Radiation-induced polymerization initiation

Solution polymerization of VDE in fluorinated and fluorochlorinated hydrocarbons such as CEC-113 and initiated with organic peroxides (99), especially bis(perfluoropropionyl) peroxide (100), has been claimed. Radiation-induced polymerization of VDE has also been investigated (101,102). Alkylboron compounds activated by oxygen initiate VDE polymerization in water or organic solvents (103,104). Microwave-stimulated, low pressure plasma polymerization of VDE gives polymer film that is <10 pm thick (105). Highly regular PVDE polymer with minimized defect stmcture was synthesized and claimed (106). Perdeuterated PVDE has also been prepared and described (107). 

Radiation-Induced Polymerization. In 1956 it was discovered that D can be polymerized in the soHd state by y-irradiation (145). Since that time a number of papers have reported radiation-induced polymerization of D and D in the soHd state (146,147). The first successhil polymerization of cychc siloxanes in the Hquid state (148) and later work (149) showed that the polymerization of cycHc siloxanes induced by y-irradiation has a cationic nature. The polymerization is initiated by a cleavage of Si—C bond and formation of silylenium cation. 

An analogous mechanism should also produce polymers on irradiation of epoxies. Crivello s recent mechanistic suggestions [29] are consistent with the mechanisms given above. One can conclude that radiation-induced polymerization of epoxies can proceed via several mechanisms. However, further work is needed to determine the relative contributions of the different mechanisms, which might vary from one epoxy to another. As part of the Interfacial Properties of Electron Beam Cured Composites CRADA [37], an in-depth study of the curing mechanism for the cationic-initiated epoxy polymerization is being undertaken. 

The creation of active sites as well as the graft polymerization of monomers may be carried out by using radiation procedures or free-radical initiators. This review is not devoted to the consideration of polymerization mechanisms on the surfaces of porous solids. Such information is presented in a number of excellent reviews [66-68]. However, it is necessary to focus attention on those peculiarities of polymerization that result in the formation of chromatographic sorbents. In spite of numerous publications devoted to problems of composite materials produced by means of polymerization techniques, articles concerning chromatographic sorbents are scarce. As mentioned above, there are two principle processes of sorbent preparation by graft polymerization radiation-induced polymerization or polymerization by radical initiators. We will also pay attention to advantages and deficiencies of the methods. 

The quantitative aspects of track reactions are involved some details will be presented in Chapter 7. The LET effect is known for H2 and H202 yields in aqueous radiation chemistry. The yields of secondary reactions that depend on either the molecular or the radical yield are affected similarly. Thus, the yield of Fe3+ ion in the Fricke dosimeter system and the initiation yield of radiation-induced polymerization decrease with LET. Numerous examples of LET effects are known in radiation chemistry (Allen, 1961 Falconer and Burton, 1963 Burns and Barker, 1965) and in radiation biology (Lamerton, 1963). 

The kinetics of radiation-induced polymerization of bulk nitroethylene was also studied at 10° C by the use of hydrogen bromide as an anion scavenger (27). The value of Gt (yield of the initiation by 100 eV energy absorbed) was found to be about 3, which was much larger than the value obtained for many radiation-induced cationic polymerizations. The propagation rate constant, kp, was estimated to be 4 x 107 M-1 sec-1. The large kp value was attributed to the concept that the propagating chain ends were free ions in contrast to the existence of counter ions in catalytic polymerization. 

Table I shows the effect of visible light illumination before raising the temperature of the irradiated glasses. It appears that polymerization is not initiated at the polymerization temperature in the absence of anion radicals in the glasses. The small but not zero values of conversion for the illuminated glasses may result from incomplete bleaching of the anion radicals, the diameter of the polymerization vessels (20 mm) being much larger than that of the ESR sample tubes (4 mm). The effect of pre-illumination on the conversion indicates that the anion radicals are involved in the initiation process of the radiation-induced polymerization of nitroethylene.

These results indicate that n-butylvinylether forms the cation radicals through positive charge transfer rather than by capturing an electron to form the anion radical and suggests that the ionization potential of n-butylvinylether is lower than that of 3-methylpentane (according to the measurements by the present authors, this is the case) and its electron affinity is negative. The observed behavior of n-butylvinylether seems to coincide with its cationic nature in the radiation-induced polymerization. Though the formation of carbonium ions from the cation radicals has not yet been elucidated, the cation radicals may play an important role in the initiation process of polymerization. 

Pulse radiolysis studies concerning the polymerization as well as the degradation, crosslinking and radiation resistance of polymers are surveyed. Initiation mechanisms of the radiation-induced polymerization of styrene and other monomers are discussed on the basis of the direct measurements of the reaction intermediates. Optical and kinetic data on the short-lived chemical intermediates produced in the solution of polymers and in the rigid polymers are surveyed and discussed with special reference to the degradation mechanism of polymers. 

