナッタ触媒系の調製のための多くの方法は成分のブレンドを使用する。不運なことに、そのようなブレンドは一般に高い製造コストを有する特殊化学品である。
本発明の態様は、触媒系の調製方法を含む。方法は一般的に、マグネシウムジアルコキシドを含む第1の化合物を準備し、第1の化合物を、一般的に式:
Ti(OR1)4;
[式中、R1はC1〜C10直鎖状から分枝鎖状アルキルから選ばれる]
により示される第2の化合物と接触させて反応生成物「A」の溶液を調製し、反応生成物「A」の溶液を第1の金属ハライドと接触させて固体反応生成物「B」を生成させ、固体反応生成物「B」を第2の金属ハライドと接触させて反応生成物「C」を生成させ、反応生成物「C」を還元剤と接触させて触媒成分を調製することを含む。
Al(OR2)3;
により示され、式中、R2はC1〜C10直鎖状もしくは分枝鎖状アルキルから選ばれる。
図1及び2は、調製される触媒の容量平均粒度分布を示す。
序論及び定義
ここで詳細な説明を与える。添付の請求項のそれぞれは別々の発明を定義し、それは侵
害の目的に関し、請求項中に規定される種々の要素又は制限への同等事項を含むと認識される。状況によって、下記の「発明」へのすべての言及は、いくつかの場合にはある特定の態様のみを指し得る。他の場合、「発明」への言及は1つもしくはそれより多くの、しかし必ずしもすべてではない請求項中に挙げられる主題を指すことが認識されるであろう。ここで特定の態様、変形及び実施例を含む本発明のそれぞれを下記でさらに詳細に説明するが、本発明はこれらの態様、変形又は実施例に制限されず、それらは、本特許中の情報を利用可能な情報及び技術と組み合わせると、当該技術分野における通常の熟練者が本発明を作り且つ利用することを可能にするために含まれる。
チーグラー・ナッタ触媒系は一般に金属成分(例えば触媒前駆体)と1種もしくはそれより多い追加の成分、例えば触媒担体、助触媒及び/又は1種もしくはそれより多い電子供与体の組み合わせから調製される。
MRA x;
により示される金属成分を含み、式中、Mは遷移金属であり、RAはハロゲン、アルコキシ又はヒドロカルビル基であり、xは遷移金属の原子価である。例えばxは1〜4であることができる。
トン、ニトリル、エーテル、ホスフィン、ジエーテル、スクシネート、フタレート又はジアルコキシベンゼンが含まれ得る(引用することによりそれらの記載事項が本明細書の内容となる米国特許第5,945,366号明細書及び米国特許第6,399,837号明細書を参照されたい。)。
1)MgR3R4+2R5OH→Mg(OR6)2
2)Mg(OR6)2+ClA(OxR7)y→“A1”
3)“A1”+TiCl4/Ti(OR8)4→“A2”
4)“A2”+TiCl4→“B”
5)“B”+TiCl4→“C”
6)“C”+AR9 3→触媒
MgR3R4; (I)
により示され、式中、R3及びR4は独立してC1−C10アルキル基から選ばれた。アルキルマグネシウム化合物の制限ではない例には、例えばブチルエチルマグネシウム(BEM)、ジエチルマグネシウム、ジプロピルマグネシウム及びジブチルマグネシウムが含まれる。
R5OH; (II)
により示され、式中、R5はC2〜C20直鎖状もしくは分枝鎖状アルキル基から選ばれた。アルコールの制限ではない例には一般に、例えばブタノール、イソブタノール及び2−エチルヘキサノールが含まれる。
ClA(OxR7)y; (III)
により示され、式中、Aはチタン、ケイ素、アルミニウム、炭素、錫及びゲルマニウムから選ばれ、R7はC1〜C10直鎖状もしくは分枝鎖状アルキル、例えばメチル、エチル、プロピル及びイソプロピルから選ばれ、xは0又は1であり、yはAの原子価マイナス1であった。第1の薬品の制限ではない例には、例えばクロロチタントリイソプロポキシドClTi(OiPr)3及びClSi(Me)3が含まれる。
TiCl4/Ti(OR8)4; (IV)
により示され、式中、R8はC2〜C20アルキル基から選ばれた。第2の薬品の制限ではない例には、塩化チタンとチタンアルコキシドのブレンド、例えばTiCl4/Ti(OBu)4が含まれる。
Ti(OR1)4; (V)
により示され、式中、R1はC1〜C10直鎖状から分枝鎖状アルキルから選ばれる。1つもしくはそれより多い特定の態様において、第2の化合物は例えばチタン2−エチルヘキシルアルコキシド、チタンn−ブトキシド及びそれらの組み合わせから選ばれる。
