致 谢
寒来暑往，时光飞逝。不知不觉间，我的研究生生涯也走到了最后。值此论文完成之际，首先向我校内校外两位导师刘春华副教授和湖南晟通科技纳米新材料有限公司总经理董其宝老师致以我最衷心的感谢。在过去的两年半中，两位老师渊博的知识、活跃的思维方式和严谨务实的科研态度让我崇敬不已，他们对待科学工作的真诚热情和生活态度上的乐观豁达更让我从中受益匪浅！在此真心感谢两位老师在两年半间对我的教诲、关心和鞭策。
感谢实习期间陪伴我的湖南晟通科技纳米新材料的同事：王芳、夏杰、吴正龙、杨凯、李韬、谭莉萍等。实习期间大家一起为共同目标努力，创造出了良好积极的工作氛围，一起为产品的研发和生产而奋斗。感谢你们在一年半间的陪伴和帮助。
感谢理化楼的课题组成员：米炎鑫、翟松涛、王渴、唐开菊、吴成高等对我的关心帮助。学校期间大家和谐相处，互帮互利，使我最后的校园时光充满回忆。 感谢我的室友汪玉辛、方文超和朱明生。研究生期间分配到一个寝室也是缘分，感谢在生活和学习上提供的帮助与鼓励。
在合肥工业大学的七年的学生生活是我人生中最重要的成长经历。感谢母校对我教育与培养，感谢求学期间所有给予我帮助与鼓励的同学和老师。 最后感谢我的父母在读研期间的支持与鼓励，没有你们我走不到这一天，希望日后能与你们一起继续幸福快乐的生活。
求学生涯即将告一段落，希望在和大家继续努力共同开创美好的未来。
作者：张驭 2016年3月
摘 要
氟碳化合物因其出色的低表面能、高热稳定性和高化学惰性等优良性质，使其在低表面能涂料领域取得了广泛的应用。随着人们对氟碳低表面能涂料研发的深入，人们发现氟碳化合物的分子结构对涂料的表面性能有着很大的影响。只有含氟碳原子数大于等于8的长链氟碳化合物才能达到较好的表面性能，但长链氟碳化合物具有难降解、生物累积毒性高和环境危害大的缺点，其使用范围已逐渐受到限制。在这种情况下，氟碳化合物的另一重要成员全氟聚醚，因为其生物可降解和累积毒性低的天然优势，使其成为可以取代传统氟碳化合物的理想材料。 本论文主要旨在研究全氟聚醚在低表面能涂料上的应用，重点考察了不同间隔基基团对涂层表面疏水疏油性能的影响。研究工作由以下几部分组成：
（1）设计思路制备了4种不同间隔基结构的全氟聚醚硅烷：FA-1、FA-2、FA-3及FA-4。通过傅里叶红外测试仪表征所得产物的结构。将所合成的全氟聚醚硅烷应用于手机玻璃抗指纹涂料，均匀涂布在手机触屏玻璃上，通过热固化方式成膜，着重考察了不同间隔基结构、不同固化温度、不同分子量和不同稀释浓度对其疏水疏油性能的影响。所合成的PF-1、PF-2、PF-3、PF-4在150 ℃烘烤下水接触角分别为109°、94°、112°、110°，正十六烷接触角分别为58°、58°、68°、64°，均表现出了较好的疏水疏油性能。其中PF-3与PF-4在25℃常温条件下也能达到较高的疏水疏油角，分别为105°、100°和55°、59°。说明分子内极性大小、间隔基结构长短和苯环刚性基团都对全氟聚醚硅烷的自组装过程有促进作用。同时固化温度升高、分子量增大和浓度升高也能提高全氟聚醚硅烷固化膜的疏水疏油性，但也带来了成本升高和膜层表面质量下降等问题。
（2）设计合成了两种全氟聚醚丙烯酸酯和全氟聚醚苯乙烯两种不同间隔基单体。将所合成的全氟聚醚单体应用到一种用于聚酯薄膜抗指纹的光固化涂料中，通过测试薄膜涂层的水接触角和抗指纹能力，比较不同间隔基结构、含氟链段长短和含氟单体含量等对性能的影响。全氟聚醚丙烯酸酯、全氟聚醚苯乙烯两种结构单体制成的光固化的薄膜疏水角最大为104°和112°，抗指纹等级最佳分别为B、A。由实验实验数据可知，含苯环结构的的全氟聚醚苯乙烯单体制得的光固化薄膜具有更佳的疏水性和抗指纹能力，六聚全氟聚醚单体固化薄膜展现出了更加的疏水性与抗指纹性，这是因为含氟链段长度增加，其涂层表面含氟量增加。说明全氟聚醚链段长度对膜层的疏水疏油也有较大影响。
关键词：全氟聚醚；间隔基；疏水疏油；自组装
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ABSTRACT
Fluorocarbons is widely used in low surface energy coatings because of their excellent properties such as low surface free energy, high chemical inertness and high thermal stability, etc. With the development of the fluorocarbon coatings with low surface energy, it is found that the molecular structure of fluorocarbon has a great influence on the surface properties of the coatings. Only fluorocarbons(CnF2n+1, n≥8) with long chain can achieve the sufficient surface properties, but long chain fluorocarbons have some fatal defects, ie, hardly degradable, bioaccumulation , high toxicity and environmental hazards, so its scope of application have been restricted in these years. In this case, another important members，i.e.， the fluorocarbon compound perfluoropolyethercan replace the traditional fluorocarbons because its biodegradable and low cumulative toxicity. The aim of this paper is to study the application of the perfluoropolyether in the low surface energy coatings, and the effect of different spacer groups on the performance of hydrophobic and hydrophobic property of the coating. The main works is described as follows:
