摘要
润湿是大自然中最为常见的一类界面现象，也是固体表面的重要特征之一，它直接影响着自然界中动、植物的种种生命活动，如科学家在对动植物的表面进行研究时发现，自然界中通过形成超疏水表面来达到自洁功能的现象更为普遍，最典型的例如以莲叶为代表的多种植物叶子的表面(荷叶效应Lotus-effect)、蝴蝶等鳞翅目昆虫的翅膀以及水鸟的羽毛等等，这是大自然对我们的暗示。润湿在人类日常生活与工农业生产中也起着重要的作用，如洗涤、印染、纺织、建筑涂料、矿物浮选、航空航天、传感器以及防污防腐等方面也得到了广泛的应用。
固体表面的润湿性由其化学组成和微观几何结构共同决定。众所周知，润湿性能主要受固体表面化学组成的影响，固体表面自由能越大，就越容易被一些液体所润湿，反之亦然。寻求和制备高表面自由能或低表面自由能的固体表面是制备超亲水和超疏水的先决条件，因此，金属或金属氧化物等高能表面常用来制备超亲水表面，而超疏水表面的制备常需在表面覆盖氟碳链或硅烷链来降低其表面能。
被称为“塑料王”的聚四氟乙烯(PTFE)的表面自由能很低(只有18mN／m)，它具有许多独特的性能，如双疏(疏水、疏油)性、不粘性、耐腐蚀性、自洁性等。具有类似PTFE表面性质的材料同样受到人们的极大关注。国际上对双疏材料的研究始于上世纪50年代初，至90年代末，随着表面研究技术手段的提高和纳米科学技术的不断发展，以及越来越多的行业对特殊表面性能材料的迫切需求，人们对微观结构在生命科学和材料科学中的应用有了更多的认识，对于固体表面微细结构与润湿性之间的关系也有了更为深入的理解。
本论文在前人工作的基础上，制备了新的含氟的疏水、疏油(双疏)材料，具有一定的创新性，对这类新材料的合成进行了初步的探索和研究。
论文共分为四部分：
第一章文献综述
本章对润湿及双疏材料的相关理论，低自由能固体表面的制备技术，制备方法与原理，含氟丙烯酸酯聚合物结构与性能表征，含氟双疏材料的应用研究进展，本课题的提出及设计思路都进行了阐述。
第二章溶液聚合法以全氟辛酸丙烯酯(Ⅰ)为单体合成含氟聚合物
通过一步法合成了单体全氟辛酸丙烯酯(Ⅰ)(实验室合成)，用此单体通过溶液聚合合成了含氟的均聚物，此均聚物涂成的薄膜基本是透明、均一的，有较好的疏水、疏油性。但是合成单体Ⅰ的收率较低，溶液聚合虽然操作简单，但是选用的溶剂三氟甲苯(TFT)对环境有一定的危害，而且聚合物薄膜的制备过程较为复杂，对基底的要求较高。综合考虑以上各因素，本实验在合成含氟聚合物方面，采用溶液聚合的方法进行了一些尝试和探索。
第三章乳液聚合法以2-甲基丙烯酸-β-异氰酸乙酯-4-N-异氰酸乙酯全氟辛酰胺-甲苯(Ⅱ)为主要单体合成含氟三元共聚物乳液
本章以2-甲基丙烯酸-β-异氰酸乙酯-4-N-异氰酸乙酯全氟辛酰胺-甲苯(Ⅱ)(实验室合成)、丙烯酸(AA)、丙烯酸丁酯(BA)为单体，用SDS和OP-10混合乳化剂，选用过硫酸钾(PPS)为引发剂，以水为介质用一次投料法制备了一种新的含氟丙烯酸酯三元共聚物乳液。结果显示，该聚合物乳液具有良好的贮存和离心稳定性，很好的环保性和成膜性，同时将聚合物乳液涂膜后发现，该聚合物膜具有较好的耐腐蚀性和热稳定性，该聚合物膜比较光滑、透明，聚合物乳液的TEM照片中纳米颗粒的存在也证明了这一点。对涂膜进行退火处理后，其双疏性明显增强，因此，该聚合物乳液在材料行业具有潜在的应用前景。
第四章乳液聚合法以全氟辛酸甲基丙烯酰氧基乙酯(Ⅲ)为主要单体合成具有核／壳结构的含氟四元共聚物乳液
本章以全氟辛酸甲基丙烯酰氧基乙酯(Ⅲ)(实验室合成)、丙烯酸(AA)、丙烯酸丁酯(BA)、苯乙烯(ST)为单体，用SDS和OP-10作复合乳化剂，选用过硫酸铵(APS)为引发剂，以水为介质采用半连续乳液聚合法制备了一种新的具有核／壳结构的含氟丙烯酸酯四元共聚物乳液。结果显示，该聚合物乳液具有良好的贮存和离心稳定性，很好的环保性和成膜性，同时将聚合物乳液涂膜后发现，由于聚合物乳液的TEM照片中纳米颗粒的存在使得该聚合物膜光滑、透明，AFM照片也进一步证明该聚合物膜具有优异的双疏(疏水、疏油)性，耐腐蚀性和热稳定性，对涂膜进行退火处理后，其双疏性明显增强，因此，该聚合物乳液的制备为这类新材料的商品化提供了理论依据，有潜在的应用前景。
Wetting phenomenon is one of interface phenomena which are often seen in nature, it is also one of solid surface important features .It can affect some living activity of organisms, such as animal skin and plant's surface, super-hydrophobic and self-cleaning phenomenon are more common in nature. For example, lotus-effect, butterfly' wing and feather of bird. All of those phenomena indicated that wetting plays an important role in everyday life, industry and agriculture production.
Wetting property of solid surface is depended on the surface micro structure and on the chemical composition of outermost surface layer. It is well known that wetting property of solid surface is mainly influenced by the chemical composition of solid surface, the larger the surface free energy, the much moist the solid is, vice versa. Thus, perfluoroalkyi or siliconalkyl chain are utilized in industry for the production of various surface functional chemicals such as hydrophobic or oleophobic material to reduce surface free energy.