Al(OR2)3; (VI)
により示され、式中、R2はC1〜C10直鎖状から分枝鎖状アルキルから選ばれる。1つもしくはそれより多い特定の態様において、第3の化合物はアルミニウム2−エチルヘキシルアルコキシドである。
4又は約0.45〜約2.0の当量において加えることができる。さらに、第2の金属ハライドを段階的なやり方で加えることができ、それは、触媒性能に影響を与えるために、第1に半分を加え、次いで洗浄後に第2の半分を導入することである。
AlR9 3; (VII)
を有するアルミニウムアルキルが含まれ得、式中、R9はC1〜C10アルキル化合物である。アルミニウムアルキル化合物の制限ではない例には一般に、例えばトリメチルアルミニウム(TMA)、トリイソブチルアルミニウム(TIBAl)、トリエチルアルミニウム(TEAl)、n−オクチルアルミニウム及びn−ヘキシルアルミニウムが含まれる。
本明細書の他の場所で示す通り、触媒系を用いてポリオレフィン組成物を生成させる。上記に記載の通り、及び/又は当該技術分野における熟練者に既知の通りに触媒系が調製されたら、その組成物を用いて多様な方法を実施することができる。重合法において用いられる装置、プロセス条件、反応物、添加物及び他の材料は、生成されているポリマーの所望の組成及び性質に依存して、与えられる方法内で変わるであろう。そのような方法には、例えば溶液相、気相、スラリ相、バルク相、高圧法又はそれらの組み合わせが含まれ得る(引用することによりそれらの記載事項が本明細書の内容となる米国特許第5,525,678号明細書;米国特許第6,420,580号明細書;米国特許第6,380,328号明細書;米国特許第6,359,072号明細書;米国特許第6,346,586号明細書;米国特許第6,340,730号明細書;米国特許第6,339,134号明細書;米国特許第6,300,436号明細書;米国特許第6,274,684号明細書;米国特許第6,271,323号明細書;米国特許第6,248,845号明細書;米国特許第6,245,868号明細書;米国特許第6,245,705号明細書;米国特許第6,242,545号明細書;米国特許第6,211,105号明細書;米国特許
第6,207,606号明細書;米国特許第6,180,735号明細書及び米国特許第6,147,173号明細書を参照されたい。)。
本明細書に記載される方法を介して生成するポリマー(及びそのブレンド)には、例えば線状低密度ポリエチレン、エラストマー、プラストマー、高密度ポリエチレン、低密度ポリエチレン、中密度ポリエチレン、ポリプロピレン及びポリプロピレンコポリマーが含まれ得るが、これらに限られない。
エチレンに基づくポリマーを指す。
ポリマー及びそのブレンドは、成形作業(forming operation)(例えばフィルム、シート、パイプ及び繊維押出し及び共押出しならびに吹込成形、射出成形及び回転式成形)のような当該技術分野における熟練者に既知の用途において有用である。フィルムには、例えば食品と接触するか又は食品と接触しない用途における、収縮フィルム、クリングフィルム、延伸フィルム(stretch film)、シーリングフィルム、配向フィルム(oriented film)、スナック包装、重包装袋、野菜袋、焼成及び冷凍食品包装、医療用包装、産業用ライナー(industrial liners)及び膜として有用な、押出し又は共押出しにより、あるいは積層により成形される吹込み、延伸又はキャストフィルムが含まれる。繊維には、例えば袋(sacks)、袋(bags)、ロープ、トワイン(twine)、カーペット裏地、カーペット糸、フィルター、おむつ生地、医療用衣服及びジオテキスタイルの製造のための編織又は不織形態における使用のためのスリットフィルム、モノフィラメント、溶融紡糸、溶液紡糸及び溶融吹込み繊維作業が含まれる。押出し製品には、例えば医療用チューブ、ワイア及びケーブルコーティング、シート、熱成形シート(形材(profiles)及びプラスチック波形板紙を含む)、ジオメンブレン(geomambranes)及び池ライナー(pond liners)が含まれる。成形品には、例えばビン、タンク、大中空製品、剛性食品容器及びおもちゃの形態の単層及び多層構造物が含まれる。
Claims (18)
- マグネシウムジアルコキシドを含む第1の化合物を準備し;
第1の化合物を、一般的に式:
Ti(OR1)4;
