Polymerization Mechanism in Methyl Methacrylate–Grignard Reagent System. I. Phenylmagnesium Bromide
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Phenylmagnesium bromide
Cationic polymerization
Chain-growth polymerization
Ionic polymerization
Kinetic features and the mechanism of proton-transfer anionic polymerization of vinyl monomers (2-hydroxyethylacrylate (HEA) and l-hydroxyethylmethacrylate (HEMA) bearing groups with mobile hydrogen atom are discussed. It is established that polymerization combines features of chain growth and step growth polymerization. The living chain polymerization mechanism dominates at heterogeneous proceeding of the reaction. The peculiarities of the HEA and HEMA polymerization mechanism under the action of alkaline metals and their alcoholates are established. Polymerization initiated by tert-BuOLi is accompanied by a transesterification reaction with formation, along with macromonomer as main target product, of polyester di(met)acrylates, polyester diols and macrocycles. In addition to the transesterification reaction at HEMA polymerization initiated by potassium, formation of carbon chain fragments caused by interaction of enolate anion with double bond is revealed.
Chain-growth polymerization
Chain transfer
Ionic polymerization
Living polymerization
Living anionic polymerization
Bulk polymerization
Kinetic chain length
Macromonomer
Living free-radical polymerization
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Cationic polymerization
Ionic polymerization
Living polymerization
Chain transfer
Chain-growth polymerization
Living anionic polymerization
Living cationic polymerization
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The self-condensing vinyl polymerization (SCVP) of 2-((2-bromopropionyl)oxy)ethyl acrylate (BPEA) has resulted in the formation of hyperbranched polyacrylates. The polymerization mechanism used to polymerize the BPEA was atom transfer radical polymerization (ATRP), a "living"/controlled radical polymerization. This paper details the study of the kinetics of polymerization and the growth of the macromolecule during the polymerization. The results obtained in the polymerization were compared to the theoretical predictions for SCVP. It was determined that the polymerization deviated from the ideal case, as a consequence of the establishment of a dynamic equilibrium in ATRP resulting in the addition of more than one monomer unit in a single activation step.
Chain transfer
Chain-growth polymerization
Living free-radical polymerization
Ionic polymerization
Cationic polymerization
Catalytic chain transfer
Living polymerization
Bulk polymerization
Atom-transfer radical-polymerization
Kinetic chain length
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The "living" free radical ring-opening polymerization of 2-methylene-4-phenyl-1,3-dioxolane (MPDO) in the presence of ethyl α-bromobutyrate/CuBr/2,2′-bipyridine at various temperatures has been investigated. In comparison with the conventional ring-opening polymerization of MPDO, a lower content of ring-opened unit in the polymer was found. The results of ln[M]0/[M]) against polymerization time, (Mn)th and (Mn)NMR vs conversion, and GPC of the polymers are strongly indicative of the "living" polymerization process. Initiator efficiency was measured. The mechanism of polymerization, and the effect of pyridine on the polymerization mechanism were discussed.
Living free-radical polymerization
Ionic polymerization
Chain-growth polymerization
Chain transfer
Living polymerization
Cobalt-mediated radical polymerization
Precipitation polymerization
Methylene
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Anionic ring-opening polymerization of ε-thionocaprolactone was examined. When organolithiums, Grignard reagents, and lithium tert-butoxide were used as the initiators, the corresponding polythiocarboxylic-O-ester was selectively formed. When potassium tert-butoxide and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) were used, the corresponding polythiocarboxylic-S-ester was predominantly formed. The monomer conversion and Mn of the obtained polymer increased with the polymerization temperature. Elongation of polymerization time resulted in decrease of the polymer yield and Mn. The polymerization in tetrahydrofuran (THF) proceeded faster compared with the polymerization in toluene. Formation of a cyclic dimer was observed in the polymerization in THF.
Ionic polymerization
Chain-growth polymerization
Tetrahydrofuran
Precipitation polymerization
Chain transfer
Bulk polymerization
Cationic polymerization
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A liquid crystalline monomer was photopolymerized under a variety of conditions by both free radical and cationic processes. Comparison of the polymerization rates and the polymer formed by the two mechanisms gives insight into polymerization in ordered phases. The polymerization exotherms generated by the free radical polymerization in the ordered cholesteric nematic and isotropic media were compared to those generated for a similar system upon polymerization in smectic and isotropic media.
