含氟聚甲基丙烯酸酯/聚异丁烯嵌段共聚物的成膜性质研究  

Film Properties of Fluorinated Polymethacrylate/Polyisobutylene Based Block Copolymers

作　　者：李森[1] 张明祖[1] 何金林[1] 倪沛红[1] 

机构地区：[1]苏州大学材料与化学化工学部江苏省先进功能高分子材料设计及应用重点实验室,苏州215123

出　　处：《高分子学报》2014年第12期1648-1658,共11页Acta Polymerica Sinica

基　　金：国家自然科学基金项目(基金号21374066;21304061);江苏省基础研究计划(自然科学基金)-滚动(基金号BK2011045);江苏省自然科学基金(基金号BK20130286);中国博士后科学基金(基金号2013M531396);江苏高校优势学科建设工程资助项目

摘　　要：利用氧负离子聚合方法制备含氟聚异丁烯三嵌段共聚物,聚异丁烯-b-聚甲基丙烯酸-2-(N,N-二甲氨基)乙酯-b-聚甲基丙烯酸-(2,2,3,3,4,4,5,5-八氟)戊酯(PIB-b-PDMAEMA-b-POFPMA),对PIB60-bPDMAEMA63-b-POFPMA11的物理化学性质和成膜性能进行了研究.利用1H-NMR和GPC表征了聚合物的化学结构、分子量及分子量分布;通过TGA和DSC测试了聚合物的热分解温度与玻璃化转变温度(Tg).实验结果表明,PIB60以及PDMAEMA63的Tg分别为-61℃和5℃,PIB60-b-PDMAEMA63在-4℃左右存在一个Tg,而PIB60-b-PDMAEMA63-b-POFPMA11不仅在-4℃存在玻璃化转变,而且在26℃存在另一个玻璃化转变,对应于POFPMA嵌段的Tg.将聚合物制成薄膜,通过接触角测试发现聚合物薄膜具有一定的疏水疏油性质.根据Owens-Wendt公式计算了聚合物薄膜的自由能、分散能和极性能.利用原子力显微镜(AFM)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)和X射线衍射分析(XRD)研究了聚合物中含氟嵌段向薄膜表面迁移富集和堆积结构,结果显示,在退火之后,含氟嵌段向薄膜的表面迁移、富集,并在表面排列形成双层堆积结构.Fluorinated triblock terpolymers PIB-b-PDMAEMA-b-POFPMA was synthesized by oxyanioninitiated polymerization and characterized by1H-NMR and GPC.The physicochemical and film properties were studied in detail.Firstly,the thermal decomposition behavior and glass transition temperature（Tg） were studied by thermogravimetric analysis（TGA） and differential scanning calorimetry（DSC）,respectively.These results showed that PIB60-b-PDMAEMA63 have one transition temperature at-4 ℃ due to the compatibility of PIB and PDMAEMA segments,and the triblock terpolymer PIB60-b-PDMAEMA63-b-POFPMA11 have an additional Tgat 26 ℃ which corresponded to the glass transition temperature of POFPMA.Subsequently,the polymeric thin films were prepared by casting polymer / THF solutions on glass slides or PTFE panel substrates.It was found that the triblock terpolymers have a certain hydrophobic and oleophobic properties by contact angle test.The surface free energy,dispersion and polar components were calculated according to Owens-Wendt formulas.The results of AFM,SEM and XPS showed the migration of fluoride part to the surface and accumulation after annealing to minimize interfacial free energy.Ordered structure of fluorinated chains on the surface was studied by XRD.The results of XRD showed that the fluorinated chains would be rearranged to transform into a double-layer packing after annealing.

关 键 词：聚合物薄膜 聚异丁烯 含氟嵌段共聚物 氧负离子聚合 

分 类 号：O631.1[理学—高分子化学]