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Free Radical Polymerization

  • Chapter
Macromolecules

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:

EquationSource% MathType!MTEF!2!1!+- % feaagCart1ev2aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaGymaiabgk % ziUkaaikdacaWGsbWaa0baaSqaaiaaigdaaeaacqGHIaYTaaaaaa!3C9C!]]</EquationSource><EquationSource Format="TEX"><![CDATA[$$1 \to 2R_1^ \bullet $$
(20-1)

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:

EquationSource% MathType!MTEF!2!1!+- % feaagCart1ev2aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamOuamaaDa % aaleaacaaIXaaabaGaeyOiGClaaOGaey4kaSIaamytaiabgkziUkaa % dkfadaWgaaWcbaGaaGymaaqabaGccaWGnbWaaWbaaSqabeaacqGHIa % YTaaaaaa!412F!]]</EquationSource><EquationSource Format="TEX"><![CDATA[$$R_1^ \bullet + M \to {R_1}{M^ \bullet }$$
(20-2)

and then, further monomer molecules are added on in the actual propagation reactionn

EquationSource% MathType!MTEF!2!1!+- % feaagCart1ev2aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn % hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr % 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9 % vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x % fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamOuamaaBa % aaleaacaWGjbaabeaakiaad2eadaahaaWcbeqaaiabgkci3caakmaa % oqcaleaacqGHRaWkcaWGnbaabeGccaGLsgcacaWGsbWaaSbaaSqaai % aadMeaaeqaaOGaamytamaaDaaaleaacaaIYaaabaGaeyOiGClaaOWa % a4ajaSqaaiabgUcaRiaad2eaaeqakiaawkziaiaadkfadaWgaaWcba % GaaGymaaqabaGccaWGnbWaa0baaSqaaiaaiodaaeaacqGHIaYTaaGc % caGGSaGaamyzaiaadshacaWGJbGaaiOlamaaoqcaleaacqGHRaWkca % WGnbaabeGccaGLsgcacaWGqbWaa0baaSqaaiaadMgaaeaacqGHIaYT % aaaaaa!561B!]]</EquationSource><EquationSource Format="TEX"><![CDATA[$${R_I}{M^ \bullet }\xrightarrow{{ + M}}{R_I}M_2^ \bullet \xrightarrow{{ + M}}{R_1}M_3^ \bullet ,etc.\xrightarrow{{ + M}}P_i^ \bullet $$
(20-3)

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Authors and Affiliations

  1. Michigan Molecular Institute, Midland, Michigan, USA

    Hans-Georg Elias

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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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  • DOI: https://doi.org/10.1007/978-1-4899-2809-2_6

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