Multihydroxyl End Functional Polyethylenes: Synthesis, Bulk and Interfacial Properties of Polymer Surfactants

Abstract

Multihydroxyl end functional polyethylenes have been prepared with controlled molecular weight, microstructure, and functionalization. These materials, designed as interfacially active blend additives for polar interfaces, are thermally stable up to 250 °C and to have similar crystallinity and dynamics to their unfunctionalized homopolymer analogues. The polymers segregated strongly to silicon oxide interfaces, with adsorbed layers forming spontaneously at annealed polymer interfaces, having surface excess concentrations approaching 2Rg and a maximum areal density of approximately 0.6 adsorbed chains per nm2. This interfacial activity is achieved almost without detriment to the bulk physical properties of the polymer as evidenced by thermal analysis, quasi-elastic neutron scattering, and small-angle neutron scattering (SANS). SANS experiments show little evidence for aggregation of the dihydroxyl functionalized polymers in blends with PE homopolymers, which is thought to explain why these additives have particularly strong interfacial adsorption, even at relatively high concentrations. A modest level of segregation of the additives to exposed blend surfaces was also seen, particularly when the additive molecular weight was significantly lower than that of the matrix. We attribute this to a combination of the relatively low molecular weight of the additives and the marginally lower surface energy associated with deuterated polymers.