B. Anionic Ligands 302 IX. Group 9 Catalysts 302 X. Group 10 Catalysts 303 A. Neutral Ligands 303 1. R-Diimine and Related Ligands 303 2. Other Neutral Nitrogen-Based Ligands 304 3. Chelating Phosphorus-Based Ligands 304 B. Monoanionic Ligands 305 1. [PO] Chelates 305 2. [NO] Chelates 306 3. Other Monoanionic Ligands 306 4. Carbon-Based Ligands 306 XI. Group 11 Catalysts 307 XII. Group 12 Catalysts 307 XIII. Group 13 Catalysts 307 XIV. Summary and Outlook 308 XV. Glossary 308 XVI. References 308

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Advances in non-metallocene olefin polymerization catalysis.

Ordered mesoporous materials in catalysis

Selectivity in propene polymerization with metallocene catalysts.

Precise control of polyolefin stereochemistry using single-site metal catalysts.

Preparation of polymer-supported ligands and metal complexes for use in catalysis.

Copolymerizations of ethylene with propene, ethylene with 1-hexene and propene with 1-hexene were performed at 40°C under atmospheric using three kinds of Kaminsky-Sinn-type catalysts which differ in stereospecificity: Cp2ZrCl2-methylaluminoxane (MAO) (aspecific); Et[IndH4]2 ZrCl2-MAO (isopecific); i-Pr(Cp)(Flu)ZrCl2-MAO (syndiospecific).

The 13C NMR analysis of copolymers showed that the incorporation of higher olefins decreases in the following order: i -Pr(Cp)(Flu)ZrCl2-MAO > Et[IndH4]2ZrCl2-MAO > Cp2ZrCl2-MAO, and that stereospecificity is retained even in the copolymerization.

The product of monomer reactivity ratios (r1 · r2) indicates that poly(propene-co-1-hexene) is a statistically random copolymer whereas both poly(ethylene-co-propene) and poly(ethylene-co-1-hexene) have somewhat alternating character regardless of catalyst stereospecificity.

Copolymerization of olefins with Kaminsky‐Sinn‐type catalysts

Polymerization of ethylene and copolymerizations of ethylene with 1-octene and oligoethylene having a vinyl end group were conducted with Cp 2 ZrCl 2 and [(C 5 Me 4 )Si-Me 2 N(t-Bu)]TiCl 2 a) as catalysts, and the structures of the resulting polymers were analyzed in detail. The Cp 2 ZrCl 2 catalyst combined with methylalumoxane (MAO) gives polyethylene with vinyl, vinylidene and trans-vinylene groups. The use of Al(iC 4 H 9 ) 3 /(C 6 H 5 ) 3 C.B(C 6 F 5 ) 4 as cocatalyst produces polyethylene predominantly containing trans-vinylene groups. Polyethylene with vinyl end groups was obtained selectively with [(C 5 Me 4 )SiMe 2 N(t-Bu)]TiCl 2 -MAO as catalyst. The types and contents of C=C double bonds in polyethylene markedly depend upon the metallocene compound as well as as the cocatalyst. In the copolymerizations the [(C 5 Me 4 )SiMe 2 N(t-Bu)]TiCl 2 -MAO catalyst system, on the other hand, gives poly[ethylene-co-(1-octene)] with a high content of 1-octene and a polyethylene containing an appreciable amount of long-side-chain oligoethylene.

Structures of polyethylene and copolymers of ethylene with 1‐octene and oligoethylene produced with the Cp2ZrCl2 and [(C5Me4)SiMe2N(t‐Bu)]TiCl2 catalysts

The mesoporous siliceous SBA-15 molecular sieve was synthesized
and post-synthesis alumination was carried out using trimethylaluminium (TMA).
It was found that the aluminium could be easily incorporated into the siliceous
framework of SBA-15 without serious structure deformation. From detailed characterization
of the prepared aluminium-containing SBA-15 (AlSBA-15) it was also
found that it is difficult to keep the aluminium in the framework position
after calcination. The hydrothermal stability of SBA-15 was considerably improved
by the TMA processing. The results of the cumene cracking reactions and the
pyridine adsorption experiments indicated that the Bronsted acid sites
of AlSBA-15 are stronger than those of AlMCM-41 prepared by the same method.

Characterization of AlSBA-15 prepared by post-synthesisalumination with trimethylaluminium

Several kinds of polystyrene-supported metallocene catalysts were prepared and used in the polymerizations of propylene and ethylene with methylaluminoxane (MAO) as cocatalyst. It was found that these catalysts are stable even at 70°C. They display fairly high activities when the polymerizations are conducted at high temperatures.

Toshiya Uozumi

Papers

Copolymerization of olefins with Kaminsky‐Sinn‐type catalysts

Structures of polyethylene and copolymers of ethylene with 1‐octene and oligoethylene produced with the Cp2ZrCl2 and [(C5Me4)SiMe2N(t‐Bu)]TiCl2 catalysts

Characterization of AlSBA-15 prepared by post-synthesisalumination with trimethylaluminium

Polystyrene-supported metallocene catalysts for olefin polymerizations

Synthesis of large mordenite crystals in the presence of aliphatic alcohol