Emulsion polymerization of styrene in the presence of reversible addition-fragmentation chain transfer agents

Hodgson, Marcelle (2000-03)

Thesis (MSc)--Stellenbosch University, 2000.

Thesis

ENGLISH ABSTRACT: This work involves the study of the effects of Reversible Addition-Fragmentation Chain Transfer (RAFT) agents on the emulsion polymerization of styrene. The feasibility of RAFT as a method for obtaining controlled radical polymerizations in emulsion systems is also investigated. Both seeded and ab initio systems were studied with three RAFT agents of varying structure. Inhibition and retardation effects on addition of various amounts of the RAFT agents to the emulsion systems were observed and the trends noticed. The effect of the RAFT agents on the average number of radicals per latex particle was calculated from reaction rates. The effect of the RAFT agent on the molecular weight and the molecular weight distribution was monitored by gel permeation chromatography. Exit of free radicals from the latex particles proves to be a major feature in the studied RAFT emulsion systems. Fragmentation of the RAFT agent in the latex particles, gives rise to free radical species that can exit from the particle and enter other particles where they can either terminate instantaneously or propagate. The exit and termination processes presumably result in both the inhibition and retardation of the emulsion polymerizations. A linear increase in Mn with conversion is observed, however the low concentration of RAFT agent in the latex particles is responsible for the obtained number average molecular weights being much higher than predicted. The low concentrations of RAFT agents in the latex particles is also responsible for the broad molecular weight distributions that are obtained. Reaction conditions for RAFT experiments should to be chosen so that the effects of exit processes are minimized and that the RAFT agent is primarily situated in the latex particles. These conditions must be met if the RAFT process is to be successful as a method of controlled radical polymerization in emulsions.

AFRIKAANSE OPSOMMING: Hierdie navorsing behels die studie van die effek van In bygevoegde addisie-fragmentasie kettingsoordragsreagent (RAFT1) op die emulsie polimerisasie van stireen. Die uitvoerbaarheid van RAFT as 'n metode om gekontroleerde radikale polimerisasies in emulsiesisteme te verkry is ook ondersoek. Eksperimente met drie RAFTkettingoordragsreagente van gevarieerde strukture is uitgevoer in beide seeded en ab initia sisteme. Die effek van die RAFT-reagent op die inhibisie en vertraging van die emulsie polimerisasie is waargeneem en die invloed van RAFT op die gemiddelde aantal radikale per partikel is bepaal. Die ontwikkeling van die molekulêre massa en die molekulêre massadistribusie is waargeneem deur middel van gel permeasie- kromatografiese tegnieke. Die ontsnapping van vrye radikale vanuit die partikels was 'n belangrike faktor in RAFT emulsiesisteme wat ondersoek is. Hierdie radikale is gegenereer deur die fragmentasie van die oorspronklike RAFT-reagent. Fragmentasie van die RAFT-reagent in die lateks partikels lei tot die vorming van vrye radikale spesies wat uit een partikel kan ontsnap en ander partikels kan binnedring waar dit onmiddellik kan termineer of propageer. Die ontsnappings- en terminasieprosesse van vrye radikale lei oënskynlik tot die inhibering en vertraging van die emulsie polimerisasie. 'n Lineêre verhoging in die gemiddelde molekulêre massa tydens konversie is waargeneem, alhoewel die Mn-waardes baie hoër was as wat verwag is. Die verskil kan toegeskryf word aan die klein hoeveelhede van die RAFT-reagent wat in die partikels teenwoordig is. Hierdie lae RAFT-konsentrasies is ook verantwoordelik vir die breë molekulêre massa distribusie wat waargeneem is. Vir die RAFT-proses om suksesvol te wees in gekontroleerde radikale polimerisasies in emulsies, moet reaksie kondisies so gekies word dat die ontsnapping van vrye radikale tot 'n minimum beperk word en die RAFT-reagent hoofsaaklik in die lateks partikels teenwoordig is.

Please refer to this item in SUNScholar by using the following persistent URL: http://hdl.handle.net/10019.1/51739
This item appears in the following collections: