Novel, well‐defined polystyrene with a fluorine cluster end‐capped group: Synthesis, characterization, and surface properties

Abstract

Novel, well‐defined fluorinated polystyrene was synthesized for the first time via the controlled radical polymerization of styrene through a relatively simple process and was characterized with 1H NMR, 19F NMR, and gel permeation chromatography. The surface properties of polystyrene and poly(acrylonitrile‐co‐butadiene‐co‐styrene) films were modified with the obtained polymers. X‐ray photoelectron spectroscopy measurements of the air‐side surface composition of the modified poly(acrylonitrile‐co‐butadiene‐co‐styrene) films showed that fluorine enriched the outermost surface, resulting in fantastic surface properties that came close to those of poly(tetrafluoroethylene). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3853–3858, 2006

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

“…The synthesis of both PS and PI additives using 1CF end capping agent follows well known and previously described methods 52 . PS1CF and PI1CF functionalised additives were prepared with molecular weights from 6,000 -40,000 gmol -1 and molecular weights are 45 reported in Table 1. In the case of PI1CF additives the constant error between target and actual molecular weight was subsequently found to be due to the use of a bottle of initiator which had been contaminated and therefore the concentration of active lithium was less than the 1.4M indicated.…”

“…45 The near-surface concentration of fluorocarbon was determined by Rutherford backscattering (RBS) analysis using an NEC 5SDH Pelletron accelerator. A 1.3 MeV 4 He + beam was brought onto the sample surface at 85 ° (i.e.…”

“…The solution was stirred at room 40 temperature for at least three hours (longer for higher molecular weights) before the addition of THF (25 ml) to the reaction flask by distillation using a CO 2 /acetone bath. Meanwhile, in a 25 ml round bottom flask (part of the same reactor and adjacent to the main reaction flask, 3,4,5-(tri-3- 45 (perfluorooctyl)propyloxy)benzyl bromide (0.58 g, 0.36 mmol, 1.2 equiv w.r.t lithium), purified as described above, was dissolved in 10 ml purified THF. The THF solution of the end capping agent was then cooled in a CO 2 /acetone bath and then decanted into the living polystyrene solution, at -78 o 50 Celsius, which resulted in the instant disappearance of the orange colour.…”

“…The use of fluorinated polymers to deliver these desirable properties is often impractical given their expense and the difficulty in processing such polymers. Poly(tetrafluoroethylene) (PTFE) for example, has a very high 45 melting point (330 o C) and its melt viscosity is such that it cannot easily be processed via melt extrusion or injection moulding. However, since in many cases only the surface layer of a product needs to possess these specific properties, a much more efficient approach involves the use of a relatively 50 cheap commodity polymer to provide the desirable, mechanical bulk properties and modification of the surface to introduce the desired surface properties.…”

“…More recently we have devised a structure for an end functionalised polymer, with the 40 aim of developing the optimal molecular parameters for efficient surface modification when the functionalised polymers are used as additives in low concentrations. The structure is extremely versatile and consists of two distinct components; a multifunctional head group carrying a pre- 45 determined yet low number of fluoroalkyl groups, to which is attached a pendant polymer chain. This pendant polymer chain is intended to play two roles, firstly to provide long term durability for the modified surface through chain entanglement with the bulk sub phase and secondly to 50 compatibilise the highly fluorinated head group with the bulk phase.…”