Self‐crosslinking borate anions for the production of tough UV‐cured polyelectrolyte surfaces

Abstract

The first anion with four polymerizable groups has been synthesized and used to produce durable, crosslinked polyelectrolyte (PE) coatings in a single step. Sodium tetrakis(4‐vinylphenyl)borate (NaBSty4) was produced by the reaction of BCl3 and the Grignard of 4‐bromostyrene. The full series of borates NaBPhxSty4−x, x = 1−3, were also synthesized analogously by reaction of the styryl‐Grignard and PhBCl2, Ph2BCl, or Ph3B. Anion exchange of the borates with tributyl 4‐vinylbenzylphosphonium chloride gave a family of organic salts developed for applications in photopolymerized coatings. The percent UV cure of the polymer films was determined by infrared spectroscopy and this relative level of curing was corroborated by differential scanning calorimetry analysis. The degree of crosslinking imparted to the polymer films by the different monomers has resulted in varied mechanical properties, which were probed by diamond tip scratch tests and nanoindentation. These clearly demonstrated that as the number of polymerizable groups increased, the film hardness increased correspondingly. The final hardness of the films exceeds those of other related systems and identifies styryl borates as viable crosslinking additives in UV curable technologies, especially in the production of durable PE films. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

Synthesis, properties, and antibacterial activity of polyphosphonium semi-interpenetrating networks

“…27 By tuning the chemical structure of the phosphonium monomer, counterion, and cross-linker, it has been possible to readily tune properties such as coating hardness, hydrophobicity, swellability, and ion exchange rate. [28][29][30] The deposition of gold nanoclusters through ion exchange was also explored. 31 To the best of our knowledge, there are only two prior reports of SIPNs incorporating polyphosphoniums.…”

Fluorinated polymerizable phosphonium salts from PH3: Surface properties of photopolymerized films

“…By manipulating the molecular architecture around the phosphonium centre, both the physical and chemical properties can be varied. Our research focus in this context includes chemical functionality of the phosphonium cation for hydrophobic performance, and synthetic tunability of the counter anion to alter material hardness . Recently, there has been a growing interest in using phosphonium salts in polymerizable systems.…”

“…Much of the work of Long and coworkers in this context is based on thermal polymerization methodologies with the synthesis of various phosphonium homopolymers and copolymers. We are interested in applying similar monomers to polymer networks synthesized using photoinitiated processes . Despite the rich chemistry of phosphorus and ease with which it can be manipulated, the utility of the polymerizable phosphonium salt has not been widely exploited within photopolymer applications…”

Recent Advances in the Synthesis and Applications of Organoborane Polymers

“…Highly cross-linked films were generated by photoinitiated polymerization of styryl-functionalized phosphonium borate salts (Fig. 20) [157]. With an increasing number of styrene moieties in the phosphonium borates, the polymer films became harder and more scratch resistant, indicating the tunability of the material properties by simple structural modifications.…”