We have known PTFE has a very low surface free energy (18mN/m), it has many particular properties, such as water- and oil- repellency, non-sticking, chemical resistance and self-cleaning. The series material is paid attention by people. The research of hydrophobic or oleophobic material began from the middle 1950s, with the development of life science and material technology the deep understanding has been made.
Base on the survey of previous literatures, in the present paper we reported a series novel fluorine-containing hydrophobic or oleophobic material.
The paper is divided into four parts:
Chapter one: A review
This chapter elaborated the relative theory of wetting and hydrophobic or oleophobic material, such as preparing technology of low free energy solid surface, the principle and methods of preparation, the structure and characteristics of perfluoroalkylethylacrylate polymer, the application and progress of fluorine -containing material, the proposition and design of this theme.
Chapter two: syntheses of fluorine-containing polymer with monomer I by solution polymerization.
In this chapter, we synthesize the monomer I by one step, then synthesize fluorine-containing polymer with monomer I . The thin film of polymer is clear and uniform, with being hydrophobicity and oleophobicity. However, the yield of monomer I is not satisfactory. Moreover, the procedure is not simple, concerning harmful solvent TFT.
Chapter three: syntheses of fluorine-containing polymer emulsion with monomer II by emulsion polymerization.
In this chapter, we synthesize a novel fluorine-containing polymer emulsion in water phase by using the monomer II ,MMA, BA as starting material, SDS and OP-10 as emulsifier, and PPS as initiator. The results show that the product has good stability and film-forming property. Meanwhile, the thin film of latex is clear and smooth with good hydrophobicity and oleophobicity, the higher thermal stability and chemical resistance.
Chapter four: syntheses of fluorine-containing polymer with core/shell structure by emulsion polymerization.
In this chapter, a novel fluorine-containing polymer emulsion with core/shell structure was prepared in water phase through a two-stage emulsion polymerization method. That is, using a nonfluorine monomer(BA, ST) as core, and the fluorine-containing monomer III, BA, ST, AA as shell, to create a hydrophobic and oleophobic surface and raise the efficiency of fluorine compared with other particle structures such as random copolymer or latex blending. The final product is a clear, clearness, smooth polymer film coating, indicating the presence of nanophases as shown by TEM. The fluoropolymer latex has good stability and no pollution in surrounding. The surface of polymer film was found to have an excellent hydrophobicity and oleophobicity. At the same time, the outstanding thermal stability, chemical resistance and good film-forming properties were also tested. The film's hydrophobicity and oleophobicity are more strength after annealing, AFM photos have verified it.
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