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Low Temperature Aqueous Living/Controlled (RAFT) Polymerization of Carboxybetaine Methacrylamide up to High Molecular Weights
Author(s) -
RodriguezEmmenegger Cesar,
Schmidt Bernhard V. K. J.,
Sedlakova Zdenka,
Šubr Vladimir,
Alles Aldo Bologna,
Brynda Eduard,
BarnerKowollik Christopher
Publication year - 2011
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.201100176
Subject(s) - methacrylamide , reversible addition−fragmentation chain transfer polymerization , chain transfer , polymerization , polymer chemistry , radical polymerization , living polymerization , chemistry , atom transfer radical polymerization , raft , polymer , copolymer , acrylamide , organic chemistry
Among the class of zwitterionic polymers poly(carboxybetaine)s (poly(CB)s) are unique, emerging as the only ultra‐low fouling materials known allowing the preparation of biosensors, fouling resistant nanoparticles, and non‐adhesive surfaces for bacteria. Poly(carboxybetaine methacrylate) and poly(carboxybetaine acrylamide) have been prepared via atom transfer radical polymerization (ATRP), however a polymerization with living characteristics has not been achieved yet. Herein, the first successful living/controlled reversible addition fragmentation transfer (RAFT) polymerization of (3‐methacryloylamino‐propyl)‐(2‐carboxy‐ethyl)‐dimethyl‐ammonium (carboxybetaine methacrylamide) (CBMAA‐3) in acetate buffer (pH 5.2) at 70 and 37 °C is reported. The polymerization afforded very high molecular weight polymers (determined by absolute size exclusion chromatography, close to 250 000 g · mol −1 in less than 6 h) with low PDI (<1.3) at 70 °C. The polymerization was additionally carried out at 37 °C allowing to achieve yet lower PDIs (1.06 ≤ PDI ≤ 1.15) even at 90% conversion, demonstrating the suitability of the polymerization conditions for bioconjugate grafting. The living character of the polymerization is additionally evidenced by chain extending poly(CBMAA‐3) at 70 and 37 °C. Block copolymerization from biologically relevant poly[ N ‐(2‐hydroxypropyl)methacrylamide] macroCTAs was additionally performed.