Synthesis, multilayer film assembly, and capsule formation of macromolecularly engineered acrylic acid and styrene sulfonate block copolymers

Yap, H. P., Hao, X., Tjipto, E., Gudipati, C., Quinn, J. F., Davis, T. P., Barner-Kowollik, C., Stenzel, M. H., & Caruso, F. (2008) Synthesis, multilayer film assembly, and capsule formation of macromolecularly engineered acrylic acid and styrene sulfonate block copolymers. Langmuir, 24(16).

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We report the use of copolymers synthesized with specific block ratios of weakly and strongly charged groups for the preparation of stable, pH-responsive multilayers. In this study, we utilized reversible addition-fragmentation chain transfer (RAFT) polymerization in the synthesis of novel pH-sensitive copolymers comprising block domains of acrylic acid (AA) and styrene sulfonate (SS) groups. The PAAX-b-SSy copolymers, containing 37%, 55%, and 73% of AA groups by mass (denoted as PAA37-b-SS63, PAA55-b-SS45, and PAA73-b-SS27, respectively), were utilized to perform stepwise multilayer assembly in alternation with poly(allylamine hydrochloride), PAH. The ratio of AA to SS groups, and the effect of the pH of both anionic and cationic adsorption solutions, on multilayer properties, were investigated using ellipsometry and atomic force microscopy. The presence of SS moieties in the PAA X-b-SSy copolymers, regardless of the precise composition, lead to films with a relatively consistent thickness. Exposure of these multilayers to acidic conditions postassembly revealed that these multilayers do not exhibit the characteristic large swelling that occurs with PAA/PAH films. The film stability was attributed to the presence of strongly charged SS groups. PAAx-b-SSy/PAH films were also formed on particle substrates under various adsorption conditions. Microelectrophoresis measurements revealed that the surface charge and isoelectric point of these core-shell particles are dependent on assembly pH and the proportion of AA groups in PAAx-b-SSy. These core-shell particles can be used as precursors to hollow capsules that incorporate weak polyelectrolyte functionality. The role of AA groups in determining the growth profile of these capsules was also examined. The multilayer films prepared may find applications in areas where pH-responsive films are required but large film swelling is unfavorable. © 2008 American Chemical Society.

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ID Code: 99199
Item Type: Journal Article
Refereed: Yes
Additional Information: Cited By :23
Export Date: 5 September 2016
Correspondence Address: Caruso, F.; Centre for Nanoscience and Nanotechnology, Department of Chemical and Biomolecular Engineering, University of Melbourne, Melbourne, VIC 3010, Australia; email:
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Keywords: ABS resins, Acids, Acrylics, Block copolymers, Carboxylic acids, Chemical reactions, Copolymerization, Copolymers, Monomers, Multilayer films, Multilayers, Organic acids, Plastic products, Styrene, Acrylic acid, Charged groups, Styrene sulfonate, Polymers
DOI: 10.1021/la8011074
ISSN: 07437463
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: 10 Oct 2016 01:27

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