Half-Titanocenes Containing Anionic Ancillary Donor Ligands: Effective Catalyst Precursors for Ethylene/Styrene Copolymerization

Abstract

This review summarizes recent results for ethylene/styrene copolymerization using half-titanocenes containing anionic donor ligands, Cp'TiX 2 (Y) (X = halogen, alkyl; Y = aryloxo, ketimide etc.)-cocatalyst systems. The product composition, the styrene incorporation and microstructures in the resultant copolymers are highly influenced by the anionic donor employed. A methodology for an exclusive synthesis of the copolymers even under high temperature and high styrene concentrations has been introduced on the basis of a proposed catalytically-active species in this catalysis.

Olefin–Styrene Copolymers

“…Later efficient systems based on (cyclopentadienyl)(aryloxy) titanium(IV) have been deeply investigated by the Nomura group ( Figure 1 f) [ 9 , 10 , 11 ]. The same author achieved the living ethylene–styrene copolymerization by using a (cyclopentadienyl)(ketimide) titanium (IV) complex activated by MAO ( Figure 1 g) [ 12 ].…”

Formal aryne/ethylene copolymerization to form polyethylene containing o-arylene units in the main chain

“…The introduction of functional groups or different comonomers into linear polyethylenes by the copolymerization method is known to be effective for the modification of both the surface and material properties of the resulting polyethylenes. 23 For such a copolymerization, a range of comonomers, including α-olefins, 24 styrenes, 25,26 norbornenes, 27,28 polar vinyl monomers, 23,29-31 allyl monomers [32][33][34] and carbon monoxide, [35][36][37] has been examined thus far, but the use of aryne or its congeners for the introduction of an o-arylene linkage has been unexplored. In this study, we report a formal copolymerization of aryne and ethylene that was successfully catalyzed by palladium/phosphine-sulfonate complexes 23,29,30 to generate the corresponding copolymers containing o-arylene units in the main chain (Scheme 1b).…”

Homopolymerization of styrenic monomers and their copolymerization with ethylene using group 4 non‐metallocene catalysts

“…However, a styrene moiety can be introduced instead of 1-olefin into the polyethylene backbone which results in better viscoelastic performance, thermo-mechanical properties and compatibility with other polymeric materials. [2,3] Moreover, ethylene/ styrene copolymers may offer considerably different properties depending on the copolymer composition and its microstructure. That aspect was described inter alia in review papers.…”

“…That aspect was described inter alia in review papers. [2,4,5] As a result, materials with a broad range of properties can be obtained that can be converted into products with various possible applications, among them are packaging, foams, films, sheets, compatibilizers for PS/PE blends, bitumen modifiers and others. [5][6][7] It should, however, be mentioned that the copolymerization process of ethylene and styrene is much harder to conduct than that of ethylene and 1-olefin due to highly different reactivities of those monomers toward most catalysts.…”