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Advances in Materials Science and Engineering
Volume 2015, Article ID 973632, 13 pages
Research Article

Kinetic Studies of Atom Transfer Radical Polymerisations of Styrene and Chloromethylstyrene with Poly(3-hexyl thiophene) Macroinitiator

1Division of Materials Technology, School of Energy, Environment and Materials, King Mongkut’s University of Technology Thonburi (KMUTT), Bangkok 10140, Thailand
2Nanotec-KMUTT Center of Excellence on Hybrid Nanomaterials for Alternative Energy (HyNAE), Bangkok 10140, Thailand
3Pilot Plant Development and Training Institute, King Mongkut’s University of Technology Thonburi, Bangkok 10140, Thailand
4National Metal and Materials Technology Center (MTEC), Pathumthani 12120, Thailand
5National Nanotechnology Center (NANOTEC), Pathumthani 12120, Thailand

Received 15 October 2014; Revised 9 February 2015; Accepted 10 February 2015

Academic Editor: Doo-In Kim

Copyright © 2015 Nattawoot Rattanathamwat et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


Poly(3-hexyl thiophene)-b-poly(styrene-co-chloromethylstyrene) copolymers, to be used as a prepolymer for preparing donor-acceptor block copolymers for organic solar cells, have been synthesised by reacting P3HT macroinitiators with styrene and chloromethylstyrene via three types of atom transfer radical polymerisation (ATRP) systems, which are (1) a normal ATRP, (2) activators generated by electron transfer (AGET), and (3) a simultaneous reverse and normal initiation (SR&NI). The kinetics of these ATRP systems were studied as a function of monomers to the macroinitiator molar ratio. It was found that all of the three types of ATRP systems led to first order kinetics with respect to monomers. The highest rate constant (k) of 3.4 × 10−3 s−1 was obtained from the SR&NI ATRP system. The molecular weights of the product determined by the GPC were lower than were the theoretical values. The result was discussed in light of the chain transfer reaction to the poly(chloromethylstyrene) repeating units. Morphology of the synthesized block copolymers, examined by an atomic force microscopy (AFM), were also compared and discussed.