Search results for "Coordination polymerization"
showing 10 items of 18 documents
Polymerization with heterogeneous metalorganic catalysts. VI. Differences in polymerization activity of α-olefins and some kinetic results on butene-…
1967
Relative changes in polymerization activity of ethylene, propylene, and butene-1 in Ziegler-Natta polymerization were compared by use of TiCl3 samples contaminated with O2 and H2O to various extents. Catalyst depletion varied for the three monomers which supported the existence of different active centers. In butene-1 polymerizations with the system Al(C2H5)2Cl–TiCl3, the formation of active centers involves an irreversible and a reversible (adsorption) reaction, the former pertaining to the formation of Al(C2H5)Cl2 and dependent upon the purity of the TiCl3. The kinetic treatment of the rate curves suggests a mixed order of catalyst deactivation and again points to the importance of Al(C2H…
Transition Metal Catalyzed Olefin, Cycloolefin, and Styrene Polymerization
2013
The sections in this article are History and Trends Polymerization Processes Supported Catalysts and Morphology Control Polymerization Mechanisms and Stereoselectivity History and Principles of Metallocene Catalysis Regio- and Stereoselective Polymerization of α-Olefins Polymerization of Cyclic Olefins, Cyclopolymerization, and Stereoselective Polymerization of Styrene Late Transition Metal Catalysts Transition Metal Catalyzed Copolymerization Acknowledgements
Achieving branched polyethylene waxes by aryliminocycloocta[b]pyridylnickel precatalysts: Synthesis, characterization, and ethylene polymerization
2017
Cycloocta[b]pyridin-10-one was prepared to form the corresponding imino derivatives, which then reacted with (DME)NiBr2 to form 10-aryliminocycloocta[b]pyridylnickel bromides (Ni1–Ni5). The new compounds were characterized by means of FT-IR spectroscopy as well as elemental analysis and the organic ligands were also analyzed by the NMR measurements. Furthermore, the molecular structure of a representative complex Ni3 was determined by the single crystal X-ray diffraction, indicating the distorted tetrahedral geometry around the nickel atom. Upon the activation with either methylaluminoxane (MAO) or diethylaluminium chloride (Et2AlCl), the title nickel complexes exhibited high activity in et…
Metal-free polymerization of phenylsilane: tris(pentafluorophenyl)borane-catalyzed synthesis of branched polysilanes at elevated temperatures.
2013
The strong organoborane Lewis acid B(C6F5)3 catalyzes the polymerization of phenylsilane at elevated temperatures forming benzene and SiH4 as side-products. The resulting polymer is a branched polysilane with an irregular substitution pattern, as revealed by 2D NMR spectroscopy. Having explored the mechanism of this novel metal-free polymerization by computational chemistry methods at the DFT level, we have suggested that unusual cationic active species, namely monomer-stabilized silyl cations, propagate the polymerization. Hydride abstraction of SiH3 moiety by the catalyst in the initiation step was found to be kinetically preferred by around 9 kcal mol(-1) over activation by coordination …
Polymerization of Ethylene Oxide, Propylene Oxide, and Other Alkylene Oxides: Synthesis, Novel Polymer Architectures, and Bioconjugation.
2015
The review summarizes current trends and developments in the polymerization of alkylene oxides in the last two decades since 1995, with a particular focus on the most important epoxide monomers ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO). Classical synthetic pathways, i.e., anionic polymerization, coordination polymerization, and cationic polymerization of epoxides (oxiranes), are briefly reviewed. The main focus of the review lies on more recent and in some cases metal-free methods for epoxide polymerization, i.e., the activated monomer strategy, the use of organocatalysts, such as N-heterocyclic carbenes (NHCs) and N-heterocyclic olefins (NHOs) as well as phosphazen…
Effective copolymerization of ethylene with α,ω-alkenols and homopolymerization of α,ω-alkenols catalyzed by aminophenolate zirconium complex
2019
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…
Branched and Functionalized Polybutadienes by a Facile Two-Step Synthesis
2008
Anionic polymerization was used to prepare silane-endfunctionalized polybutadiene macromonomers with different molecular weights ranging from 9 000 to 34000 g .mol- 1 . These were polymerized by a hydrosilylation reaction in bulk to obtain branched polymers, using Karstedt's catalyst. Surprisingly, the addition of monofunctional silanes during the polymerization showed only a minimal effect concerning the degree of polymerization. Furthermore, it was possible to introduce a variety of functional silanes without increasing the overall number of reaction steps by a convenient AB 2 + A type "pseudocopolymerization" method. All branched polymers were analyzed by SEC, SEC-MALLS, SEC-viscosimetry…
Star-Like Polymers of tert -Butyl Acrylate via Controlled Radical Polymerization - Synthesis and Properties
2011
Summary: Star polymers with different numbers and lengths of poly(tert-butyl acrylate) arms were obtained by the core-first method via atom transfer and iodine mediated radical polymerization. Multifunctional initiators with different numbers of initiating groups (from 3 to 28) were used to initiate the polymerization of tert-butyl acrylate, yielding stars with different numbers of arms. The structures of the stars were characterized by NMR and gel permeation chromatography with refractive index, multiangle laser light scattering and viscosimetric detectors.
High crystallinity polyethylene obtained in biphasic polymerization using pyridinium chloroaluminate ionic liquid
2014
A series of N-n-alkylpyridinium chloroaluminate ionic liquids [C n -py][AlCl4] (where n-alkyl = n-butyl, n-hexyl, and n-octyl) was applied as a medium of the Cp2TiCl2 catalyst, activated by AlEtCl2 or AlEt2Cl, to evaluate the influence of the studied ionic liquids on the performance of the biphasic ionic liquid/hexane ethylene polymerization and the properties of the produced polyethylene (PE). The best results were obtained using N-n-butylpyridinium chloroaluminate. The polyethylene obtained in the biphasic polymerization have the high crystallinity, which was confirmed by DSC, WAXS and PALS methods, as well as the bulk density comparable to commercial HDPE. These unique properties results…
Effect of hydrogen on the ethylene polymerization process over Ziegler-Natta catalysts supported on MgCl2(THF)2. II. Kinetic studies
2000
This article reports on a study of the effects of hydrogen on the activity of vanadium and titanium catalysts supported on MgCl 2 (THF) 2 in ethylene polymerization. It was found that hydrogen did not change the stable nature of the active sites and the polydispersity index of the polyethylene obtained. The propagation rate, expressed as k p , was found to be independent of the presence and concentration of hydrogen, indicating that this reacting agent does not modify the reactivity of the active sites. However, the presence of hydrogen in the polymerization medium is responsible for partial deactivation of the active sites just before polymerization is initiated.