Reversible Addition-Fragmentation Chain Transfer Aqueous Dispersion Polymerization of 4-Hydroxybutyl Acrylate Produces Highly Thermoresponsive Diblock Copolymer Nano-Objects

Abstract

The reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA) using a poly(glycerol monomethacrylate) (PGMA) precursor is an important prototypical example of polymerization-induced self-assembly. 4-Hydroxybutyl acrylate (HBA) is a structural isomer of HPMA, but the former monomer exhibits appreciably higher aqueous solubility. For the two corresponding homopolymers, PHBA is more weakly hydrophobic than PHPMA. Moreover, PHBA has a significantly lower glass transition temperature (Tg) so it exhibits much higher chain mobility than PHPMA at around ambient temperature. In view of these striking differences, we have examined the RAFT aqueous dispersion polymerization of HBA using a PGMA precursor with the aim of producing a series of PGMA57-300-PHBA100-1580 diblock copolymer nano-objects by systematic variation of the mean degree of polymerization of each block. A pseudo-phase diagram is constructed using transmission electron microscopy to assign the copolymer morphology after employing glutaraldehyde to cross-link the PHBA chains and hence prevent film formation during grid preparation. The thermoresponsive character of the as-synthesized linear nano-objects is explored using dynamic light scattering and temperature-dependent rheological measurements. Comparison with the analogous PGMAx-PHPMAy formulation is made where appropriate. In particular, we demonstrate that replacing the structure-directing PHPMA block with PHBA leads to significantly greater thermoresponsive behavior over a much wider range of diblock copolymer compositions. Given that PGMA-PHPMA worm gels can induce stasis in human stem cells (see Canton et al., ACS Central Science, 2016, 2, 65-74), our findings are likely to have implications for the design of next-generation PGMA-PHBA worm gels for cell biology applications.