“Living Polymers” on Polymerization with Extremely Productive Ziegler Catalysts

Sinn, Hansjörg; Kaminsky, Werner; Vollmer, Hans‐Jürgen; Woldt, Rüdiger

doi:10.1002/anie.198003901

Cited by 654 publications

(303 citation statements)

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“…The bulk density depends on the kind of activator, and has the values 198-307 and 170-280 g/dm 3 , for AlEt 2 Cl and AlEtCl 2 , respectively. An increase in the time of duration of the reaction results in an increase of the bulk density of the polyethylene.…”

Section: Effects Of the Catalyst Recycling And Reaction Timementioning

confidence: 99%

“…Metallocenes are a consecutive generation of organometallic catalysts for olefin polymerization, which make possible to tailor the structure of polymers in a way which has not been achieved before [1][2][3][4][5]. Unfortunately, the metallocene systems, both homogeneous and heterogeneous, have disadvantageous features hindering their application in industrial scale processes [6][7][8].…”

Section: Introductionmentioning

confidence: 99%

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Effect of immobilization of titanocene catalyst in aralkyl imidazolium chloroaluminate media on performance of biphasic ethylene polymerization and polyethylene properties

2012

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], were applied as media of the Cp 2 TiCl 2 catalyst for biphasic ethylene polymerization. The studied aralkyl ionic liquids ensure greater stability of the catalyst at higher temperatures and more regular morphology of the produced polyethylene than analogous 1-n-alkyl-3-methylimidazolium chloroaluminates. The alkylaluminium compound participates in the termination reaction of the polymer chain. The catalyst is stable and enables recycling of the ionic liquid phase in the consecutive polymerization reactions. The [Ph-C 2 mim][AlCl 4 ] ionic liquid and AlEt 2 Cl alkylaluminium compound turned out to be the most suitable for the biphasic process. The influence of the kind of ionic liquid, alkylaluminium compound (AlEt 2 Cl and AlEtCl 2 ), activator/catalyst molar ratio, reaction temperature, reaction time and catalyst recycling on the polymerization performance as well as polyethylene properties such as molecular weight (M w ), polydispersity, melting temperature, crystallinity degree, bulk density and particle size is presented.

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Section: Effects Of the Catalyst Recycling And Reaction Timementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Effect of immobilization of titanocene catalyst in aralkyl imidazolium chloroaluminate media on performance of biphasic ethylene polymerization and polyethylene properties

2012

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“…After informing Hansjörg Sinn, who had been Minister of Science and Research of the City State Hamburg since 1978, we decided to file a patent application covering these exciting results. 1 Later, we discovered that also the simple Cp 2 ZrCl 2 , which is much more stable than Cp 2 Zr(CH 3 ) 2 , is an active catalyst precursor in combination with MAO.…”

Section: The Discoverymentioning

confidence: 99%

“…[1][2][3] These catalyst systems have only one kind of active metal center (single site catalysts) and were the start-up for the introduction of a new family of transition metal complexes for olefin, diene, and styrene polymerization. Up to now, some 10,000 articles and more than 4000 patents have been published on the subject of polymerization with these single site catalysts.…”

Section: Introductionmentioning

confidence: 99%

The discovery of metallocene catalysts and their present state of the art

Kaminsky

2004

J. Polym. Sci. A Polym. Chem.

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352

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Metallocene and other transition metal complexes activated by methylaluminoxane are highly active catalysts for the polymerization of olefins, diolefins, and styrene, which was discovered at the University of Hamburg about 25 years ago. These catalysts allow the synthesis of polymers with a highly defined microstructure, tacticity, and stereoregularity, as well as new copolymers with superior properties such as film clarity, tensile strength, and lower extractables. A better understanding of the mechanism of olefin polymerization leads to findings of other new single site catalysts. The development of the metallocene/MAO-catalysts from their discovery to their present state of the art is presented. Keywords:metallocene catalysts; methylaluminoxane; olefin polymerization; zirconocene complexes; polyolefins; single site catalysis Dr. Kaminsky received his Ph.D. and degree in chemistry from Hamburg University, Germany in 1971 for investigating the side reactions of biscyclopentadienyl-zirconiumdichloride and triethylaluminum. He then served as lecturer and continued his research on the determination of zirconocene/aluminumalkyl-complexes and recycling of polymers by pyrolysis in a fluidized bed process. During that time he and Hansjörg Sinn discovered that the activity of metallocenes and other transition metals can be increased extremely by the addition of MAO as a cocatalyst. In 1979 he became full professor at the University of Hamburg for Technical and Macromolecular Chemistry and has served as director, dean, and president of German chemical society, Hamburg section. Dr. Kaminsky has received the following honors and rewards: elected to the

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“…Studies on variations of the Group 4 metallocene structures (Erker et al, 1989) are a topic of great interest, primarily because of their unprecedented behaviour as catalyst precursors of homogeneous Ziegler-Natta polymerization systems (Sinn, Kaminsky, Vollmer & Woldt, 1980;. The addition of stereochemistry-controlling substituents to the cyclopentadienyl (Cp) tings of zirconocene catalyst precursors influences considerably their o~-olefin-polymerization activity (Kaminsky, 1986;Kaminsky, Engehausen, Zoumis, Spaleck & Rohrmann, 1992;Chien & Razavi, 1988;Tian & Huang, 1994), their molecular weight and their specific stereoseiectivity (Erker et al, 1991).…”

Section: Commentmentioning

confidence: 99%