线性/支化Poly(St-alt-MA)-纳米碳材料多相流体的喷墨和成膜行为研究

Inkjet printing is a non-contact, dot matrix and fine processing technology that can be used as an alternative approach for membrane by micro-depositing functional materials on substrates. This technology is becoming a hotpoint in the field of membrane research. However, non-precise position printing and "coffee ring" effect in the film-forming are the two major obstacles which limit the development of this technology. Polymer-nanoscale materials multiphase fluid is an ideal system to form the membrane by inkjet printing. However, it is not yet clear how the chain structure of polymer, properties of nanoscale carbon black affect the printing performance and film-forming of the liner/hyperbranched copolymer-nanoscale materials multiphase fluid. This project aims to disclose the polymerization machism of hyperbranched poly(styrene -alt-maleic anhydride) (Poly(St-alt-MA)) which is synthesized using (4-vinylphenyl) methanethiol as a chain transfer agent. Investigating the effects of Poly(St-alt-MA) chain structure, properties of nanoscale carbon black on performance of Poly(St-alt-MA)-nanoscale carbon materials multiphase fluid helps to interpret the adsorption behavior of linear/hyperbranched Poly(St-alt-MA) toward nanoscale particles and the stability mechanism of multiphase fluid. In addition, this project will reveal the interrelationship of elongational viscosity, non-Newtonian index with printing performance and film-forming process. The successful execution of this project will contribute to understanding the fundamental theory of linear/hyperbranched Poly(St-alt-MA)-nanoscale carbon materials multiphase fluid in inkjet printing, and thus solving the non-precise position printing (e.g. satellite drops, ramp injection, merging droplets, blocking and trailing the droplets, etc.) and "coffee ring" effect in the film-forming process. This research can greatly promote and extend the application of inkjet printing for membrane technology.

喷墨制膜是非接触、点阵式在基材表面定点微量沉积功能材料的精细加工技术，"非精确定位"喷墨和成膜"咖啡环"效应是制约该技术发展的主要瓶颈。聚合物-纳米炭黑多相流体是喷墨制膜的主体材料，其喷墨和成膜行为与聚合物链结构、纳米炭黑性能的关系至今不清。本课题拟采用巯基链转移支化聚合法制备支化苯乙烯-马来酸酐共聚物Poly(St-alt-MA)，探讨Poly(St-alt-MA)链结构、纳米炭黑性能与Poly(St-alt-MA)-纳米碳材料多相流体性质、喷墨和成膜行为的关系，构建线性/支化Poly(St-alt-MA)在纳米炭黑表面的吸附模型，解析多相流体的分散稳定机理，明确该流体的流变行为、拉伸粘度和非牛顿指数等性质与喷墨和成膜行为的内在联系，解决多相流体"非精确定位"喷墨和成膜的"咖啡环"效应。项目开展对阐明共聚物-纳米材料多相流体喷墨制膜的基础科学问题有重要意义。

喷墨制膜是一种非接触、点阵式在基材表面上快速、大面积定点微量沉积或图案化功能材料的精细加工技术，具有加工过程简单，成本低，材料利用率高和节能环保等特点，在液晶显示器滤光片、太阳能电池、生物芯片、传感器、光波导、聚合物发光二极管、聚合物薄膜晶体管和集成电路等方面展现出极其重要的应用前景。由线性聚合物和纳米碳材料构成的多相流体是喷墨制膜的主体材料，该流体在喷墨中除了会发生并线、断线、斜喷、溅射等“非精确定位”喷墨外，还会出现与基材结合力不足的问题，从而造成膜厚薄不匀、图案模糊和重影等现象。支化型共聚物端基多，分子链间缠绕少，具有良好的溶解性。更重要的是该物质具有低黏度以及更易交联成膜的特性，使之成为喷墨墨水中最具发展潜力的多功能助剂之一。基于此，本项目先采用巯基链转移支化自由基聚合技术，通过控制巯基链转移单体的用量，设计合成了链结构不同的Poly(St-alt-MA)，在此基础上用不同的酯化剂对线性/支化Poly(St-alt-MA)改性，制备了不同酯化度的线性/支化Poly(St-alt-MA)部分酯化物；然后，分别以线性/支化Poly(St-alt-MA)及其部分酯化物为分散剂，通过研磨加工制备了线性/支化Poly(St-alt-MA)-纳米炭黑多相流体，研究对比了链结构、酯化度不同多相流体的胶体性质，分析了结构不同Poly(St-alt-MA)在纳米炭黑表面的吸附方式，构建了线性/支化Poly(St-alt-MA)及其酯化物与纳米炭黑的吸附模型，阐明了线性/支化共聚物-纳米炭黑多相流体的分散稳定机理；接下来我们又研究线性/支化Poly(St-alt-MA)-纳米炭黑多相流体在喷墨墨水和海藻纤维原液着色中的应用，分析了该流体在不同应用领域中的固色方式和机理；最后，阐明了不同链结构Poly(St-alt-MA)制备喷墨墨水的喷射性能和在纺织品上的固色牢度。除此之外，该项目还研究了相分离技术制备支化Poly(St-alt-MA)-纳米包覆炭黑的工艺和过程。该项目研究为常规自由基聚合聚合制备支化型共聚物，全面解决颜料墨水喷墨印花牢度提供了一条切实可行的方法，研究结果对推动纺织印花产业升级和技术改造奠定了基础。

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