Synthesis And Application Of Polyurethane Modified Fluorinated Polyacryl Late

The fabric finishing agents with long fluorocarbon chain had harmful to the environment and human,and they also had high cost.As the alternatives of long fluorocarbon chain, the fluorine polymers with short fluorocarbon chain also had low surface energy properties such as water repellency, but the property was less better. In order to increase the hydrophobicity and oleophobicity of short fluorocarbon chain containing polymers and to reduce production costs, the polyurethane segment containing a polyether group was embedded into the short fluorocarbon chain containing polymers. Based on this, using of molecular design principles, a series of polyurethane modified fluorinated polyacrylate finishing agents were designed and synthesised. Some factors infulencing the stability of polymerzation and revelent properties of polymerzation were systematically investigated. Then, the the as-prepared productions were applied in the textile finishing, and also film morphology as well as the cotton surface’s performance properties were researched.The main work are listed as follows:(1) A polyurethane modified fluorinated polyacrylate(PUAF) was prepared with 2-(perfluorohexy) ethyl acrylate(C6F) and the carbon-carbon double terminated polyurethane prepolymer(PUA)which was obtained by reaction of isophorone diisocyanate(IPDI), polyethylene glycol(PEG) and hydroxypropyl acrylate(HPAA) in the presence of azobisisobutyronitrile as a radical polymerization initiator. The chemical structure, film morphology and application performance of PUAF were studied by infrared spectroscopy(IR), nuclear magnetic resonance(1H-NMR), field spectrum scanning electron microscopy(FE-SEM), and atomic force microscopy(AFM), etc.PUAF could form a smooth resin film on the treated fabric surface under FE-SEM observation. Some peaks and lots of protuberances on that film appeared and surface was rough with AFM observation. The contact angle of water on those substrates could increase to 144.5°. And when the dosage of PUAF in solution was 1g in 100 g ethyl acetate, and the polyester fabric was treated by PUAF and then dried at 180 ℃in 1.5 min, the hydrophobicity of the treated fabric could reach 90, meanwhile the oil-repellent grade reached grade 6.(2) Aqueous polyurethane crosslinker(PUM) was synthesized by stepwise polymerization of isophorone diisocyanate(IPDI),polyethylene glycol(PEG), triethanolamine(TEOA) and ethyl methyl ketone oxime(MEKO). The fluorinated polyacrylate emulsion(FPA) was synthesized by emulsion polymerization of 2-(perfluorohexy)ethyl acrylate(C6F), hydroxypropyl acrylate(HPAA), octadecyl methacrylate(SMA) and 4-Chloromethyl styrene(CMS), in the presence of ammonium persulfate(APS) as an initiator. By mechanical stirring, PUM and FPA emulsions were mixed evenly. These two kind of emulsions were physical blended at room temperature. When the temperature was above 120 ℃, the blocked-NCO groups unsealed from polyurethane, had an addition reaction with-OH of fluorinated polyacrylate, to form a cross-linked structure. So an aqueous polyurethane modified fluorinated polyacrylate(PUMF) was obtained.The performance properties of the latex and its film were characterized by FE-SEM, TGA, IR, and 1H-NMR, etc.The IR and 1H-NMR confirmed the structure of the as-prepared product. The thermal stability of PUMF showed some improvement compared to the FPA. PUMF could form a smooth resin film on the treated fabric surface under FE-SEM observation. The treated fabric by using the concentration of PUMF as 1.25 g/100 ml H2 O and 2.5% PUM had the favorable water repellency and touching feeling. After baked at 100 ℃ in 5 min and stamped at 180 ℃ in 2 min, its static water contact angle could reach 146.9°, the hydrophobicity of the treated fabric could reach 90, meanwhile the oil repellency grade reached grade 6.(3) A novel polyurethane modified fluorinated polyacrylate emulsion(WPUAF) was obtained by the polymerization of octadecyl methacrylate(SMA), 4-Chloromethyl styrene(CMS), 2-(perfluorohexy) ethyl acrylate(C6F), and polyurethane prepolymer terminated by hydroxypropyl acrylate. Various of factors that had effect on the emulsion polymerization was investigated. The emulsions component structure and particle size distribution was characterized by IR and nano-emulsion particle sizer. And the application effect of the fabric’s surface treated by emulsion was researched and analysised. Finally, FE-SEM was used to observe the surface morphology of finishing fabric.The results showed that: the emulsion was white with a blue fluorescent appearance. The better reaction conditions were that: the amount of emulsifier was 5%, and the concentration of APS caused by 0.9% to 1.1%. The gelation rate and conversion ratio was 2.62% and 93.3% under the optimum reaction conditions. WPUAF had the expected structure under IR characterization. The results measured by nanoparticle size analyzer showed that: the particle size distributed evenly, and the average particle size was 132.7 nm. With FE-SEM’s observation, the fabric surface by using the concentration of WPUAF as 3 g/100 ml H2 O was covered with a smooth resin film. While baked at 100 ℃ in 5 min and shaped at 180 ℃ in 2 min, its static water contact angle can reach 136.9°, the hydrophobicity of the treated fabric could reach 90, meanwhile the oil-repellent grade reached grade 6. After washed 10 times, finishing fabric’s hydrophobicity was 80 points, the oil-repellent grade reached grade 5.