Overview
Free radical polymerization is induced by free radicals, and propagated by means of growing macroradicals. The inducing initiator free radicals are mostly produced in pairs by disproportionating reactions of purposely added initiator molecules, I:
or, more rarely, singly, or, of the monomers themselves. Initiator free radicals formed in this way then react, each with a monomer molecule M in the start reaction:
and then, further monomer molecules are added on in the actual propagation reactionn
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Literature
20.1. General Reviews
I. Kuchler, Polymerisationskinetik, Springer, Heidelberg, 1951.
G. M. Burnett, Mechanism of Polymer Reactions, Interscience, New York, 1954.
C. H. Bamford, W. G. Barb, A. D. Jenkins, and P. F. Onyon, Kinetics of Vinyl Polymerization by Radical Mechanism, Butterworths, London, 1958.
J. C. Bevington, Radical Polymerization, Academic Press, London, 1961.
G. H. Williams (ed.), Advances in Free Radical Chemistry, Academic Press, New York, Vol. l ff. (from 1965 ).
A. M. North, The Kinetics of Free Radical Polymerization, Pergamon Press, Oxford, 1965.
H. Fischer, Freie Radikale während der Polymerisation, nachgewiesen und identifiziert durch Elektronenspinresonanz, Adv. Polym. Sci.—Fortschr. Hochpolym. Forschg. 5 463 (1967/68).
Kh. S. Bagdarsar’yan, Theory of Free Radical Polymerization, Israel Program for Scientific Translations, Jerusalem, 1968 (translation of the Russian edition of 1966 ).
G. E. Scott and E. Senogles, Kinetic relationships in radical polymerization, J. Macromol. Sci. C (Rev. Macromol Chem.) 9, 49 (1973).
P.-O. Kinell, B. Ranby, and V. Runnström-Reio (eds.), ESR Applications to Polymer Research (Nobel Symposium 22), Wiley, New York, 1973.
H. Fischer and D. O. Hummel, Electron spin resonance, Monogr. Mod. Chem. 6, 289 (1974).
C. H. Bamford and C. F. H. Tipper (eds.), Free Radical Polymerization (Comprehensive Chem. Kinetics 14 A), Elsevier, Amsterdam, 1976.
B. Ranby and J. F. Rabek, ESR Spectroscopy in Polymer Research, Springer, Berlin, 1977.
C. H. Bamford and C. F. H. Tipper, eds., Comprehensive Chemical Kinetics, Vol. 14A, Free-Radical Polymerization, Elsevier, Amsterdam, 1976.
R. N. Haward, ed., Dev. Polym., Vol. 2, Free Radical, Condensation, Transition Metal, and Template Polymerization, Appl. Sci. Publ., London, 1979.
G. Henrici-Olive and S. Olive, Kettenübertragungen bei der radikalischen Polymerization Fortschr. Hochpolvm. Forschg. 2 496 (1960/61).
20.2. Initiation and Start
C. Walling, Free Radicals in Solution, Wiley, New York, 1957.
A. C. Davies, Organic Peroxides, Butterworths, London, 1961.
A. V. Tobolsky and R. B. Mesrobian, Organic Peroxides, Interscience, New York, 1961.
B. L. Funt, Electrolytically controlled polymerizations, Macromol. Rev. 1, 35 (1967).
N. Yamazaki, Electrolytically initiated polymerizations, Adv. Polym. Sci. 6, 377 (1969).
D. Swern (ed.), Organic Peroxides, Wiley, New York, Vol. 1 (1970), Vol. 2 (1971), Vol. 3 (1972).
J. R. Ebdon, Thermal polymerization of styrene—A critical review, Brit. Polymer J. 3, 9 (1971).
J. W. Breitenbach, O. F. Olaj, and F. Sommer, Polymerisationsanregung durch Elektrolyse, Adv. Polym. Sci. 9, 47 (1972).
G. Parravano, Electrochemical polymerization, in Organic Electrochemistry, M. M. Baizer (ed.), Marcel Dekker, New York, 1973.
W. A. Pryor and L. D. Lasswell, Adv. Free Rad. Chem. 5, 27 (1975).
P. L. Nayak and S. Lenka, Redox polymerization initiated by metal ions, J. Macromol. Sci.—Revs. Macromol. Chem. C19, 83 (1980).
G. S. Misra and U.D.N. Bajpai, Redox polymerization, Progr. Polym. Sci. 8, 61 (1982).
20.3. Propagation and Termination
D. G. Smith, Non-ideal kinetics in free radical polymerization, J. Appl. Chem. 17, 339 (1967). A. M. North, Diffusion control of homogeneous free radical reactions, in Progress in High Polymers, Vol. II, J. C. Robb and F. W. Peaker (eds.), Heywood, London, 1968.
J. W. Breitenbach, Popcorn polymerizations, Adv. Macromol. Chem. 1, 139 (1968): Proliferous polymerization, Brit. Polym. J. 6, 119 (1974).