[式中、R1はC1〜C10直鎖状から分枝鎖状アルキルから選ばれる]
により示される第2の化合物と接触させて反応生成物「A」の溶液を調製し;
反応生成物「A」の溶液を第1の金属ハライドと接触させて固体反応生成物「B」を生成させ;
固体反応生成物「B」を第2の金属ハライドと接触させて反応生成物「C」を生成させ;そして
反応生成物「C」を還元剤と接触させて触媒成分を調製する
ことを含んでなる触媒系の調製方法。 - 第1の化合物が一般に式Mg(OEt)2により示される請求項1の方法。
- 第2の化合物がチタン2−エチルヘキシルアルコキシド、チタンn−ブトキシド及びそれらの組み合わせから選ばれる請求項1の方法。
- 第1の化合物が約0.75〜約1.75の当量において第2の化合物に接触する請求項1の方法。
- さらに第1の化合物を第2の化合物の存在下で第3の化合物と接触させることを含んでなり、ここで第3の化合物は一般に式:
Al(OR2)3;
により示され、式中、R2はC1〜C10直鎖状もしくは分枝鎖状アルキルから選ばれる請求項1の方法。 - 第3の化合物がアルミニウム2−エチルヘキシルアルコキシドを含む請求項5の方法。
- 第3の化合物が約0.1〜約0.5の当量において第1の化合物に接触する請求項5の方法。
- 第2の化合物及び第3の化合物が第1の化合物との接触の前に互いに接触する請求項5の方法。
- 還元剤が有機リチウム化合物、有機マグネシウム化合物、有機アルミニウム化合物及びそれらの組み合わせから選ばれる請求項1の方法。
- 還元剤がトリエチルアルミニウムを含む請求項1の方法。
- 金属ハライドがTiCl4を含む請求項1の方法。
- 請求項5の方法から調製されるチーグラー・ナッタ触媒。
- さらに、少なくとも約5ミクロンの容量平均粒度を含んでなる請求項12の触媒。
- 触媒が第3の化合物と接触しない触媒の容量平均粒度より大きい容量平均粒度を示す請求項12の触媒。
- 反応領域内にオレフィンモノマーを導入し;
オレフィンモノマーを請求項1の触媒と接触させてポリオレフィンを生成させ;そして
反応領域からポリオレフィンを回収する
ことを含んでなる重合法。 - 請求項15の方法により生成するポリオレフィン。
- 触媒系が二峰性粒度分布を示す請求項1の触媒。
- 反応生成物「A」が1つのプロセス段階で第2の化合物及び第1の化合物から生成する請求項1の方法。
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ES2586235T3 (es) | 2016-10-13 |
BR112012017021B1 (pt) | 2019-04-09 |
EP2523754A4 (en) | 2013-10-09 |
MX2012007812A (es) | 2012-08-31 |
KR20120112542A (ko) | 2012-10-11 |
EA201270682A1 (ru) | 2012-12-28 |
US8592535B2 (en) | 2013-11-26 |
MX357104B (es) | 2018-06-26 |
CA2785565A1 (en) | 2011-07-14 |
CN102711980A (zh) | 2012-10-03 |
US9416202B2 (en) | 2016-08-16 |
WO2011085350A8 (en) | 2012-08-09 |
EP2523754B1 (en) | 2016-05-11 |
TWI607027B (zh) | 2017-12-01 |
US20110172379A1 (en) | 2011-07-14 |
KR101861091B1 (ko) | 2018-05-28 |
JP5922039B2 (ja) | 2016-05-24 |
CA2785565C (en) | 2016-08-16 |
EA022767B1 (ru) | 2016-02-29 |
BR112012017021A2 (pt) | 2016-04-05 |
TW201144339A (en) | 2011-12-16 |
WO2011085350A1 (en) | 2011-07-14 |
EP2523754A1 (en) | 2012-11-21 |
CN102711980B (zh) | 2015-08-19 |
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