Near-Model Amphiphilic Polymer Conetworks Based on Four-Arm Stars of Poly(vinylidene fluoride) and Poly(ethylene glycol): Synthesis and Characterization

Amphiphilic polymer conetworks (APCN) were prepared in N,N-dimethylformamide (DMF) by the interconnection of four-arm star poly(vinylidene fluoride) (PVDF, Mn = 8800 Da) end-functionalized with benzaldehyde groups and four-arm star poly(ethylene glycol) (PEG, Mn = 10 kDa) end-functionalized with benzaacylhydrazide groups. The PVDF stars were prepared via the reversible addition–fragmentation chain transfer polymerization of vinylidene fluoride using a tetraxanthate chain transfer agent. Equilibrium swelling of the APCNs in various solvents was dependent on the compatibility of the APCN components with the solvent, with the degrees of swelling (DS) varying from 22 in DMF (a good solvent for both PEG and PVDF), down to 8 in water (a good and selective solvent for PEG), and even down to 3 in diethyl ether (a nonsolvent for both polymers). Characterization of the conetworks in D2O using small-angle neutron scattering (SANS) indicated phase separation at the nanoscale, as evidenced by a (broad) correlation pea...