Ethylene/POSS copolymerization behavior of postmetallocene catalysts and copolymer characteristics
Copolymerization of ethylene with iso-butyl substituted monoalkenyl(siloxy)- or monoalkenylsilsesquioxane (POSS) comonomers over bis(phenoxy-imine) and salen-type titanium and zirconium catalysts was studied. It was found that the polyreaction performance was significantly depended by the kind of the catalyst and by the structure and concentration of POSS in the feed. The POSS comonomer was efficiently incorporated into the polymer chain at up to 0.2 mol %. The differences in the copolymer compositions as the functions of the catalyst kind and the POSS comonomer were observed, including the varied number-average sequence length of ethylene and unsaturated end groups, as determined by 1H NMR…
Copolymers of ethylene with monoalkenyl- and monoalkenyl(siloxy)silsesquioxane (POSS) comonomers – Synthesis and characterization
Abstract The hybrid ethylene/POSS copolymers were obtained using the rac -Et(Ind) 2 ZrCl 2 catalyst activated by MAO. A series of monoalkenyl- and monoalkenyl(siloxy)silsesquioxanes derivatives with different structures of reactive alkenyl substituent and types of non-reactive groups attached to the T 8 POSS cage was used as comonomers. The kind and concentration of the POSS comonomer in the reaction feed as well as extended reaction time were found to strongly influence the catalyst efficiency and incorporation of POSS units into polymer chains. The comonomer reactivity was significantly dependent on the length of the alkenyl reactive substituent in the POSS molecule and it was highest for…
A library of monoalkenylsilsesquioxanes as potential comonomers for synthesis of hybrid materials
In this paper we demonstrate a facile and efficient synthesis of monoalkenylsubstituted POSS compounds, i.e., R7(Si8O12)-alkenyl and R7(Si8O12)(OSiMe2)-alkenyl with a functional alkenyl group of chain length (from vinyl to dec-9-enyl, with or without additional –OSiMe2– spacer between the silsesquioxane core and alkenyl moiety) and with five types of inert groups (Et, iBu, iOc, Cy, Ph) at the POSS core. These compounds constitute a library of monosubstituted POSS systems, including thorough spectroscopic and thermal characteristics. These findings could be especially useful for material chemists applying the compounds as modifiers or comonomers for copolymerization reaction, e.g., with olef…
Synthesis and structural characterization of ethylene copolymers containing double-decker silsesquioxane as pendant groups and cross-linkage sites by coordinative copolymerization
Abstract The copolymers of ethylene with the double-decker silsesquioxane (DDSQ) were synthesized by copolymerization with the use of metallocene and bis(phenoxy-imine) catalysts. The influence of the kind of the catalyst and polyreaction conditions on the performance of copolymerization as well as on the properties of the copolymers was studied. Depending on polyreaction parameters, the DDSQ contents in the copolymer varied in the range of 0.93–11.53 wt% which determined the compositions and the structural properties of copolymers. DDSQ incorporated into the polymer chain could constitute pendant groups in the main chain or it could act as a cross-linking agent. The ethylene/DDSQ copolymer…
Multi-Alkenylsilsesquioxanes as Comonomers and Active Species Modifiers of Metallocene Catalyst in Copolymerization with Ethylene.
The copolymers of ethylene (E) with open-caged iso-butyl-substituted tri-alkenyl-silsesquioxanes (POSS-6-3 and POSS-10-3) and phenyl-substituted tetra-alkenyl-silsesquioxane (POSS-10-4) were synthesized by copolymerization over the ansa-metallocene catalyst. The influence of the kind of silsesquioxane and of the copolymerization conditions on the reaction performance and on the properties of the copolymers was studied. In the case of copolymerization of E/POSS-6-3, the positive comonomer effect was observed, which was associated with the influence of POSS-6-3 on transformation of the bimetallic ion pair to the active catalytic species. Functionality of silsesquioxanes and polymerization par…