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where C may or may not be an excited species depending on the energy of the electron The radiolysis of ole nic monomers results in the formation of cations, anions, and free radicals as described above It is then possible for these species to initiate chain polymerizations Whether a polymerization is initiated by the radicals, cations, or anions depends on the monomer and reaction conditions Most radiation polymerizations are radical polymerizations, especially at higher temperatures where ionic species are not stable and dissociate to yield radicals Radiolytic initiation can also be achieved using initiators, like those used in thermally initiated and photoinitiated polymerizations, which undergo decomposition on irradiation Radiation-initiated ionic polymerizations, however, have been established in a number of systems This occurs under conditions where ionic species have reasonable stabilities and the monomer is susceptable to ionic propagation.



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~ { an sin ( n Ivt) + bn cos ( n Ivt) } sin ( n I [xo + ~ ]) =





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Cationic polymerizations of isobutylene, vinyl ethers, epoxies, and styrene and anionic polymerization of acrylonitrile have been observed [Chapiro, 1962; Kubota et al, 1978; Wilson, 1974] Ionic polymerizations have been observed at temperatures as high as 30 50 C, but lower temperatures are generally required, usually not because the ionic rates increase with decreasing temperature but because the radical contribution decreases The role of reaction conditions has been well-established for styrene polymerization [Machi et al, 1972; Squire et al, 1972; Takezaki et al, 1978] The dryness of the reaction system and the absence of any other species which can terminate ions (either those formed in the radiolytic reactions (Eqs 3-57 through 3-62) or the ionic propagating species) is critical Water and other similar compounds terminate ions by transferring a proton or negative fragment (see Chap 5).

(2.86) Now, as this is a solution for all times, we can multiply (2.86) by (1/21r) exp( -iw't) and integrate over t from -00 to 00. We find that

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Styrene monomer as normally puri ed and dried often has suf cient water present ($10 2 10 4 M) to prevent ionic polymerization only radical polymerization occurs With superdried monomer ([H2 O]<10 5 10 7 M), one observes a bimodal molecular weight distribution This indicates the simultaneous occurrence of cationic and radical polymerizations since the two are known to yield different-molecular-weight polymers With decreasing water concentration ($<10 7 10 10 M) the polymerization proceeds entirely by cationic propagation as evidenced by a unimodal MWD, which is characteristic of the cationic MWD The extent of the ionic contribution relative to radical polymerization also increases with increasing radiation intensity, perhaps due to the rapid depletion of water at the higher intensities Other evidence for the ionic contributions include kinetic and activation energy data The kinetics of radiation-initiated polymerizations follow in a relatively straightforward manner those of photolytic polymerization.

~ansin(nI [xo+~]) {6(nI v - w') -6(nIv+w')}

The initiation rate is determined by the radiation intensity and the concentration and susceptibility of the compound that radiolyzes to yield the initiating species (ionic and/or radical) The nal expression for Rp is determined by the exact details of the initiation, propagation, and termination steps..

You can get a quick total of cells without applying a function. Click the cells whose values you want to total. In the status bar along the bottom of the program window, Excel displays the sum, the number of cells and the average of the selected cells.

+~]) {6 (nIv -Wi) + 6(nIv +Wl)}

Szwarc, M, Ions and Ion Pairs in Ionic Polymerization, Chap 4 in Ions and Ion Pairs in Organic Reactions, Vol 2, M Szwarc, ed, Wiley-Interscience, New York, 1974 Szwarc, M and J Smid, The Kinetics of Propagation of Anionic Polymerization and Copolymerization, Chap 5 in Progress in Reaction Kinetics, Vol 2, G Porter, ed, Pergamon Press, Oxford, 1964 Szwarc, M and M Van Beylen, Ionic Polymerization and Living Polymers, Chapman & Hall, New York, 1993 Szwarc, M, M Van Beylen, and D Van Hoyweghen, Macromolecules, 20, 445 (1987) Taninaka, T and Y Minoura, J Polym Sci Polym Chem Ed, 14, 685 (1976) Tanizaki, A, M Sawamoto, and T Higashimura, J Polym Sci Polym Chem Ed, 24, 87 (1986) Tardi, M and P Sigwalt, Eur Polym J, 8, 151 (1972) Taromi, F A and P Rempp, Makromol Chem, 190, 1791 (1989).

Teyssie, Ph, R Fayt, J P Hautekeer, C Jacobs, R Jerome, L Leemans, and S K Varshney, Makromol Chem Macromol Symp, 32, 61 (1990) Throssell, J J, S P Sood, M Szwarc, and V Stannett, J Am Chem Soc, 78, 1122 (1956) Toman, L, J Spevacek, and S Polorny, J Polym Sci Polym Chem Ed, 27, 785 (1989a) Toman, L, S Pokorny, and J Spevacek, J Polym Sci Polym Chem Ed, 27, 2229 (1989b) Tsvetanov, Ch B, Eur Polym J, 15, 503 (1979) Tung, L H, G Y-S Lo, and J A Griggs, J Polym Sci Polym Chem Ed, 23, 1551 (1985) Vairon, J-P and N Spassky, Industrial Cationic Polymerizations: An Overview, Chap 8 in Cationic Polymerizations; Mechanisms, Synthesis, and Applications, K Matyjaszewski, ed, Marcel Dekker, New York, 1996 Van Beylen, M, S.

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