Reversible addition fragmentation chain transfer polymerization of sterically hindered monomers: Toward well-defined rod/coil architectures

Szablan, Z., Toy, A. A., Davis, T. P., Hao, X., Stenzel, M. H., & Barner-Kowollik, C. (2004) Reversible addition fragmentation chain transfer polymerization of sterically hindered monomers: Toward well-defined rod/coil architectures. Journal of Polymer Science, Part A: Polymer Chemistry, 42(10).

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The sterically hindered monomers dibutyl itaconate (DBI) and dicyclohexyl itaconate (DCHI) were polymerized via reversible addition fragmentation chain transfer (RAFT) free-radical polymerization. S,S′-Bis(α, α′-dimethyl-α″-acetic acid) trithiocarbonate, cumyl dithiobenzoate, and cumyl phenyldithioacetate have been used as RAFT agents to mediate a series of polymerizations at 65°C yielding rod polymers ranging in number average molecular weight from 9000 to 92,000 g mol-1. The progress of the polymerization was followed via online Fourier transform-near infrared spectroscopy. The polydispersity indices of the obtained rod polymers were relatively high at 1.4-1.7. The RAFT polymerizations of the hindered monomers used in the present study displayed both ideal living and hybrid behavior between conventional and living polymerization, depending on the RAFT agent used. DCHI rod polymers generated via the RAFT process were subsequently reinitiated in the presence of styrene to produce a range of BAAB and A-B rod-coil block copolymers of molecular weights up to 164,000 g mol-1. The chain extension yields molecular weight distributions that progressively shift to higher molecular weights and are unimodal. Thermogravimetric analysis of the pDCHI-block-pStyrene copolymers indicates thermal degradation in two separate steps for the pDCHI and pStyrene blocks. © 2004 Wiley Periodicals, Inc.

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ID Code: 99093
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :47
Export Date: 5 September 2016
Correspondence Address: Barner-Kowollik, C.; Ctr. for Adv. Macromolecular Design, Sch. of Chem. Eng./Indust. Chemistry, University of New South Wales, Sydney, NSW 2052, Australia; email:
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Keywords: Block copolymers, Kinetics (polym.), Online Fourier transform-near infrared (FT-NIR) spectroscopy, Reversible addition fragmentation chain transfer (RAFT) polymerization, Sterically hindered monomers, Free radical polymerization, Free radicals, Pyrolysis, Thermal effects, Thermodynamic stability, Thermogravimetric analysis, Vinyl resins, Bulk styrene, Mass loss, Nitroxide mediated polymerization, Styrene, polymer
DOI: 10.1002/pola.20098
ISSN: 0887624X
Divisions: Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
Deposited On: 22 Sep 2016 04:50
Last Modified: 22 Sep 2016 04:50

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