Dilute-solution structure of charged arborescent graft polymer

The solutions of charged G1 arborescent polystyrene-graft-poly(2-vinylpyridine) copolymers in methanol-d4 and D2O were investigated over a dilute concentration range ϕ=0.005-0.05 (ϕ: mass fraction) using small-angle neutron scattering (SANS). Upon addition of acid (HCl) arborescent graft polymers became charged and a peak appeared in SANS data. The interparticle distance (dexp) calculated from a peak position corresponded to the expected value (duni) for a uniform particle distribution. This indicates the formation of liquid-like ordering due to long-range Coulombic repulsions. The smaller dielectric constant of methanol-d4 resulted in long-range electrostatic repulsions persisting to lower polymer concentration than in D2O. The slow mode scattering was observed by dynamic light scattering measurements for the same polymer solutions, indicating the presence of structural inhomogeneity in the solutions. Both the peak and slow mode disappeared by addition of NaCl or excess HCl into the solutions due to the screening of electrostatic interactions. The G1 polymer grafted with longer P2VP chains (Mw∼30,000 versus 5000 g mol) formed a gel on addition of HCl. This result reveals that molecular expansion is more significant for arborescent polymers with longer (Mw∼30,000) linear polyelectrolyte branches, resulting in gelation for ϕ>0.01. Upon addition of NaCl or excess HCl a gel transformed back to a liquid resulted from the screening of electrostatic interactions.