Facile hydrophobic modification of hybrid poly(urethane-urea)methacrylate aqueous dispersions and films through blending with novel waterborne fluorinated acrylic copolymers

Abstract

Aqueous dispersions of fluorinated particles (PBF) based on copolymers of butyl acrylate (BA) with 2-(perfluorononenyloxyl)ethyl methacrylate (FNEMA), 2,2,3,3-tetrafluoropropyl acrylate (TFPA), and 2,2,3,3,4,4,5,5-octafluoropentyl acrylate (OFPA), respectively, were synthesized by emulsion polymerization in the presence of unfluorinated and fluorinated anionic surfactant binary mixtures. These fluorinated dispersions showed good to excellent colloidal stability, as determined by freeze-thaw, centrifugation, and critical coagulation concentration measurements. Blending of small amounts (1-10 wt%) of PBF latex particles with a waterborne hybrid poly(urethane-urea)-methacrylate (PUUA) resulted in a series of slightly fluorinated modified PUUA (MPUUA) with good film forming properties and low surface energy. The precursor PUUA had been synthesized separately by simultaneous chain extension of a poly(ester-urethane)-diisocyanate with ethylenediamine and soapless free radical polymerization of methyl methacrylate (MMA) swelling the resulting branched or slightly crosslinked poly(urethane-urea) (PUU) self-dispersible ionomer particles. The results of dynamic light scattering and Zeta potential measurements suggest that merging of PUUA and PBF particles and either engulfing or interdiffusion of the incompatible macromolecular phases occurred to some extent already in the colloidal state. Highly hydrophobic films with surface energy as low as 17 mJ/m2 were obtained upon hybridization of PUUA with the FNEMA copolymer. Thermal annealing allowed to minimize the effects of fast surface dynamics leading ultimately to water absorption, and to promote synergistic enhancement of the resulting hybrid film hardness, as required for coating applications

UV-curable waterborne polyurethane coatings: A state-of-the-art and recent advances review

“…There are several methods for preparing UV-WPU coatings, such as physical blending, emulsion polymerization, and the interpenetrating polymer network (IPN)-based technique [26][27][28][29][30]. The most conventional method is to end-chain polyurethane with a single-hydroxyl acrylate or to introduce a double bond from hydroxyl-terminated polybutadiene, or even to incorporate vinyl groups into the polymer [31].…”

Synthesis of cross-linkable fluorinated core–shell latex nanoparticles and the hydrophobic stability of films

“…In comparison with the above-mentioned fluorinated polymers, latex nanoparticles constructed with a non-fluorinated polymer core surrounded by a thin layer of fluorinated polymer exhibit outstanding advantages. [18][19][20][21][22][23][24][25]. In this way, in course of film-formation, the fluorinated moieties in the shell are conductive to enrich on the surface whereas the non-fluorinated chains in the core coalescence and remain in the bulk so that very hydrophobic surface can be obtained by only small amount of fluorine content in the polymer, which is a significant merit for a practical application taking account of that fluorinated monomers are usually very expensive.…”

Synthesis of a Waterborne Polyurethane-Fluorinated Emulsion and Its Hydrophobic Properties of Coating Films

“…Waterborne polyurethanes (WPUs) emulsion is a nontoxic material with excellent adhesion, good chemical resistance, outstanding flexibility, and high weather resistance, − and it has been widely applied in the adhesive for fabrics, metals, wood, and coating materials, particularly in the field of coating. − In order to disperse or dissolve in water, most WPUs contain ionic groups in their molecular structure. Unfortunately, dried WPUs films are generally hydrophilic because of the presence of ionic groups, which limits the application of WPUs as hydrophobic materials. , Moreover, the WPUs are deficient in both chemical resistance and mechanical property.…”