Multi-end functionalised polymer additives synthesised by living anionic polymerisation—the impact of additive molecular structure upon surface properties

Numerous applications require specific properties at polymer surfaces that differ from the bulk. Herein we describe the novel synthesis of a series of multi-end functionalised poly(styrene) and poly(isoprene) additives carrying 1 to 3 fluoroalkyl (CF) groups. The additives were prepared by endcapping the living chain ends of polymers prepared via living anionic polymerisation. The resulting polymers have been used as additives to render the surface of polymer films hydrophobic/lipophobic and we have characterised these polymer films using static contact angle measurements with water as the contact fluid. We have found that the additive molecular weight, the number of CF groups, additive concentration and annealing conditions have a significant impact upon the resulting surface properties. Increasing the additive concentration and/or number of CF groups resulted in higher contact angles whereas increasing the molecular weight of additive reduced contact angles and surface hydrophobicity. It has been discovered that these additives undergo rapid adsorption to the surface of a thin film in the time taken to produce the film by spin coating and the result is significantly enhanced surface properties. Annealing polystyrene films above the glass transition temperature revealed some interesting behaviour in so much that it demonstrated that on many occasions it is preferable to anneal films containing very small quantities of additive rather than to simply add greater quantities of additive. In addition to contact angles measurements, Rutherford backscattering (RBS) analysis has been carried out on examples of modified poly(isoprene) films to quantitatively analyse the effect of additive molecular weight and number of fluoroalkyl groups on the near surface elemental composition of the modified thin films and confirming the relationship (described above) between these additive molecular parameters and surface adsorption. Finally, we have described a model which compares the behaviour of the additives in thin films to surfactants in solution.