Molecular weight standards from sulfonation of polystyrene

Abstract

Polystyrene was sulfonated with sulfur trioxide–triethyl phosphate complexes in dichloroethane, the object being to prepare polystyrene sulfonates substantially free of sulfone links between polymer chains. Variations in the sulfone content with reaction conditions were conveniently followed by exclusion chromatography, the sulfone peak appearing at about twice the molecular weight of the main peak. The desired products were obtained from polystyrenes with molecular weights between 1.1 × 105 and 8.7 × 105 by using (at −20 to +25°C) a 5:1 excess of a 1.5:1 complex, the last at a concentration of 0.5M. Completely soluble polystyrene sulfonate was also obtained from polystyrene of molecular weight 2.05 × 106. Requirements for the successful use of the 1.5:1 complex include careful purification of the dichloroethane and, if 2 g or more polystyrene is to be sulfonated, formation of the complex at −20°C. A method is given for measuring the sulfonating capability of the reagent before adding the polymer.

Sulfonation of polystyrene: Toward the “ideal” polyelectrolyte

“…as a scavenger for potassium ions, and personal care products . As a reference material, PSS is an important molecular weight standard . It is one of the few polyelectrolytes that are widely provided as a “fully charged” polymer with precisely known molecular weight and polydispersity.…”

“…Several approaches are available for transforming polystyrene, PS, standards into PSS. These, summarized in Scheme , include sulfonation by concentrated sulfuric acid alone (liquid or vapor), concentrated sulfuric acid with a catalyst, sulfur trioxide, chlorosulfonic acid, silica sulfuric acid, and acetyl sulfate . Catalysts include silver and mercury ions .…”

“…Even sulfur trioxide "softened" by complexation with triethylphosphate, TEP, 28 shows evidence of crosslinking if the ratio of SO 3 to TEP is not correctly adjusted. 7 In the present work, we explore a reliable method for generating fully sulfonated, narrow PDI sulfonated polystyrene and its deuterated analog.…”

Structural Modification of Poly(2,6-Dimethyl-1,4-Phenylene Oxide)

“…(For comparison, the contact angle of a films made from cellulose acetate measured in the same arrangement is 32 "). Hydrophilic modifications of synthetic polymers have found use in membrane applications (Huang et al, 1984a;1984b) and in the synthesis of water-soluble polymers (Brown et al, 1979;Noshay et al, 1976). Examples of hydrophilic modifications of PPO are carboxylation (Chalk et al, 1969;Xie et al, 1984) and sulfonation (Chludzinski et al, 1971;Huang et al, 1984).…”

Synthesis of perfectly sulfonated sodium polystyrene sulfonate over a wide molar mass range via reversible‐deactivation radical polymerization

“…For accurate experimental results, the polymer must be perfectly and completely substituted with sulfonate groups, yet this is not always the case. Whether commercially obtained or synthesized in‐house, NaPSS displays significant variations in purity, stated molecular weights, and polydispersity …”