Preparation And Application Of Hyperbranched Polyurethane Fluorinated Polyacrylate

The fuorine-containing polyacrylate occupies the main market of fabric waterproof products by its outstanding hydrophobic and oleophobic performance, stain resistance, solvent resistance and nice weatherability. It can reduce the surface energy of fabric surface significantly, and has efficient outstanding water and oil repellency for the C8 and more over carbon chain of fuorine-containing polyacrylate especially. Plenty of researches and experiments proved that C8 waterproofing agent products contained PFOA/PFOS which were refractory, and bioaccumulative, and they were a threat for human health. As a result, They have already been limited by the European Union and US from 2015. Hyperbranched polyurethanes have a large number of terminal functional groups, and a spatial three-dimensional network structure, and easy to film, And the same time, the fluorine-containing short carbon chain polymer can be degraded, and environmentally friendly and this speciality matchs the trend of green chemistry. Therefore, taking these two factors into consideration, hyperbranched polyurethane fluorinated polyacrylate and waterborne hyperbranched polyurethane fluorinated polyacrylate emulsion were prepared and this wonderful method can solve the problem of C8 waterproofing agent products which were hard to degraded effectively, and having high application value and development prospects. In this paper, the synthesis conditions of the product were discussed, and its properties and application properties were studied. The main contents are as follows.Under the condition of the reaction temperature of 70 ? and the reaction time of 8 h, hyperbranched polyurethane(HPU) with carboncarbon double bond terminated, as performed polymer, was synthesised using HDI, TMP, HEA as raw material. Then,hyperbranched polyurethane fluorinated polyacrylate(HPUFA) was synthesised by solution polymerization with HPU and perfluorinated hexyl ethyl acrylate (C6F), and other acrylate monomers. The structure was characterized by Fourier transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance (NMR). The micromorphology and static contact angle measurement of the treated fabric surface were observed by the scanning electron microscope (SEM) and the static contact angle measuring instrument. The results showed that:the product(HPUFA) had the hyperbranched structure and the branching degree was 0.526; The surface of the fabric treated by HPUFA was covered with a layer of uniform film, when nNCO/nOH was equal to 1.4 and the content of HPUFA was 1.5 gram per one hundred ethyl acetate and the baking temperature of 180 ?, and baking time of 90 s, the static contact angle of fabric with HPUFA treated reached to 137.5°, water repellency reached to 90 points, oil-repellent grade rised up to level 5.Under the condition of the reaction temperature of 70 ? and the reaction time of 8 h, waterborne hyperbranched polyurethane fluorinated polyacrylate emulsion(WHPU), as performed polymer, was prepared after neutralization of triethyl amine, using HDI, TMP, DMBA, HEA as raw material. Secondly, waterborne hyperbranched polyurethane fluorinated polyacrylate(WHPUFA) was prepared by core-shell emulsion polymerization with WHPU and Perfluorinated hexyl ethyl acrylate (C6F), and other acrylate monomers, using ammonium sulfate (APS) as initiator. WHPUFA emulsion appeared to be milky white with blue fluorescence, and the solid content,the viscosity, the conversion rate, the gel rate of emulsion were 19.64%,70 mPa·s,90.16%,1.78%, and emulsion had a good stability. The structure of product was characterized by Fourier transform infrared spectroscopy (FT-IR). The properties of emulsion were analyzed by transmission electron microscope (TEM) and nano particle size analyzer. The micromorphology and static contact angle measurement of the treated fabric surface were observed by the scanning electron microscope (SEM) and the static contact angle measuring instrument. The results showed that:the product(WHPUFA) had the expected structure. TEM demonstrated that the emulsion had obvious core-shell structure, and the average particle size of emulsion was 66.3 nm. The surface of the fabric treated by WHPUFA was covered with a layer of uniform film. When the emulsifier content was 3%?5%, and the content of DMBA was equal to 3%?5%, and the emulsion content was 2 g/100 g water, the static contact angle of fabric with WHPUFA treated reached to 137.5°, and water repellency reached to 90 points, and oil-repellent grade rised up to level 4, and the time of static water absorption was more than 5 h,and could be washed 20 times.