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Effect of shear on intramolecular and intermolecular association during cross-linking of hydroxyethylcellulose in dilute aqueous solutions.

Intramolecular and intermolecular associations of dilute aqueous alkali solutions of hydroxyethylcellulose (HEC) in the presence of a chemical cross-linker agent (divinyl sulfone, DVS) are studied with the aid of dynamic light scattering (DLS) and rheological methods. At quiescent state, DLS detected only interchain aggregation of HEC during the cross-linker reaction, and the magnitude and start of this effect depend on the cross-linker concentration. The growth of clusters has been investigated at various stages in the course of the cross-linking process by quenching the reaction mixture to a lower pH. After quenching, no further association of the species occurred. When the dilute reaction mixtures are subjected to shear, intrapolymer cross-linking with contraction of the molecules is observed, and at moderate shear rates this effect is followed by interpolymer cross-linking and the formation of aggregates at longer times. The rate of the growth of the multichain aggregates decreases with increasing shear rate, and at sufficiently high shear rates no cross-linking effect is observed. Depending on the shear rate, the aggregates continue to grow until they reach a certain size where an incipient breakup of interaggregate chains can be observed. The delicate interplay between intramolecular and intermolecular association effects is governed by factors such as the magnitude of the shear rate, polymer concentration, and cross-linker density.