基于短氟碳链的环氧基自分层低表面能涂层的设计与构筑

Aim at the project for designing and fabricating the epoxy-based coating containing the short-chain fluorocarbons design, the project proposes firstly to design and synthesize the epoxy-based self-stratification coating containing short-chain fluorocarbons. We plan to blend different types of umbrella and comb-like short-chain fluorine-containing polymers with the epoxy resin, after stratification and crosslinking curing, obtaining a kinds of epoxy-based self-stratifying coating material with excellent hydrophobic and oleophobic performance and high adhesion based on self-stratifying effect. On the one hand, the factors, laws and mechanism of the self-stratification effect in the epoxy-based self-stratification coating containing short-chain fluorocarbons are revealed by studying the factors influencing thermodynamics and kinetics during the film-forming process of the epoxy-based self-stratifying coating. On the other hand, based on the design of the umbrella fluoropolymers and comb-like epoxy fluorocarbon and the study on self-stratification performance, the effect of the aggregation effect and space shielding of the fluorine chains on improving the mobility of fluorine-containing chains and surface properties of the coating is in detail investigated, obtaining the influence rules of the type and structure of the short-chain fluorocarbon on the surface properties of the resin. These studies are expected to providing theoretical data for the design and fabrication of the epoxy-based self-stratification coating containing short-chain fluorocarbons, further enriching and developing the theory of self-layered coatings, promoting basic research and application of fluorinated self-stratification coatings and having important implications for solving enviromental pollution problems of fluoropolymers with long fluorocarbon chains.

本项目针对基于短氟碳链的环氧基自分层涂层设计与构筑的课题，提出设计合成具有伞形结构或梳状结构的短氟碳链含氟聚合物，并将其与环氧树脂共混获得基于短氟碳链的环氧基自分层涂料；利用自分层效应使环氧基含氟涂料发生分层，经交联固化，获得具有优异低表面能和高附着力的环氧基自分层涂层材料。一方面，通过对环氧基含氟自分层涂层成膜过程热力学及动力学过程的影响因素的研究，揭示基于短氟碳链的环氧基含氟涂层自分层效应的影响因素、规律及作用机理。另一方面，通过对伞形结构含氟聚合物和梳状结构环氧基氟碳聚合物的设计及对自分层性能研究，详细考察氟链聚集效应和空间屏蔽作用对提高含氟聚合物的迁移性和涂层表面性能的影响，获得短氟碳链类型、结构等对树脂表面性能的影响规律。通过这些研究，有望为短氟碳链的环氧基自分层涂层材料的设计、合成提供基础数据，推动含氟自分层涂层材料的研究和应用，对解决长氟碳链聚合物的环境污染有重要意义。

氟碳低表面能涂料由于其表面能低，作为涂料在金属等基材上存在严重的附着力差的问题，成本也较高；而环氧树脂为基质的环氧涂料对水泥、金属等无机材料具有较强的附着力。同时，现有的环氧涂料为底漆、氟碳涂料为面漆的复合体系，由于氟碳涂料与环氧涂料的层间附着力较差，难于解决氟碳低表面能涂料的附着力难题。因此，本项目在低表面能涂料中引入自分层效应，利用低表面能氟碳树脂与其他表面能较高且与基材附着力好的树脂共混，这样不仅可以很好的解决单独使用低表面能涂料附着力差的问题，并且通过自分层效应，将氟链更多的迁移于涂层表面，有效降低氟碳树脂的用量，降低成本。本项目围绕新型“伞形”和“树形”结构的短氟碳链含氟单体的结构设计与制备，并将其用于含氟环氧树脂的聚合，最终将此新型结构的聚合物与环氧树脂聚合物共混，采用自分层技术，获得了具有优良拒水拒油性能的环氧基短氟碳链聚合物涂层。.首先，制备了具有“伞形”和“树形”结构的短氟碳链含氟单体，并将其与其他丙烯酸酯类单体进行溶液共聚，考察了实验条件及“伞形”和“树形”结构单体对溶液聚合的影响。将上述制备的“伞形”和“树形”结构的短氟碳链含氟聚合物进行表面性能测试，并将其与“线性”结构的短氟碳链含氟聚合物进行对，研究涂膜的拒水拒油性的机理及影响规律。.其次，合成了含氟羟基丙烯酸酯树脂，并利用这类树脂制备了可高温固化的含氟自分层涂料，详细考察了自分层涂层中含氟树脂用量、成膜时间、固化剂用量、固化温度、含氟树脂含氟量对涂膜分层、附着力及水接触角的影响。.最后，基于自分层效应构建“伞形”结构的短氟碳链含氟聚合物的环氧基低表面能自分层涂料，并探究了自分层效应的影响因素与自分层涂膜的性能，从而最终实现自分层涂层在纺织物表面的应用。.