Application of pulse radiolysis to polymers and polymerization was motivated at first by the success of radiation-induced polymerization as a novel technique for polymer synthesis. It turned out that a variety of monomers could be polymerized by means of radiolysis, but only a little was known about the reaction mechanisms. Early studies were, therefore, devoted to searching for initiators of radiation-induced polymerization such as radicals, anions and cations derived from monomers or solvents. Transient absorption spectra of those reactive intermediates were assigned with the aid of matrix isolation technique. Thus the initiation mechanisms were successfully elucidated by this method. Propagating species also were searched for enthusiastically in some polymerization systems, but the results were rather negative, because of the low steady state concentration of the species of interest. 

It is from these perspectives that we have reviewed the pulse radiolysis experiments on polymers and polymerization in this article. The examples chosen for discussion have wide spread interest not only in polymer science but also in chemistry in general. This review is presented in six sections. Section 2 interprets the experimental techniques as well as the principle of pulse radiolysis the description is confined to the systems using optical detection methods. However, the purpose of this section is not to survey detail techniques of pulse radiolysis but to outline them concisely. In Sect. 3, the pulse radiolysis studies of radiation-induced polymerizations are discussed with special reference to the initiation mechanisms. Section 4 deals with applications of pulse radiolysis to the polymer reactions in solution including the systems related to biology. In Sect. 5 reaction intermediates produced in irradiated solid and molten polymers are discussed. Most studies are aimed at elucidating the mechanism of radiation-induced degradation, but, in some cases, polymers are used just as a medium for short-lived species of chemical interest We conclude, in Sect. 6, by summarizing the contribution of pulse radiolysis experiments to the field of polymer science. 

It was found in this experiment that both anionic and cationic species reacted efficiently with methanol in bulk styrene. The bonded dimer cations and the radical anions were converted to long-lived benzyl radicals, which initiated the radical polymerization. The G value of the propagating benzyl radical was only 0.7 in pure styrene, but it increased up to 5.2 in the presence of methanol. A small amount of methanol converted almost all the charge carriers to propagating free radicals this explains why the mechanism of radiation-induced polymerization is changed drastically from cationic to radical processes on adding methanol. 

Apart from the relevance to the radiation-induced polymerizations, the pulse radiolysis of the solutions of styrene and a-methylstyrene in MTHF or tetrahy-drofuran (THF) has provided useful information about anionic polymerization in general [33]. Anionic polymerizations initiated by alkali-metal reduction or electron transfer reactions involve the initial formation of radical anions followed by their dimerization, giving rise to two centers for chain growth by monomer addition [34]. In the pulse radiolysis of styrene or a-methylstyrene (MS), however, the rapid recombination reaction of the anion with a counterion necessarily formed during the radiolysis makes it difficult to observe the dimerization process directly. Langan et al. used the solutions containing either sodium or lithium tetrahydridoaluminiumate (NAH or LAH) in which the anions formed stable ion-pairs with the alkali-metal cations whereby the radical anions produced by pulse radiolysis could be prevented from rapid recombination reaction [33],... 

Radiation-Induced Polymerization. Polymerization induced by irradiation is initiated by free radicals and by ionic species. On very pure vinyl monomers, D. J. Metz demonstrated that ionic polymerization can become the dominating process. In Chapter 12 he postulates a kinetic scheme starting with the formation of ions, followed by a propagation step via carbonium ions and chain transfer to the vinyl monomer. C. Schneider studied the polymerization of styrene and a-methylstyrene by pulse radiolysis in aqueous medium and found results similar to those obtained in conventional free-radical polymerization. She attributes this to a growing polymeric benzyl type radical which is formed partially through electron capture by the styrene molecule, followed by rapid protonation in the side chain and partially by the addition of H and OH to the double vinyl bond. A. S. Chawla and L. E. St. Pierre report on the solid state polymerization of hexamethylcyclotrisiloxane by high energy radiation of the monomer crystals. 

The evidence in the case of styrene, where both modes of radiation-induced polymerization can be conveniently studied, is quite convincing that reduction of the concentration of water changes the predominating mode of propagation from purely free radical to essentially ionic. Evidence for an ionic propagation initiated by radiation has also been obtained in pure a-methylstyrene (3, 24), isobutylene (12, 32), cyclopenta-diene (5), / -pinene (2), 1,2-cyclohexene oxide (II), isobutyl vinyl ether (6), and nitroethylene (38), although the radical process in these monomers is extremely difficult, if not impossible, to study. 

The following reactions have been offered as a modified description of the radiation-induced polymerization of several vinyl monomers. The symbolism and nomenclature is that used by Williams et al. (36), wherein, after eliminating the contribution of anionic initiation and/or propagation, the principal propagating species is considered to be a carbonium ion. Thus,... 

Tabata and coworkers studied extensively the radiation-induced polymerization of vinylcarbazole (VC) in various solvents27-32. In one paper27 they studied the initial species formed in the polymerization of VC in benzonitrile solutions. To identify the products, they used the optical spectrum obtained for glassy solutions of vinylcarbazole in butyl chloride and 2-methyltetrahydrofuran irradiated at 77 K with y-rays. Irradiation in butyl chloride matrix is known, similarly to that in other organic chlorides, to give... 

