0000000001314029
AUTHOR
Julia Fryga
Homopolymerization of styrenic monomers and their copolymerization with ethylene using group 4 non‐metallocene catalysts
Homopolymerization of styrenic monomers (St, p ‐Me‐St, p ‐t Bu‐St, p ‐t BuO‐St) and their copolymerization with ethylene, with the use of [( t Bu2O2NN′)ZrCl]2(μ‐O) (1 ) and ( t Bu2O2NN′)TiCl2 (2 ), where t Bu2O2NN′ = Me2N(CH2)2N(CH2‐2‐O−‐3,5‐t Bu2‐C6H2)2, is explored in the presence of MMAO and (i Bu)3Al/Ph3CB(C6F5)4. The ethylene/styrenic monomers copolymerization with 1 /MMAO produces exclusively copolymers with high activity and good comonomer incorporation whereas the other catalytic systems yield mixtures of copolymers and homopolymers. The use of p ‐alkyl styrene derivatives instead of styrene raises the catalytic activity, comonomer incorporation and molecular weights of the copolyme…
Copolymerization of Ethylene with Selected Vinyl Monomers Catalyzed by Group 4 Metal and Vanadium Complexes with Multidentate Ligands: A Short Review
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.
Effect of AlR3 (R = Me, Et, iBu) addition on the composition and microstructure of ethylene/1-olefin copolymers made with post-metallocene complexes of group 4 elements
The effect of trialkylaluminum compound (AlR3, where R = Me, Et, iBu) addition on the performance of the [LigZrCl]2(μ-O)/AliBu3/Ph3CB(C6F5)4 and LigTiCl2/AliBu3/Ph3CB(C6F5)4 (Lig = Me2N(CH2)2N(CH2-2-O-3,5-tBu2-C6H2)2) catalysts in ethylene/1-olefin copolymerization was investigated. The presence of AlMe3 in the feed during the copolymerization process catalyzed by the diamine-bis(phenolate) zirconium catalyst greatly increases the amount of incorporated comonomer and leads to microstructural changes, e.g., the formation of blocky and alternating sequences of 1-olefin units. Moreover, the use of AlMe3 limits the reaction yield and decreases the molecular weight of the produced copolymers. Th…
Effective copolymerization of ethylene with α,ω-alkenols and homopolymerization of α,ω-alkenols catalyzed by aminophenolate zirconium complex
Abstract A zirconium complex of diamine-bis(phenolate) ligand, [(tBu2O2NN’)ZrCl]2(μ-O) where (tBu2O2NN’) = Me2N(CH2)2N(CH2–2-O−-3,5-tBu2-C6H2)2, activated with (iBu)3Al/Ph3CB(C6F5)4, was for the first time used in copolymerization of ethylene with unsaturated alcohols (CH2 = CH(CH2)nCH2OH, where n = 7, 8, 3). The hydroxyl groups of comonomers were protected with R3-xAlClx (where x = 0 or 1, R = iBu, Et). In contrast to the formerly reported catalysts, the activity of this catalyst is much higher in ethylene/alkenols copolymerization than in ethylene homopolymerization and its lifetime is long. Moreover, the copolymers with high polar comonomer contents (up to 16.4 mol%, 52.3 wt%) were produ…
Ethylene homo- and copolymerization catalyzed by vanadium, zirconium, and titanium complexes having potentially tridentate Schiff base ligands
Abstract New potentially tridentate Schiff base ligands, 2-[({4-[(3-N,N-dimethylamino)propyl] phenyl}imino)methyl]-4,6-di-tert-butylphenol (L1H) and 2-[{2-(N-phenyl-N-methylaminomethyl)-phenylimino}-methyl]-4,6-di-tert-butylophenol (L2H) were prepared and after deprotonation they were reacted with VOCl3 or MCl4 (where M = Zr or Ti) to produce corresponding complexes (L1-V, L2-V, L1-Zr, L2-Ti) with good yields. All new compounds were characterized by the 1H and 13C NMR as well as FTIR spectroscopic methods. Upon activation with Et2AlCl or EtAlCl2, both the vanadium complexes exhibited exceptionally high catalytic activities in the ethylene polymerization (up to 69,000 kg/(molV⋅h) for L1-V an…
Synthesis and olefin homo- and copolymerization behavior of new vanadium complexes bearing [OSSO]-type ligands
Novel vanadium complexes bearing [OSSO]-type ligands having two phenolato units linked through the –CH2S(CH2)4SCH2– (1V) or –CH2S(CH2)2SCH2– (2V) bridge are synthesized with good yields by reacting a deprotonated ligand with VCl4. They are then used in ethylene (co)polymerization after activation with EtAlCl2 and Et2AlCl. In the presence of EtAlCl2, both complexes promote ethylene polymerization with very high activities, over 4 × 107 g/(mol h), leading to PEs with high molecular weight and narrow molecular weight distribution. The prepared complexes exhibit lower activity for ethylene/1-octene copolymerization. It is also revealed that the catalyst based on the –CH2S(CH2)4SCH2– bridged com…
Ring opening polymerization of ε-caprolactone initiated by titanium and vanadium complexes of ONO-type schiff base ligand
AbstractA phenoxy-imine proligand with the additional OH donor group, 4,6-tBu2-2-(2-CH2(OH)-C6H4N = CH)C6H3OH (LH2), was synthesized and used to prepare group 4 and 5 complexes by reacting with Ti(OiPr)4 (LTi) and VO(OiPr)3 (LV). All new compounds were characterized by the FTIR, 1H and 13C NMR spectroscopy and LTi by the single-crystal X-ray diffraction analysis. The complexes were used as catalysts in the ring opening polymerization of ε-caprolactone. The influence of monomer/transition metal molar ratio, reaction time, polymerization temperature as well as complex type was investigated in detail. The complexes showed high (LTi) and moderate (LV) activity in ε-caprolactone polymerization a…
CCDC 1877301: Experimental Crystal Structure Determination
Related Article: Julia Fryga, Marzena Białek, Grzegorz Spaleniak, Błażej Dziuk|2021|J.Poly.Res.|28||doi:10.1007/s10965-021-02419-y