【作者】 李文娟；

【导师】 王忠刚；

【作者基本信息】 大连理工大学 ， 高分子化学与物理， 2008， 硕士

【摘要】 含氟材料由于存在键能很高的C-F键,且氟原子在高聚物中所起到的高度屏蔽效应和空间位阻作用,使其具有非含氟聚合物所不具备的优异性能,如化学稳定性、低表面能（耐水性、耐油性和耐沾污性）等。传统的氟烯烃树脂如聚四氟乙烯存在成本高和难加工等缺点,本文通过分子设计,合成了系列不同氟含量的聚酯,研究了其化学结构以及氟含量变化对表面性能的影响。本文以全氟辛酸、乙醇胺为原料,合成了全氟单体N-羟乙基全氟辛酰胺,通过红外光谱和质谱等方法对其化学结构进行表征。再以全氟单体为封端剂,和苯二甲酸二甲酯,1,4-丁二醇反应,钛酸四丁酯为催化剂,合成了一系列不同氟含量的线型聚对苯二甲酸丁二醇酯（FPBT）,通过红外光谱对其化学结构进行表征,并测试了聚合物的水接触角。结果显示随着氟含量的增加,水接触角显著增大。表明氟含量的增加大幅度降低了材料的表面能,提高材料的疏水疏油能力。以间苯二甲酸二甲酯,1,4-丁二醇,全氟单体为原料,钛酸四丁酯为催化剂,合成了一系列不同氟含量的线型聚间苯二甲酸丁二醇酯（FPBI）。通过红外光谱、表面全反射红外光谱、X射线衍射分析及X射线光电子能谱对其化学结构、聚集态结构和表面化学性质进行了表征。研究表明:氟元素在薄膜表面富集,且从表面至薄膜内部呈梯度分布。随着氟含量的增加,水接触角逐渐增大,表面能降低。当氟含量为10mol%时,表面能为15.07mJ/m²,低于聚四氟乙烯的表面能22mJ/m²,通过加入少量氟单体就可以大幅度降低材料表面能,提高材料的疏水疏油性。实现了分子设计的目的。以季戊四醇,间苯二甲酸二甲酯,1,4-丁二醇和全氟单体为原料,钛酸四丁酯为催化剂,季戊四醇为支化中心,合成了一系列不同氟含量的多羟基超支化聚酯（HBFP）。通过红外光谱对其化学结构进行表征,用乙酸酐—吡啶法测其羟值在27-107mg/g之间。通过核磁共振碳谱(¹³C-NMR)对其支化度进行表征,并以二异氰酸酯为固化剂,采用DSC方法对其固化行为进行了研究。结果表明该固化反应为一个复杂反应,近似一级反应。反应表观活化能（E_a）为158.67kJ·mol^-1,频率因子（A）为2.25×10¹⁵,反应级数（n）为0.95。可以为同类多羟基聚酯固化成型工艺提供依据。更多还原

【Abstract】 Fluorinated materials have excellent performance such as chemical stability, water resistance, oil resistance and pollution resistance etc. However, the high fluorine content （76 % fluorine content for PTFE） results into the traditional fluorinated polymers high cost and poor processability. Fluorinated polymers possessing both low fluorine content and low surface energy are desirable for broadening their application field. In an effort to overcome the above drawbacks, the present work was carried out to synthesize a series of polyesters with different fluorine content. Their chemical structure and surface properties were investigated.Fluorinated monomer N-hydroxyethyl perfluorooctanamide （HPFOA） was synthesized from perfluorooctanoic acid （PFOA） and ethanolmine. Its chemical structure was confirmed by FTIR, Mass spectroscopy and metling measurement methods.Fluorinated Polybutylene terephthalates （FPBT） containing different content from 0% to 10% were synthesized from dimethyl terephthalate, 1,4-Butanediol and N-hydroxyethyl perfluorooctanamide（HPFOA）, using tetrabutyl titanate as catalyst. Their chemical structures and surface properties were examined through FTIR, DSC and water contact angle measurement etc. The effects of fluorine content on surface properties of FFPBT films were discussed. The results showed that surface energies of FPBT decreased evidently with the increase of fluorine content.Fluorinated polybutylene isophthalates （FPBI） containing different fluorine content were synthesized from dimethylisophthalate, 1,4-Butanediol and N-hydroxyethyl perfluorooctanamide, using tetrabutyl titanate （TBT） as the catalyst. Their chemical structures and surface properties were investigated by FTIR spectroscopy, attenuated total reflection FTIR spectra （ATR-FTIR）, X ray photoelectron spectroscopy （XPS） as well as water and hexadecane contact angle measurement methods. The results showed that the fluorine-containing groups could migrate and enrich on the surfaces. When the fluorine content was 10 mol%, the calculated surface energy was 15.07 mJ/m² which was lower than polytetrafluorethylene （22 mJ/m²）, exhibiting excellent water and oil repellency.A series of hyperbranched fluoropolymer（HBFP） which contained different fluorine content were synthesized from pentaerythritol, dimethylisophthalate, 1,4-butanediol, N-hydroxyethyl perfluorooctanamide, using tetrabutyl titanate as the catalyst. The hydroxyl values of HBFPs, which was determined by acetic anhydride-pyridine method, were 27-107mg/g. The chemical structures were confirmed by FTIR spectroscopy. The degree of branch was regulated by the pentaerythritol content and determined by ^13C-NMR. Their curing kinetics was studied by DSC using diisocyanate as curing agent. The curing kinetics parameters, including the activation energy, frequency factor and reaction order were calculated with Kissinger and Crane methods. Their values were 158.67 kJ /mol, 2.25×10¹⁵ and 0.95, respectively. The results show that the curing reaction was complex reaction, closing to the first order reaction. The experiment provides reference to curing process of identical polyhydroxy hyperbranched polyester.更多还原