Free radical polymerisation. The synthesis of graft copolymers

  • Terence Corner
Conference paper
Part of the Advances in Polymer Science book series (POLYMER, volume 62)


This review considers the use of the matched chain-transfer, free-radical, solution-polymerisation method for the preparation of macromonomers. Thus, the various experimental parameters which can be manipulated so as to produce low molecular weight polymers possessing a single, terminal, functional group are critically appraised in respect of the likely molecular weight distribution of the polymers and the weight fraction of polymer molecules produced which possess the desired functionality. The free radical polymerisation method described can in fact be used to prepare macromonomers which compare favourably to those synthesised by ‘living’ polymerisation methods in terms of molecular weight distribution and degree of functionalisation provided that the polymerisation experiments are carefully designed and controlled.


Molecular Weight Distribution Graft Copolymer Chain Transfer Polymer Molecule Methyl Acrylate 
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List of Abbreviations


2,2′-azo-bis-2-methyl propionitrile


4,4′-azo-bis-4-cyano valeric acid




thioglycollic acid






methyl methacrylate


vinyl acetate




N-vinyl pyrrolidone


lauryl methacrylate


ethyl acrylate

PST, PMMA etc.

polystyrene, polymethylmethacrylate etc.






transfer agent

P and P

dead polymer and polymeric free radical, respectively



Mc, Md

monomers for which the dominant modes of radical-radical termination are combination and disproportionation, respectively


average radical lifetime

\(\overline M _n ,\overline M _\eta\)

number and viscosity molecular weights, respectively


a dimensionless parameter: g=1.0 for Md monomers and g=2.0 for Mc monomers


a factor which denotes the proportion of radicals produced during the decomposition of an initiator which actually initiate growth of polymer chains typically 0.8>f>0.5

kt, ktr, kp, kd

termination, transfer, propagation and decomposition rate constants

CX, CM etc.

chain transfer constants to X, M etc.

\(\overline {DP} _0 ,\overline {DP} _X\) etc.

average degrees of polymerisation. See text for definitions.

ωt, ωtr

the weight fractions of polymer with unwanted functionality produced by termination and transfer reactions, respectively


the total weight fraction of polymer produced with unwanted functionality


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Copyright information

© Springer-Verlag 1984

Authors and Affiliations

  • Terence Corner
    • 1
  1. 1.International Paint P.L.C. 0-5 LaboratoryHeavy Duty Services Stoneygate Lane, Felling GatesheadTyne & WearEngland

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