Living free-radical polymerization of sterically hindered monomers: Improving the understanding of 1,1-disubstituted monomer systems

Szablan, Z., Ah Toy, A., Terrenoire, L., Davis, T. P., Stenzel, M. H., Müller, A. H. E., & Barner-Kowollik, C. (2006) Living free-radical polymerization of sterically hindered monomers: Improving the understanding of 1,1-disubstituted monomer systems. Journal of Polymer Science, Part A: Polymer Chemistry, 44(11).

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Abstract

The sterically hindered, 1,1-disubstituted monomers di-n-butyl itaconate (DBI), dicyclohexyl itaconate (DCHI), and dimethyl itaconate (DMI) were polymerized with reversible addition-fragmentation chain transfer (RAFT) free-radical polymerization and atom transfer radical polymerization (ATRP). Cumyl dithiobenzoate, cumyl phenyl dithioacetate, 2-cyanoprop-2-yl dithiobenzoate, 4-cyanopentanoic acid dithiobenzoate, and S- methoxycarbonylphenylmethyl dithiobenzoate were employed as RAFT agents to mediate a series of polymerizations at 60°C yielding polymers ranging in their number-average molecular weight from 4500 to 60,000 g mol-1. The RAFT polymerizations of these hindered monomers displayed hybrid living behavior (between conventional and living free-radical polymerization) of various degrees depending on the molecular structure of the initial RAFT agent. In addition, DCHI was polymerized via ATRP with a CuCl/methyl benzoate/N,N,N′N″N‴-pentamethyldiethylenetriamine/ cyclohexanone system at 60°C. Both the ATRP and RAFT polymerization of the hindered monomers displayed living characteristics; however, broader than expected molecular weight distributions were observed for the RAFT systems (polydispersity index = 1.15-3.35). To assess the cause of this broadness, chain-transfer-to-monomer constants for DMI, DBI, and DCHI were determined (1.4 × 10-3, 1.3 × 10-3, and 1.0 × 10 -3, respectively) at 60°C. Simulations carried out with the PREDICI program package suggested that chain transfer to monomer contributed to the broadening process, In addition, the experimental results indicated that viscosity had a pronounced effect on the broadness of the molecular weight distributions. © 2006 Wiley Periodicals, Inc.

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ID Code: 99133
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :29
Export Date: 5 September 2016
CODEN: JPACE
Correspondence Address: Müller, A.H.E.; Makromolekulare Chemie II, Universität Bayreuth, Bayreuth, 95447, Germany; email: axel.mueller@uni-bayreuth.de
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Keywords: Atom transfer radical polymerization (ATRP), Chain transfer to monomer, PREDICI modeling, Reversible addition fragmentation chain transfer (RAFT), Sterically hindered monomers, Viscosity, Computer simulation, Free radical polymerization, Molecular structure, Molecular weight, Chain transfer to monomers, Reversible addition fragmentation chain transfer, Monomers
DOI: 10.1002/pola.21470
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: 05 Oct 2016 04:54

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