Copolymerization of Ethylene with Selected Vinyl Monomers Catalyzed by Group 4 Metal and Vanadium Complexes with Multidentate Ligands: A Short Review

Abstract

This paper gives a short overview of homogeneous post-metallocene catalysts based on group 4 metal and vanadium complexes bearing multidentate ligands. It summarizes the catalytic behavior of those catalysts in copolymerization of ethylene with 1-olefins, with styrenic monomers and with α,ω-alkenols. The review is focused on finding correlations between the structure of a complex, its catalyst activity and comonomer incorporation ability, as well as the microstructure of the copolymer chains.

Dipicolinate Oxovanadium(IV) Complexes – Well‐Defined, Universal Precatalysts for Ethylene Polymerization and Polar Monomers Oligomerization

“…To date, diverse vanadium(III, IV, V) complexes have been synthesized and evaluated in olefin polymerization (for example [9,14] ) and achievements in catalytic polymerization with the latest generation of vanadium catalysts are summarized in detail in the reviews. [1,13,15,16] Some representative vanadium(IV) complexes for ethylene polymerization are shown in Figure 1. [15] In 2019 Zanchin and co-workers developed several (imido)vanadium(IV) dichloride complexes, which catalyzed the polymerization of ethylene after the addition of Et 2 AlCl and ETA.…”

Catalytic making of ethylene‐1‐hexene elastomers: Thermodynamic guide to process development

“…Figure 3 partially lists several such precatalysts, which are usually Spaleck 17,19,[21][22][23] and constrained geometry types, 5,[24][25][26][27][28] tridentate titanium, 29,30 and tetradentate zirconium post-metallocenes, 29,31 and Nomura (cyclopentadienyl)(aryloxy)titanium post-metallocenes. 32 One F I G U R E 1 Copolymer morphology progression in a thermoplastic elastomer due to increasing comonomer incorporation.…”

“…Figure 3 partially lists several such precatalysts, which are usually Spaleck 17,19,21–23 and constrained geometry types, 5,24–28 tridentate titanium, 29,30 and tetradentate zirconium post‐metallocenes, 29,31 and Nomura (cyclopentadienyl)(aryloxy)titanium post‐metallocenes 32 . One can review the references listed above, including the corresponding cross‐references, for learning this subject in further detail.…”

Bidentate Pyridyl‐Amido Hafnium Catalysts for Copolymerization of Ethylene with 1‐Octene and Norbornene

“…The incorporation of some polar functionalized comonomers can efficiently alter the nonpolar nature of polyolefins and introduce new material properties [20–25] . The incorporation of a large content of α‐olefins can decrease crystallinity and enable elastic properties, leading to the generation of polyolefin elastomers (POEs) [26,27] . Interestingly, recent studies have shown that the elastic properties can also be installed through branching formation via chain walking homopolymerization of ethylene [28–32] .…”

“…[20][21][22][23][24][25] The incorporation of a large content of α-olefins can decrease crystallinity and enable elastic properties, leading to the generation of polyolefin elastomers (POEs). [26,27] Interestingly, recent studies have shown that the elastic properties can also be installed through branching formation via chain walking homopolymerization of ethylene. [28][29][30][31][32] The incorporation of cyclic comonomers such as norbornene endows cyclic olefin copolymers (COC) with unique properties such as high heat stability, good chemical resistance, low density and high transparency.…”