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Title: Dilute-solution Structure of Charged Arborescent Graft Polymer

Journal Article · · Polymer

The solutions of charged G1 arborescent polystyrene-graft-poly(2-vinylpyridine) copolymers in methanol-d4 and D{sub 2}O were investigated over a dilute concentration range {phi} = 0.005-0.05 ({phi}: 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 (d{sub exp}) calculated from a peak position corresponded to the expected value (d{sub uni}) 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 D{sub 2}O. 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 (M{sub w} {approx} 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 (M{sub w} {approx} 30,000) linear polyelectrolyte branches, resulting in gelation for {phi} > 0.01. Upon addition of NaCl or excess HCl a gel transformed back to a liquid resulted from the screening of electrostatic interactions.

Research Organization:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). High Flux Isotope Reactor (HFIR)
Sponsoring Organization:
USDOE Office of Science (SC)
DOE Contract Number:
DE-AC05-00OR22725
OSTI ID:
1003547
Journal Information:
Polymer, Vol. 47, Issue 8; ISSN 0032-3861
Country of Publication:
United States
Language:
English