(1) Four different spacer group of perfluoropolyether silane was prepared: FA-1, FA-2, FA-3 and FA-4. The structure of the product was detected by FT-IR. Then，theresultant product were used as anti-fingerprint coatings on the mobile phone touch screen glass. After thermal curing, the effect of the different spacer groups, curing temperature,
the
molecular
weight
and
the
concentration of
the
coating on hydro-oleophobic performance of the film were investigated.The water contact angle of PF-1, PF-2, PF-3, PF-4were 109°, 94°, 112°, 110°and thehexadecane contact angle were 58°, 58°, 68°, 64°, repectively. All those coating film have good hydrophobic and oleophobic properties. additionally, the film of PF-3 and PF-4 which was cured at room temperature(25℃) also has a great hydrophobic and oleophobic properties, their water contact angle were 105°, 100° and their hexadecane contact angle were 55°, 59°. It is found that the molecular polarity, the spacer group and the rigid group have the huge impact on the self assembly process of the perfluoropolyether silane. And the increase of temperature, the increase of molecular weight and the increase of the concentration of the total fluorine can improve the hydrophobic and oleophobic properties, but also reduce the surface quality of the film. (2) Synthesis of two different types of monomers: the fluorinated polyether styrene and the fluorinated polyether acrylate, and let these perfluoropolyether monomers used
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in UV curing anti-fingerprint coatings for the polyester film. By testing the water contact angle and fingerprint resistant ability of the film coating to compare different spacer group, containing fluorine chain length and fluorinated monomer content on the properties of impact. Two monomers’ film coating’ water contact angle up to 104° and 112° and the best level of anti fingerprint were B, A. The experiment datas were shown that, containing perfluoropolyether styrene monomer UV-cured film has better performance, and perfluoropolyether’s hexamer monomer cured film showed better hydrophobic and fingerprint resistance. This is because the fluorine chain length increases, the surface coating’s fluorine content increased. The perfluoropolyether chain length also affected the the hydrophobic and oleophobic properties.
Keywords: perfluoropolyether; spacer group; hydrophobic; oleophobic; self-assemble
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