NDLI: Effect of initiators on grafting in the initial stage of the emulsion polymerization of methyl methacrylate using poly(vinyl alcohol) as a protective colloid

Content Provider	Springer Nature Link
Author	Okaya, T. Suzuki, A. Kikuchi, K.
Copyright Year	2002
Abstract	To make clear the reason of unsuitability of poly(vinyl alcohol) (PVA) protective colloid for the emulsion polymerization of conjugated monomers, a model experiment of emulsion polymerization of methyl methacrylate (MMA) was carried out with ammonium persulfate (APS) or azobis(isobutyronitrile) (AIBN) initiators, where a small amount of MMA (1/100th of the concentration compared with ordinary emulsion polymerization) was employed. This corresponds to the initial stage of the emulsion polymerization. Grafting of MMA onto PVA took place remarkably irrespective of the kind of the initiators. Formation of homo-poly(MMA) was observed to a small extent. The formation of new emulsion particles smaller than 100 nm continued to increase to almost the end of the polymerization. PVA molecules in the grafted polymer are supposed to act as stabilizers of newly formed particles. From kinetic treatment using the experimental data, the important issues were derived as follows. Firstly, the sulfate anion radical from APS is much more reactive than the isobutyronitrile radical from AIBN in terms of hydrogen abstraction from PVA. Secondly, high grafting ability of the latter initiator system, notwithstanding the much lower reactivity in the hydrogen abstraction compared with the APS system, is attributed to the relative reactivity of the primary radicals, i.e., hydrogen abstraction reaction from PVA to initiation reaction with MMA. The much slower rate of addition of the isobutyronitrile radical to the monomer compared with that of hydrogen abstraction from PVA facilitates the grafting, although the rate constant of hydrogen abstraction is far smaller than that with the sulfate anion radical by 10−4 times.
Starting Page	188
Ending Page	192
Page Count	5
File Format	PDF
ISSN	0303402X
Journal	Colloid and Polymer Science
Volume Number	280
Issue Number	2
e-ISSN	14351536
Language	English
Publisher	Springer-Verlag
Publisher Date	2002-02-01
Publisher Place	Berlin/Heidelberg
Access Restriction	One Nation One Subscription (ONOS)
Content Type	Text
Resource Type	Article
Subject	Colloid and Surface Chemistry Materials Chemistry Physical and Theoretical Chemistry Polymers and Plastics

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