S. Tazuke, Effects of metal salts on radical polymerization, Prog. Polym. Sci. Japan 1, 69 (1969).
V. I. Volodina, A. I. Tarasov, and S. S. Spasskij, Polymerization of allylic compounds, Usp. Khim (Russian Chem. Rev.) 39, 276 (1970).
W. J. Bailey, P. V. Chen, W.-B. Chiao, T. Endo, L. Sidney, N. Yamamoto, and K. Yonezawa, Free-radical ring-opening polymerization, in Contemporary Topics in Polymer Science, Vol. 3, M. Shen (ed.), Plenum, New York, 1979.
C. S. Sheppard and V. R. Kamath, The selection and use of free radical initiators, Polym. Eng. Sci. 19, 597 (1979).
G. P. Gladyschew and K. M. G. Gibov, Polymerization at Advanced Degrees of Conversion, Israel Program for Scientific Translations, Jerusalem, 1970 (translation of the Russian edition of 1968 ).
K. Takemoto, Preparation and polymerization of vinyl heterocyclic compounds, J. Macromol. Sci. C (Rev. Macromol Chem.) 5, 29 (1970).
S. Nozakura and Y. Inaki, Radical polymerization of internal olefins; steric effects in polymerization, Prog. Polym. Sci. Japan 2, 109 (1971).
M. Oiwa and A. M. Matsumoto, Radical polymerizations of diallyl dicarboxylates, Progr. Polym. Sci. 7, 107 (1974).
G. R. Gladyshev and V. A. Popov, Radikalische Polymerisation bis zu hohen Umsätzen, Akademic-Verlag, Berlin, 1978.
20.4. Transfer
C. Starks, Free Radical Telomerization, Academic Press, New York, 1974.
R. K. Freidlina and A. B. Terent’ev, Free-radical rearrangements in telomerization, Acc. Chem. Res. 10, 9 (1977).
20.5. Stereocontrol
H.-G. Elias, P. Göldi, and B. L. Johnson, Monomer constitution and stereocontrol in free radical polymerizations, Adv. Chem. Ser. 128, 21 (1973).
B. Englin, 1,3-Asymmetric induction in stereoregular radical reactions, J. Polym. Sci. (Symp.) 55, 219 (1976).
M. Kamachi, Influence of solvent on free radical polymerization of vinyl compounds, Adv. Polym. Sci. 38, 55 (1981).
20.6. Industrial Polymerizations
F. A. Bovey, I. M. Kolthoff, A. J. Medalia, and E. J. Mehan, Emulsion Polymerization, Interscience, New York, 1955.
H. Gerrens, Kinetik der Emulsionspolymerisation, Fortschr. Hochpolym. Forschg. 1 234 (1958/60).
D. C. Blackley (ed.), High Polymer Latices, MacLaren, London, 1966.
J. C. H. Hwa and J. W. Vanderhoff (eds.), New Concepts in Emulsion Polymers, Wiley, New York, 1969.
A. E. Alexander and D. H. Napper, Emulsion polymerization, Progr. Polym. Sci. 3, 145 (1971).
D. C. Blackley, Emulsion Polymerization: Theory and Practice, Halsted, New York, 1975.
K. E. J. Barrett (ed.), Dispersion Polymerization in Organic Media, Wiley—Interscience, New York, 1975.
J. Ugelstad and F. K. Hansen, Kinetics and mechanism of emulsion polymerization, Rubber Chem. Technol. 49, 536 (1976).
I. Piirma and J. L. Gardon (eds.), Emulsion polymerization, ACS Symp. Ser. 24 (1976)
H. Gerrens, Polymerization Reactors and Polyreactions, A Review, Proc. 4th Internat./6th
Europ. Symp. Chem. Reaction Engng.,Dechema, Frankfurt, Vol. 2, 1976.
T. C. Bouton and D. C. Chappeler (eds.), Continuous polymerization reactors, AIChE Symp.
Ser. 160 Vol. 72, Amer. Inst. Chem. Engng., New York, 1976.
J. L. Gardon, Emulsion polymerization, in Polymerization Processes, C. E. Schildknecht and I. Skeist (eds.), Wiley, New York, 1977.
V. I. Eliseeva, S. S. Ivanchev, S. I. Kuchanov, and A. V. Lebedev, Emulsion Polymerization and Its Application in Industry, Consultants Bureau, New York, 1981 ( Engl. transi. of a 1976 Russian book).
D. R. Bassett and A. E. Hamielee, eds., Emulsion polymers and emulsion polymerization, ACS Symp. Ser. 165, Amer. Chem. Soc., Washington, (1981).
I. Piirma, Emulsion Polymerization, Academic Press, New York, 1982.
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Elias, HG. (1984). Free Radical Polymerization. In: Macromolecules. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-2809-2_6
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