Tuning the properties of hydrogen-bonded block copolymer worm gels prepared polymerization-induced self-assembly.

Polymerization-induced self-assembly (PISA) is exploited to design hydrogen-bonded poly(stearyl methacrylate)-poly(benzyl methacrylate) [PSMA-PBzMA] worm gels in -dodecane. Using a carboxylic acid-based RAFT agent facilitates hydrogen bonding between neighboring worms to produce much stronger physical gels than those prepared using the analogous methyl ester-based RAFT agent. Moreover, tuning the proportion of these two types of end-groups on the PSMA chains enables the storage modulus (') of a 20% w/w worm gel to be tuned from ∼4.5 kPa up to ∼114 kPa. This is achieved two complementary routes: (i) an approach using binary mixtures of acid- and ester-capped PSMA stabilizer chains during PISA or (ii) a post-polymerization processing strategy using a thermally-induced worm-to-sphere transition to mix acid- and ester-functionalized spheres at 110 °C that fuse to form worms on cooling to 20 °C. SAXS and rheology studies of these hydrogen-bonded worm gels provide detailed insights into their inter-worm interactions and physical behavior, respectively. In the case of the carboxylic acid-functionalized worms, SAXS provides direct evidence for additional inter-worm interactions, while rheological studies confirm both a significant reduction in critical gelation concentration (from approximately 10% w/w to 2-3% w/w) and a substantial increase in critical gelation temperature (from 41 °C to 92 °C). It is remarkable that a rather subtle change in the chemical structure results in such improvements in gel strength, gelation efficiency and gel cohesion.