Preparation and Properties of Fluorinated Block Acrylate Polymer／Epoxy Self-Stratifying Coatings
Ge Panfeng1， Ren Qiang1， Bian Jianhua2， Fang Jianbo1， Deng Jian1， Li Jian1
1. Jiangsu Key Laboratory of Environmentally Friendly Polymeric Materials， School of Materials Science and Engineering， Changzhou University， Changzhou，Jiangsu 213164， China；
2. Shanghai Zhenhua Heavy Industry Changzhou Coating Co.， Ltd.，Changzhou，Jiangsu 213164， China
Abstract: A series of diblock copolymers，poly （butyl methacrylate-co-glycidyl methacrylate）-b-poly-dodecafluoroheptyl methacrylate（P（BMA-co-GMA）-b-PDFHMA，BGF），containing fluorinated acrylates and glycidyl methacrylate （GMA） polymer with controlled structure were synthesized by means of the initiators for continuous activator regeneration atom transfer radical polymerization （ICAR-ATRP）. The diblock copolymers was mixed with epoxy resin to prepare self-stratifying coatings. When the 10％ content of fluorine-containing resin having a number average molecular weight of 53k-b-23k and GMA content of 20％ was added， fourier transform infrared spectroscopy （FT-IR） and energy dispersive spectrum-electron scanning microscopy （EDS-SEM） testing revealed that parts of fluorinated acrylate blocks migrated to the surface of coating. Fluorine element of the film had good self-migration effect， and the fluorine content in the surface layer reached more than 20％. The increasingly introduction of GMA could further restrict the migration of fluorine-containing resin. UV resistant testing indicated that gloss retention rate of self-stratifying coating is much higher than the pure epoxy coating. The resistance to yellowing perforamance is not changed obviously. Water contact angle and salt spray testing revealed that addition of 10％ diblock copolymer could increase the water contact angel to above 100°. The anticrrosive performance of all self-stratifying coatings were improved. Blistering was surpressed effectively. The basic mechanical properties of the coating film was not affected when the addition of diblock copolymer was less than 4％， but the gloss was decreased.
FUNKE W.Preparation and properties of paint films with special morphological structure[J].Journal of the Oil and Colour Chemists Association, 1976, 59(11):389-403孙培勤， 孙绍晖， 刘大壮.自分层涂料的机理和研究现状[J].涂料工业, 2005, 35(2):54-57孙培勤， 常静， 孙绍晖， 等.环氧树脂与丙烯酸树脂的自分层行为研究[J].涂料工业, 2008, 38(2):13-16李金凤， 刘立柱， 张笑瑞， 等.三层“核-壳”型环氧-丙烯酸酯乳液的合成及其室温固化反应[J].涂料工业, 2015, 45(3):24-28LANGER E， KUCZYN＇SKA H， KAMIN＇SKATARNAWSKA E， et al.Changes of solubility parameters during evaporation of solvents as a factor influencing the self-stratification of epoxy／acrylic systems[J].Progress in Organic Coatings, 2009, 66(3):228-234LANGER E， KUCZYN＇SKA H， KAMIN＇SKATARNAWSKA E， et al.Self-stratifying coatings containing barrier and active anticorrosive pigments[J].Progress in Organic Coatings, 2011, 71(2):162-166BEAUGENDRE A， DEGOUTIN S， BELLAYER S， et al. Self-stratifying epoxy／silicone coatings[J]. Progress in Organic Coatings，.[J].，103：, 2017, :101-110.-BAGHDACHI J， PEREZ H， TALAPATCHAROENKIT P， et al. Design and development of self-stratifying systems as sustainable coatings[J]. Progress in Organic Coatings，.[J].，78：, 2015, :464-473.-YAGCI M B， BOLCA S， HEUTS J P A， et al.Self-stratifying antimicrobial polyurethane coatings[J].Progress in Organic Coatings, 2011, 72(3):305-314BEAUGENDRE A， DEGOUTIN S， BELLAYER S， et al. Self-stratifying coatings： A review[J]. Progress in Organic Coatings，.[J].，110：, 2017, :210-241.-WANG X， HU J， LI Y， et al. The surface properties and corrosion resistance of fluorinated polyurethane coatings[J]. Journal of Fluorine Chemistry，.[J].，176：, 2015, :14-19.-