Systematic investigation of radiation-induced polymerization was conducted in Leeds by F. S. Dainton and his group (8) and in Paris by M. Magat and co-workers (9). The results of these studies convincingly demonstrated that radiation could initiate polymerization at any desired (low) temperature and led to a fundamental conclusion, viz., radiation-induced polymerizations occurred by conventional free radical mechanisms. This concept was extended to other radiation-chemical processes, and in the 1950 s most radiation chemists used free radical theories for interpreting their experimental data. 

The yields of radiation-induced polymerizations can be very high. No additives are required, which makes it possible to synthesize very pure polymers. The initiation step is temperature independent giving rise to an easily controlled process at any desired temperature. These features account for the commercial interest in radiation polymerization. The very high speeds attainable within the layers of monomers subjected to powerful electron beams explain the wide use of this technique in radiation curing of adhesives, inks and coatings. The corresponding formulations are "solvent-free" and involve pre-polymers and monomers as reactive diluents. 

Note that the initiation step dominates the overall temperature dependence of the rate of polymerization. When the method of initiation varies, Er will also change. For redox initiation, for example, d is of the order of 40-60 kJ/mol and R for redox polymerizations is about 40 kJ/mol. For photochemical or radiation-induced polymerizations, d is practically zero and the rate of polymerization in such cases does not change much with the reaction temperature. 

Radiation-induced polymerization, which generally occurs in liquid or solid phase, is essentially conventional chain growth polymerization of a monomer, which is initiated by the initiators formed by the irradiation of the monomer i.e., ion radicals. An ion radical (cation radical or anion radical) initiates polymerization by free radical and ionic polymerization of the respective ion. In principle, therefore, radiation polymerization could proceed via free radical polymerization, anionic polymerization, and cationic polymerization of the monomer that created the initiator. However, which polymerization dominates in an actual polymerization depends on the reactivity of double bond and the concentration of impurity because ionic polymerization, particularly cationic polymerization, is extremely sensitive to the trace amount of water and other impurities. 

There seems little doubt that in radiation induced polymerizations the reactive entity is a free cation (vinyl ethers are not susceptible to free radical or anionic polymerization). The dielectric constant of bulk isobutyl vinyl ether is low (<4) and very little solvation of cations is likely. Under these circumstances, therefore, the charge density of the active centre is likely to be a maximum and hence, also, the bimolecular rate coefficient for reaction with monomer. These data can, therefore, be regarded as a measure of the reactivity of a non-solvated or naked free ion and bear out the high reactivity predicted some years ago [110, 111]. The experimental results from initiation by stable carbonium ion salts are approximately one order of magnitude lower than those from 7-ray studies, but nevertheless still represent extremely high reactivity. In the latter work the dielectric constant of the solvent is much higher (CHjClj, e 10, 0°C) and considerable solvation of the active centre must be anticipated. As a result the charge density of the free cation will be reduced, and hence the lower value of fep represents the reactivity of a solvated free ion rather than a naked one. Confirmation of the apparent free ion nature of these polymerizations is afforded by the data on the ion pair dissociation constant,, of the salts used for initiation, and, more importantly, the invariance, within experimental error, of ftp with the counter-ion used (SbCl or BF4). Overall effects of solvent polarity will be considered shortly in more detail. 

A major difference between the two methods of initiation is that the solvent in y-ray studies is almost inevitably the monomer itself, and these generally have lower dielectric constants than the chlorocarbon solvents most often used in the chemically initiated systems. As a result, it is not possible to compare the values of kp +) obtained from each technique without accounting for this difference in solvation. Classically, propagation involves charge dispersion in forming the transition-state complex and hence a reduction in the polarity of the system. Thus media of lower solvation power should favourably influence the process. (See reference 114 for more detailed discussion.) Experimentally the values of kp(+) from radiation-induced polymerizations are consistently higher than those obtained using stable salts as initiators, and this simplistic picture therefore seems to be confirmed. Dunn has recently carried out a detailed compilation of the available data on / p(+) and readers will find this an excellent distillation of the current position. 

In the case of photo-initiated polymerizations bimodal distributions can occur as a result of concurrent free-radical and cationic growth, these intermediates not being in chemical equilibrium. This arises in the bulk polymerizations of styrene photo-initiated in the presence of tetracyanobenzene and also in the radiation-induced polymerization of alkyl-substituted styrenes.In the former system the higher molecular weight fraction is attributed to a cationic... 

Radiation-induced polymerization can be carried out in bulk, in solution, in emulsion (suspension), in the gas and solid states, and in the glassy state in other words, just as in other methods of initiation (conventional, thermal, photochemical initiation, etc.). 

It should be noted that with increasing conversion, when macromolecules formed in radiation-induced polymerization accumulate in the system, in principle as a result of radiolysis they can also form free-radical initiation centres characterized by their radiation-chemical yield G . Their effect on initiation is reflected in the equation... 

When monomer initiation is of free-radical nature, solvents accelerate radiation-induced polymerization. Moreover, the higher the radiation-chemical yield of radicals, GSR, the greater is this acceleration. 

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