PPEN-b-FPSO嵌段共聚物合成及其疏水涂层的初探

SYNTHESIS OF HETEROCYCLIC POLY( PHTHALAZINONE ETHER NITRILE)-FLUORIDE POLYSILOXANE BLOCK COPOLYMERS AND THEIR HYDROPHOBIC THIN FILMS

以4-(4-羟基-苯基)-2H-二氮杂萘-1-酮(DHPZ)和2,6-二氟苯腈(DFBN)为反应物,通过芳香亲核取代反应合成数均分子量为3000的羟基封端的聚芳醚腈(PPEN-OH),再经二丙烯基醚化和硅氢加成反应合成桥连型硅氧烷产物(PPEN-Si),进而与二苯基硅二醇和十七氟癸基三甲氧基硅烷进行异官能团缩合反应,制备出含芳环桥连结构的氟硅杂化材料(PPEN-b-FPSO).考察了反应温度、反应时间等因素对各阶段反应的影响,并采用FTIR,1H-NMR和19F-NMR对结构进行表征,证明结构正确.以PPEN-b-FPSO为基体,添加50%氟硅烷修饰的纳米二氧化硅初步制备超疏水涂层.采用扫描电子显微镜测试涂层表面形貌,发现涂层表面具有微纳米级的粗糙结构,用光学接触角测量仪测试其水接触角最大为159°,表现出较好的疏水性能,涂膜的附着力为一级.

The poly（ arylene ether nitrile） s containing phthalazinone moiety end-capped by hydroxyl group（ PPEN-OH） were successfully synthesized by the nucelophilic displacement reaction of the bisphenol-like monomer,4-（ 4-hydroxyphenyl）-phthlazin-1（ 2H）-one（ DHPZ） and 2,6-difluorobenzonitrile（ DFBN） using tetramethylene sulfone as solvents and K2CO3as catalyst at 190 ℃ with stirring for 5 h. Then the reaction of PPEN-OH and allyl bromide in the presence of tetramethylene sulfone as solvent was carried out,following the hydrosilylation of methyltrimethoxysilane with the solvents of tetrachloroethane and the catalyst of 4-Pt at105 ℃ with stirring for 23 h to get trimethoxysilane endcapped PPEN（ PPEN-Si）. Then the fluorine silicone hybrid material（ PPEN-b-FPSO） was prepared from triethoxy-1H,1H,2H,2H-tridecafluoro-n-octylsilane,PPEN-Si and diphenylsilanediol using N-methyl-pyrrolidone as solvents and barium-hydroxide monohydrate as catalyst at room temperature with stirring for 36 h. The effects of reaction temperature and reaction time on the yield of target product were investigated. The structures of copolymers obtained were comfirmed by FTIR,1HNMR and19F-NMR,respectively. The film was fabricated from the SiO2modified by（ heptadecafluoro-1,1,2,2-tetradecyl） trimethoxysilane and the resulting PPEN-b-FPSO at the weight ration of 1 ∶ 1. The thin film was dried under vacuum at the fixed temperature procedures. The surface morphology of the thin film was observed using scanning electron microscope. The film presented micro-nano rough microtextures. The contact angle of the film observed directly by DSA 100 was up to the maximum of 159°. The adhesion of the film was one grade by QFZ adherometer. The results indicate that this hydrophobic coating is a prospective candidate for the application of aviation,building,environmental protection and so on.