颜色可控聚氨酯基染料的制备与性能研究

The polymeric dyes made of small dyes are an important issue in the field of dyes for mankind in 21st century. Polyurethane-based polymeric dyes are a kind of high performance polymeric dyes. Because of rarely polymerizable dyes and difficult color tuning for polyurethane-based dyes, polyurethane-based dyes are restricted the preparation and application. This project will mainly focus on preparation, color tuning of mechanisms and methods for polyurethane-based dyes. The polymerizable dye with specific activity groups will be screened and synthesized, and Polyurethane-based dyes will be synthesized through stepwise polymerization.The research will realize the control of monochromatic light color through adjusting band gap using changes of chemical structure, chain conformation or aggregation structure, and obtain composite color through selecting different color and luminous intensity of polyurethane-based dyes using blending method and copolymerization. To investigate band gap and mechanisms of luminous intensity and further obtain pervasive regulation of color based on computer simulations and experiments. The implement of our proposal not only provides theory basis and technical possibility of color tuning for polyurethane-based dyes, but also provides the core support for the development and application.

将小分子染料高分子化是二十一世纪人类在染料领域面临的重大课题。聚氨酯基染料是一类性能优异的高分子染料。然而，可用于聚合反应的染料单体有限和聚氨酯基染料颜色很难控制，严重制约了聚氨酯基染料的应用和发展。本项目将针对这一问题，以聚氨酯基染料设计合成及其颜色的调控为研究对象。利用分子模拟技术，设计合成出带有特定活性基团的可聚合染料单体，通过逐步聚合制备聚氨酯基染料。通过控制其化学结构、链构象或聚集态结构，调控聚氨酯基染料带隙差，实现对单色光颜色的调控。选用不同颜色的聚氨酯基染料，利用共混或共聚的方法，控制其发光强度，实现对表观复合光颜色的调控。通过计算模拟和实验, 探索染料带隙差以及发光强度的调控机制，建立聚氨酯基染料颜色的调控模型，得出颜色调控普适性规律。项目实施，不仅为聚氨酯基染料的制备和颜色调控提供理论基础和技术支撑，也为其应用发展奠定基础。

采用不同方法制备聚氨酯基染颜色吸收峰不同程度的的红移或蓝移现象，得出结构调控的关键性因素。提出了聚氨酯基染颜色调控机理。经无皂乳液聚合方法合成水性聚氨酯-丙烯酸杂化高分子染料。其荧光强度发生明显增强，20-70℃范围内随温度的升高而增强，在常温下很稳定，对猝灭剂也不敏感；采用丙酮方法合成磺酸型聚氨酯染料，染色性能得到显着改善，颜色产率（K/S）为20-40％，断裂强度保持率（BSR）约为120％-135％，透气性约为450-600mm/s；通过将分散红11嵌入聚氨酯主链中成功合成了WPU-DR11，其荧光强度随着温度从40℃-70℃而增加，热迁移率显著下降，K/S值约为10-22％，而BSR约为120％-135％，透气性约为450-600mm/s；改性丙酮法制得一系列来自分散蓝60的DB60-WPU，K/S值可达到22％，而BSR约为120％-130％，透气性约为400-500mm/s。利用三基色原理，通过高分子复配技术，制得聚氨酯基黑色染料，具有优异的耐摩擦、耐迁移、耐候和安全性高特点；采用溶剂法制得制得聚氨酯丙烯酸变色染料，颜色鲜艳明亮，具有明显光致变色特性；采用后扩链法制得水性聚氨酯基指示剂，具有绿 色环保、抗菌、不污染待测试样等特点，项目的实施，为聚氨酯基染料的制备和颜色调控提供理论基础和技术支撑，也为其应用发展奠定基础。