Cationic polymerization
Ionic polymerization
Chain-growth polymerization
Bulk polymerization
Precipitation polymerization
Chain transfer
Living free-radical polymerization
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A mighty advance of anionic polymerization has been made in recent 20 years in initiator system, new monomer and polymerization theory. The new concepts, LAP (Ligated Anionic Polymerization), RAP (retarded anionic polymerization) have been put forward; and the microstructure of polymer and the polymerization dynamical process can better be controlled. In industry, the production scale and the area of product application in anionic polymerization are enlarged, and the many new products are synthesized, such as integrated SIBR and IPS prepared by anionic polymerization. A rapid development in anionic polymerization industry has been carried out, and the hydrogenated production has been commercialized in China, too.
Living anionic polymerization
Ionic polymerization
Chain-growth polymerization
Cationic polymerization
Precipitation polymerization
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Ionic polymerization
Comonomer
Living anionic polymerization
Chain-growth polymerization
Polystyrene
Living free-radical polymerization
Living polymerization
Chain transfer
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The anionic polymerization behavior of 2-methyl-4-phenyl-1-buten-3-yne (2) was investigated to get information on the effect of substituent at the 2-position. The polymerization of 2 did not proceed in tetrahydrofuran at –78°C by lithium initiators, while sodium initiators can conduct the polymerization smoothly to give polymers consisting of a specific 1,2-polymerized unit. The living nature of the polymerization of 2 by diphenylmethylsodium was supported by the post-polymerization experiment.
Living anionic polymerization
Ionic polymerization
Chain-growth polymerization
Living polymerization
Cationic polymerization
Tetrahydrofuran
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Preface. Fundamentals of Radical Polymerization. The Cutthroat Competition Between Termination and Transfer to Shape the Kinetics of Radical Polymerization. the Importance of Chain-Length Dependent Kinetics in Free-radical Polymerization: A Preliminary Guide. Propagation Kinetics of Free-Radical Methacrylic Acid Polymerization in Aqueous Solution. The Effect of Concentrating and Degree of Ionization. Investigation of the Chain Length Dependence of Kp: New Results Obtained with Homogeneous and Heterogeneous Polymerization. Propagation rate Coefficient of Nonionized Methacrylic Acid Radical Polymerization in Aqueous Solution. The Effect of Monomer Conversion. Studying the Fundamentals of Radical Polymerization Using ESR in Combination with Controlled Radical Polymerization Methods. Controlled Radical Polymerization. Competitive Equilibria in Atom Transfer Radical Polymerization. Kinetic Aspects of RAFT Polymerization. Scope for Accessing the Chain Length Dependence of the Termination rate Coefficient for Disparate Length Radicals in Acrylate Free Radical Polymerization. Synthesis of Poly(methyl acrylate) Grafted onto Silica Particles by Z-supported RAFT Polymerization. RAFT Polymerization: Adding to the Picture. Verdazyl-Mediated Polymerization of Styrene. Germanium-and Tim-Catalyzed Living Radical Polymerizations of Styrene and Methacrylates. Mechanism and Kinetics of the Induction Period in Nitroxide Mediated Thermal Autopolymerizations. Application to the Spontaneous Copolymerization of Styrene and Maleic Anhydride. NMR Spectroscopy in the Optimization and Evaluation of RAFT Agents. reverse Iodine Transfer Polymerization (RITP) in Emulsion. A Missing Reaction Step in Dithiobenzoate-Mediated RAFT Polymerization. Polymer Reaction Engineering and Polymer Materials. RAFT Polymerization in Bulk and Emulsion. Reaction Calorimetry for the Development of Ultrasound-Induced Polymerization Processes in CO2-Expanded Fluids. Size-Exclusion Effect and Protein Repellency of Concentrated Polymer Brushes Prepared by Surface-Initiated Living Radical Polymerization. Synthesis of Rod-Coil Block Copolymers using Two Controlled Polymerization Techniques. Production of Polyacrylic Acid Homo-and Copolymer Films by Electrochemically Induced Free-Radical Polymerization: Preparation and Swelling Behavior. Polymerization in Heterogeneous Systems. Designing Organic/Organic Colloids by Heterophase Polymerization. Unusual Kinetics in Aqueous Heterophase Polymerizations. Surface - Functionalized Inorganic Nanoparticles in Miniemulsion Polymerization. Reversible Addition Fragmentation Chain Transfer Mediated Dispersion Polymerization of Styrene.
Chain transfer
Ionic polymerization
Living free-radical polymerization
Chain-growth polymerization
Kinetic chain length
Living polymerization
Precipitation polymerization
Bulk polymerization
Emulsion polymerization
Cobalt-mediated radical polymerization
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