Electron spin resonance polymerization

Yoshida, H. and Hayashi, K. Initiation Process of Radiation-induced Ionic Polymerization as Studied by Electron Spin Resonance. Vol. 6, pp. 401—420. 

In addition, Bamford, Jenkins and coworkers (19) previously reported on the behavior of occluded radicals in the heterogeneous polymerizations of acrylonitrile, methyl acrylate, methyl methacrylate and vinylidene chloride. From their electron spin resonance studies, they concluded that the degree of occlusion was ... 

This article is an attempt to review possibilities in a quantum chemical treatment of open-shell systems. In order to cut down the extent of this review, we disregard some problems, especially those concerning macromolecules, polymerization reactions, and open-shell transition-metal complexes. Electron spin resonance is mentioned only briefly, because it has been a topic of many reviews. 

Depolymerization of some natural polymers is another typical example. Milling of chitin or chitosan, at ambient temperature, leads to cleavage of the cellulose polymeric chain. Scission of 1,4-glucosidic bonds takes place, and the radicals formed recombine. Based on electron spin resonance, Sasai et al. (2004) monitored both the homolysis and the radical recombination. The recombination led to the formation of midsize polymeric chains only. Some balance was established between the homolytic depolymerization and the size-limited recombination of the radicals primarily formed. 

Electron spin resonance (ESR) spectroscopy can be advantageously used to measure the radical concentrations of the nitroxide radicals (XV and XVI) produced, since these are much more stable then the R- radicals. Of greater importance, ESR can be used to determine the structure of R% since the ESR of the nitroxide radical is quite sensitive to the structure of R. (For this purpose, nitroso spin traps are more useful, since the R group in the nitroxide radical is nearer to the lone electron.) This can allow a determination of the structures of radicals first formed in initiator decomposition, the radicals that actually initiate polymerization (if they are not identical with the former) as well as the propagating radicals [Rizzardo and Solomon, 1979 Sato et al 1975],... 

The reaction involves the transfer of an electron from the alkali metal to naphthalene. The radical nature of the anion-radical has been established from electron spin resonance spectroscopy and the carbanion nature by their reaction with carbon dioxide to form the carboxylic acid derivative. The equilibrium in Eq. 5-65 depends on the electron affinity of the hydrocarbon and the donor properties of the solvent. Biphenyl is less useful than naphthalene since its equilibrium is far less toward the anion-radical than for naphthalene. Anthracene is also less useful even though it easily forms the anion-radical. The anthracene anion-radical is too stable to initiate polymerization. Polar solvents are needed to stabilize the anion-radical, primarily via solvation of the cation. Sodium naphthalene is formed quantitatively in tetrahy-drofuran (THF), but dilution with hydrocarbons results in precipitation of sodium and regeneration of naphthalene. For the less electropositive alkaline-earth metals, an even more polar solent than THF [e.g., hexamethylphosphoramide (HMPA)] is needed. 

Electron paramagnetic resonance spectroscopy (EPR) (also called electron spin resonance spectroscopy, ESR) has been scarcely applied in the field of art and art conservation. Some work can be found in which EPR is used as complementary technique to SEM-EDX, NMR, and mass spectrometry (MS) for studying free radicals occurring in polymerization, pyrolytic, oxidative, and other radical degradative processes in artwork, as well as in the characterization of varnishes and oleoresinous media [42]. 

The formation of ion radicals from monomers by charge transfer from the matrices is clearly evidenced by the observed spectra nitroethylene anion radicals in 2-methyltetrahydrofuran, n-butylvinylether cation radicals in 3-methylpentane and styrene anion radicals and cation radicals in 2-methyltetrahydrofuran and n-butylchloride, respectively. Such a nature of monomers agrees well with their behavior in radiation-induced ionic polymerization, anionic or cationic. These observations suggest that the ion radicals of monomers play an important role in the initiation process of radiation-induced ionic polymerization, being precursors of the propagating carbanion or carbonium ion. On the basis of the above electron spin resonance studies, the initiation process is discussed briefly. 

Several investigations dealing with the characterization of polymeric membrane systems have been reported lately. A. Kusumi 99> studied phase transitions, fluidity and polarity properties of polymerized and nonpolymerized methacryloyl-derivatized phosphatidylcholine (57) vesicles by DSC and electron spin resonance (ESR). 

Finally, various attempts have been reported to interpret the kinetics of radiation grafting. The study by Mock, and Vanderkooi (123) concerned the mutual radiation grafting of styrene from the vapor phase to ethyl cellulose film at 50° C. The radical flux was determined separately using electron spin resonance. The kinetic scheme rigorously took account of the diffusion controlled nature of the reaction and the appropriate diffusion constants were separately determined (124). The value for the ratio of for the graft polymerization was determined as... 

Finally, the data published by Gee (30) permit one to evaluate the sharpness of a transition involving floor temperature. Gee studied the temperature dependence of the viscosity of liquid sulfur and observed its sudden, steep increase at a critical temperature followed by its decrease at still higher temperatures. He developed the first, relatively complete theory of equilibrium polymerization of liquid sulfur (30) from which he estimated the chain length of the polymeric sulfur at various temperatures. His results have been recently confirmed by experimental measurements of magnetic susceptibility of the liquid sulphur (50) and its electron spin resonance (57). 

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