Waterborne UV-curable comb-shaped (meth) acrylate graft copolymer containing long fluorinated and/or polysiloxane side chains

A series of waterborne UV-curable comb-shaped (meth) acrylate graft copolymers containing long fluorinated and/or siloxane side chains were synthesized by conventional radical copolymerization of a novel mono-methacryloyloxy terminated fluorinated macromonomer (PHFA-GMA) and/or polysiloxane macromonomer (SiOHMAC) with (meth) acrylate monomers. The separate effects of PHFA-GMA and SiOHMAC, as well as the synergic effect of these two components, on the properties, especially the surface properties were investigated in detail. A hydrophobic surface could be obtained with extremely low content of PHFA-GMA and/or SiOHMAC due to the strong tendency of the macromonomers to migrate towards the outmost layer, resulting in abundant enrichment of fluorine and silicon atoms on the surface. XPS (X-ray photoelectron spectroscopy) results revealed that for a given weight of the two macromonomers, Si atomic concentration of the copolymer modified by SiOHMAC is higher than F atomic concentration of the copolymer modified by PHFA-GMA. AFM (atomic force microscopy) images showed that surface of the copolymer modified by SiOHMAC is rougher than that modified by PHFA-GMA. Compared to PHFA-GMA, SiOHMAC had higher efficiency and effectiveness in creating hydrophobic surfaces. In addition, the influence of PHFA-GMA and/or SiOHMAC on the physical properties, such as water dispersion particle size, water absorption, pencil hardness, adhesion, mechanical properties and thermal properties were also investigated. The novel comb-shaped copolymers prepared via conventional radical polymerization not only had excellent properties but also have potential applications in large scale industrialization.