RAFT polymerization of temperature- and salt-responsive block copolymers as reversible hydrogels

Sean T. Hemp, Adam E. Smith, W. Clayton Bunyard, Michael H. Rubinstein, Timothy Edward Long*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

16 Citations (Scopus)


Reversible-addition fragmentation chain transfer (RAFT) polymerization enabled the synthesis of novel, stimuli-responsive, AB and ABA block copolymers. The B block contained oligo(ethylene glycol) methyl ether methacrylate (OEG) and was permanently hydrophilic in the conditions examined. The A block consisted of diethylene glycol methyl ether methacrylate (DEG) and [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TMA). The A block displayed both salt- and temperature-response with lower critical solution temperatures (LCSTs) dependent on the molar content of TMA and the presence of salt. Higher TMA content in the AB diblock copolymers increased the critical micelle temperatures (CMT) in HPLC-grade water due to an increased hydrophilicity of the A block. Upon addition of 0.9 wt% NaCl, the CMTs of poly(OEG-b-DEG95TMA5) decreased from 50 °C to 36 °C due to screening of electrostatic repulsion between the TMA units. ABA triblock copolymers displayed excellent hydrogel properties with salt- and temperature-dependent gel points. TMA incorporation in the A block increased the gel points for all triblock copolymers, and salt-response increased with higher TMA composition in the A block. For example, poly(DEG98TMA 2-b-OEG-b-DEG98TMA2) formed a hydrogel at 40 °C in HPLC-grade water and 26 °C in 0.9 wt% NaCl aqueous solution. These salt- and temperature-responsive AB diblock and ABA triblock copolymers find applications as drug delivery vehicles, adhesives, and hydrogels.

Original languageEnglish
Pages (from-to)2325-2331
Number of pages7
JournalPolymer (United Kingdom)
Issue number10
Publication statusPublished - 2014 May 13
Externally publishedYes


  • Hydrogels
  • RAFT polymerization
  • Stimuli-responsive

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics


Dive into the research topics of 'RAFT polymerization of temperature- and salt-responsive block copolymers as reversible hydrogels'. Together they form a unique fingerprint.

Cite this