Polymerisationsanregung durch elektrolyse. 2. anionische, kationische und radikalische mechanismen

Breitenbach, Von J. W.; Srna, Ch.; Olaj, Oskar Friedrich

doi:10.1002/macp.1960.020420117

Cited by 29 publications

(5 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Mechanistic insight into anionic electropolymerization was done by Breitenbach et al in 1960 (Note: the original publication was written in German). 687 Indeed, the result of Yang's work was still not as good as other monomers that have been electropolymerized. Encouragingly, Funt and co-workers made a significant improvement in the electroinitiated anionic polymerization of St in 1964.…”

Section: Electrochemically Initiated Ionic Polymerizationmentioning

confidence: 99%

“…PS with a molar mass of less than 2000 g/mol was produced in their work. Mechanistic insight into anionic electropolymerization was done by Breitenbach et al in 1960 (Note: the original publication was written in German) . Indeed, the result of Yang’s work was still not as good as other monomers that have been electropolymerized.…”

Section: Electroregulated Systemsmentioning

confidence: 99%

See 1 more Smart Citation

Role of External Field in Polymerization: Mechanism and Kinetics

et al. 2020

View full text Add to dashboard Cite

The past decades have witnessed an increasing interest in developing advanced polymerization techniques subjected to external fields. Various physical modulations, such as temperature, light, electricity, magnetic field, ultrasound, and microwave irradiation, are noninvasive means, having superb but distinct abilities to regulate polymerizations in terms of process intensification and spatial and temporal controls. Gas as an emerging regulator plays a distinctive role in controlling polymerization and resembles a physical regulator in some cases. This review provides a systematic overview of seven types of external-field-regulated polymerizations, ranging from chain-growth to step-growth polymerization. A detailed account of the relevant mechanism and kinetics is provided to better understand the role of each external field in polymerization. In addition, given the crucial role of modeling and simulation in mechanisms and kinetics investigation, an overview of model construction and typical numerical methods used in this field as well as highlights of the interaction between experiment and simulation toward kinetics in the existing systems are given. At the end, limitations and future perspectives for this field are critically discussed. This state-of-the-art research progress not only provides the fundamental principles underlying external-field-regulated polymerizations but also stimulates new development of advanced polymerization methods.

show abstract

Section: Electrochemically Initiated Ionic Polymerizationmentioning

confidence: 99%

Section: Electroregulated Systemsmentioning

confidence: 99%

Role of External Field in Polymerization: Mechanism and Kinetics

et al. 2020

View full text Add to dashboard Cite

show abstract

“…Early work was also devoted to the electrolysis of tetraalkylammonium salts dissolved in acrylonitrile (8). While at that time it seemed to be a matter of course to consider all these polymerization processes mentioned before to proceed via free radicals copolymerization experiments carried out by Breitenbach et al ( 9 ) with acrylonitrile and methyl methacrylate, as well as acrylonitrile and styrene, with tetraethylammonium perchlorate as the electrolyte, (the composition of the copolymer at a given monomer feed is characteristic of the polymerization mechanism) revealed that the polymerization, which leads to a polymer rich in acrylonitrile at the cathode, proceeds via an anionic mechanism. In addition, in the latter system polymer rich in styrene was observed at the anode which due to its composition could be only formed by cationic mechanism.…”

mentioning

confidence: 99%

Electrolytically initiated vinyl polymerization

Olaj

1987

Makromolekulare Chemie. Macromolecular Symposia

View full text Add to dashboard Cite

After a short outline of the historic development of electroinitiated vinyl polymerization and a description of the early work in this field a survey is given on the most important initiation systems. The difficulties and problems which arise, in addition to conventional initiation of vinyl polymerization, are analyzed. Among others, these comprise the spatial heterogeneity of active particle production, the necessity of dissolving the electrolyte in the polymerization system, which preferably also should be a solvent for the polymer formed, the susceptibility of the electrode process to impurities, the eventual termination of the growing chains by the products of the process taking place at the counter‐electrode, and the possibility of simultaneous initiation of anionic and free radical polymerization at the cathode and of cationic and free radical polymerization at the anode. Some examples show that in spite of these numerous difficulties precise kinetic measurements are possible in some free radical as well as in some ionic initiation systems. While the initiation of free radical polymerization processes suffers from disappointingly low current yields (≈︁10−3), throughout which makes this initiation much inferior to any conventional one, there are some positive features inherent in the electroinitiation of ionic polymerization. Especially, it is the possibility to carry out cationic polymerization exclusively in presence and under control of such counterions which are known to have favorable polymerization characteristics (this is to lead to high rates and molecular weights), however, the corresponding anhydrous acids of which do not exist, by merely oxidizing the monomer in presence of salts of these counterions (e.g. AgSbF6). Due to the non‐availability of the corresponding anhydrous acid HSbF6 this cannot be accomplished in a direct manner by conventional techniques.

show abstract

“…7 These electro-initiated freeradical polymerizations of MMA an AN fall into the same category (1) as the polymerization initiated by oxidation of acetate ion. 1…”

mentioning

confidence: 99%

“…radical polymerization of methyl methacrylate. 1 (2) Radical species formed by oxidation of electrolytes abstract a hydrogen atom from solvent or monomer to form proton which initiates cationic polymerization. Tetrafluoroborate ion, BF4-, in sulpholane was electrolytically oxidized to produce a radical, BF4 ·, which reacted with sulpholane to form hydrogen fluoride and boron trifluoride and the proton of hydrogen fluoride initiated cationic polymerization of styrene.…”

mentioning

confidence: 99%