Search results for "Comonomer"
showing 10 items of 74 documents
Structural and Thermal Properties of Ethylene-Norbornene Copolymers Obtained Using Vanadium Homogeneous and SIL Catalysts
2020
The series of ethylene-norbornene (E-NB) copolymers was obtained using different vanadium homogeneous and supported ionic liquid (SIL) catalyst systems. The 13C and 1H NMR (carbon and proton nuclear magnetic resonance spectroscopy) together with differential scanning calorimetry (DSC) were applied to determine the composition of copolymers such as comonomer incorporation (CNB), monomer dispersity (MD), monomer reactivity ratio (re), sequence length of ethylene (le) and tetrad microblock distributions. The relation between the type of catalyst, reaction conditions and on the other hand, the copolymer microstructure, chain termination reaction analyzed by the type of unsaturation are discusse…
Synthesis and olefin homo- and copolymerization behavior of new vanadium complexes bearing [OSSO]-type ligands
2017
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…
Microstructure of ethylene-1-hexene and ethylene-1-octene copolymers obtained over Ziegler–Natta catalysts supported on MgCl 2 (THF) 2
2001
Abstract The ethylene copolymerizations with 1-hexene or 1-octene in the presence of hydrogen using three catalysts, MgCl 2 (THF) 2 /VOCl 3 /Et 2 AlCl, MgCl 2 (THF) 2 /VCl 4 /Et 2 AlCl, MgCl 2 (THF) 2 /TiCl 4 /Et 2 AlCl, were investigated. It was found that the addition of hydrogen into the copolymerization feed reduces the molecular weight of the copolymers produced and decreases the activity of all the studied catalysts. The microstructure of the copolymers obtained was determined on the basis of 13 C NMR investigations and the reactivity ratios of the comonomers were calculated. The lack of tendency of the olefin comonomers to the creation of the polymer block was confirmed. It was found…
DFT Study of Ethylene and Propylene Copolymerization over a Heterogeneous Catalyst with a Coordinating Lewis Base
2005
The copolymerization of ethylene and propylene over a heterogeneous Ti(III) catalyst containing tetrahydrofuran (THF) as a Lewis base and MgCl2 as a support has been studied by means of DFT. Two feasible models of active sites have been examined thoroughly, and one of them turned out to be favorable in terms of both catalytic activity and the microstructure of the resulting polymer. The external barriers of olefin insertion for this model range from 3.1 to 16.0 kcal/mol and are influenced by a variety of factors, such as the structure of the growing polymer chain and the nature of the incoming olefin as well as the orientation of the ligands around the titanium atom. Stochastic simulations …
Ethylene/1-olefin copolymerization behaviour of vanadium and titanium complexes bearing salen-type ligand
2013
Ethylene/1-olefin copolymerization using vanadium and titanium complexes bearing tetradentate [O,N,N,O]-type ligand and EtAlCl2 or MAO as a cocatalyst is carried out. In the presence of the vanadium complex activated with EtAlCl2 is observed (a) negative “comonomer effect”, (b) high comonomer incorporation and narrow chemical composition distribution (CCD), (c) unexpected copolymer microstructure, and (d) increased molecular weight of copolymers when compared with the homopolymer. In contrast, titanium catalyst gives copolymers with lower 1-olefin content and broad CCD. Supported complexes show higher activity, lower 1-olefins incorporation and give copolymers with ultra high molecular weig…
Multi-Alkenylsilsesquioxanes as Comonomers and Active Species Modifiers of Metallocene Catalyst in Copolymerization with Ethylene.
2018
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…
Copolymerization of Isoprene with p-Alkylstyrene Monomers: Disparate Reactivity Ratios and the Shape of the Gradient
2019
The statistical copolymerization of isoprene with p-ethyl- (p-ES), p-isopropyl- (p-iPS), and p-tert-butylstyrene (p-tBS) initiated by sec-butyllithium in cyclohexane was investigated with respect to kinetics, reactivity ratios, and formation of tapered block copolymers with pronounced monomer gradient. An efficient synthetic route to the monomers was developed on a multigram scale, relying on the precipitation of the side-product triphenylphosphine oxide at low temperature. The copolymerization kinetics and resulting molecular weight distributions were analyzed. The dispersity, Đ, of the copolymers depends on the p-alkyl substituent, the the degree of polymerization Pn and the comonomer mol…
Hyperbranched Polyols via Copolymerization of 1,2-Butylene Oxide and Glycidol: Comparison of Batch Synthesis and Slow Monomer Addition
2015
Hyperbranched poly(butylene oxide) polyols have been synthesized by multibranching anionic ring-opening copolymerization of 1,2-butylene oxide and glycidol. Systematic variation of the composition from 24 to 74% glycidol content resulted in a series of moderately distributed copolymers (Đ = 1.41–1.65, SEC), albeit with limited molecular weights in the solvent-free batch process in the range of 900–1300 g mol–1 (apparent Mn determined by SEC with PEG standards). In situ monitoring of the copolymerization kinetics by 1H NMR showed a pronounced compositional drift with respect to the monomer feed, indicating a strongly tapered microstructure caused by the higher reactivity of glycidol. In the …
Tuning the upper critical solution temperature behavior of poly(methyl methacrylate) in aqueous ethanol by modification of an activated ester comonom…
2012
A statistical copolymer of methyl methacrylate (MMA) and pentafluorophenyl methacrylate (PFPMA, 6 mol%) exhibits upper critical solution temperature (UCST) behavior in aqueous ethanol solutions tunable by post-polymerization modification with different amines. The phase transition behavior of the obtained copolymers in aqueous ethanol was evaluated in detail. As expected, all copolymers reveal an upper critical solution temperature with 55 vol% or higher ethanol content. Furthermore, the solubility in aqueous ethanol of the copolymer can be increased by the introduction of hydrophilic moieties. When hydrophobic substituents are introduced a decrease in solubility was observed with low conte…
Synthesis of linear polyglycerols with tailored degree of methylation by copolymerization and the effect on thermorheological behavior
2017
Abstract We introduce a two-step strategy for the synthesis of linear polyglycerols (linPG-OHx/OMey) with an adjustable degree of methylation ( y = D M 100 ). Ethoxy ethyl glycidyl ether (EEGE) and glycidyl methyl ether (GME) were copolymerized via the “activated monomer” polymerization technique, using tetraoctylammonium bromide (NOct4Br) as an initiator and triisobutylaluminum (i-Bu3Al) as a catalyst under mild conditions. Subsequent acidic cleavage of the acetal protective groups generates linear polyglycerols with different degree of methylation (DM) by varying the GME comonomer content between 10 and 91%. Size exclusion chromatography (SEC) evidenced good control over molecular weight …