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Polymers 2016, 8(6), 234; doi:10.3390/polym8060234

Effect of Very High Charge Density and Monomer Constitution on the Synthesis and Properties of Cationic Polyelectrolytes

Institut d’Ingénierie Biologique et Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne, station 15, Lausanne CH-1015, Switzerland
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Academic Editor: Marguerite Rinaudo
Received: 8 March 2016 / Revised: 16 May 2016 / Accepted: 30 May 2016 / Published: 16 June 2016
(This article belongs to the Collection Polyelectrolytes)
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Abstract

The free-radical homopolymerization of 1,3-bis(N,N,N-trimethylammonium)-2-propylmethacrylate dichloride (di-M) and 1,3-bis(N,N,N-trimethylammonium)-2-propylacrylate dichloride (di-A) in aqueous solution yields cationic polyelectrolytes (PEL) with theoretical/structural charge spacing of only ≈0.12 nm. The high charge density causes condensation of ≈82% of the chloride counterions. The high level of counterion condensation reduces the ionic strength in the polymerizing batch when the monomer molecules connect to PEL chains. This has the consequence that the hydrodynamic and excluded volume of the PEL molecules will change. Studies of the free radical polymerization revealed non-ideal polymerization kinetics already at low conversion and additionally autoacceleration above a certain monomer concentration and conversion. Similar autoacceleration was not observed for monomers yielding PEL with charge spacing of 0.25 or 0.5 nm. Coulomb interactions, monomer association, steric effects, and specific features of the monomer constitution have been evaluated concerning their contributions to the concentration dependence and conversion dependence of kinetic parameters. The different backbone constitutions of di-M and di-A not only influence the polymerization kinetics but also equip poly(di-M) with higher hydrolytic stability. The experimental results confirm the impact of electrochemical parameters and the necessity to reconsider their inclusion in kinetic models. View Full-Text
Keywords: free-radical polymerization; ionic monomers; water soluble polymers; polyelectrolytes; counterion condensation; autoacceleration free-radical polymerization; ionic monomers; water soluble polymers; polyelectrolytes; counterion condensation; autoacceleration
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Ahmadloo, H.; Losada, R.; Wandrey, C. Effect of Very High Charge Density and Monomer Constitution on the Synthesis and Properties of Cationic Polyelectrolytes. Polymers 2016, 8, 234.

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