无硫无皂聚合物-有机颜料杂化乳胶粒的制备与微结构调控

By using the organic pigment-based ink-jet inks, the digital ink-jet printing of textiles is one kind of environmentally friendly technology for cleaner dyeing. Due to the shortcomings of easy agglomeration and poor water-dispersion stability of organic pigment micro-particles, however, the encapsulation and dispersion of organic pigment micro-particles are also hot and difficult research problems in the field of digital ink-jet printing of textiles. In this project, based on these problems, an amphiphilic sulphur-free macro-RAFT with a vinyl end group is proposed to disperse organic pigment particles, where the vinyl group is considered to be the living point to mediate the reversible addition-fragmentation chain transfer (RAFT) radical polymerization of methacryloyl-terminated poly(simethylsiloxane) (PDMS-MA) and other hydrophobic monomers. And then, sulphur-free and surfactant-free hybrid latexes of polymer-organic pigments will be obtained. By the study of sulphur-free and surfactant-free RAFT emulsion polymerization, good encapsulation and dispersion properties of organic pigment particles, as well as the control of hybrid latex microstructures, will be achieved. The conditions, law and model of adsorption or dispersion between macro-RAFT and organic pigment particles will also be obtained in this project. Finally, the relationship between the dyeing properties of hybrid latexes and the groups, composition structures and sequence structures of copolymers will also be revealed. These results may be as some scientific basis for the development of environmentally friendly polymer-organic pigment hybrid latexes with good application properties.

基于有机颜料墨水的纺织品数码喷墨印花是一种环境友好的清洁着色新技术。然而，由于有机颜料微细粒子易团聚、水分散稳定性差，有机颜料微细粒子的有效包覆、分散稳定并用于数码印花墨水的制备仍是目前纺织品数码喷墨印花领域的一个热点与难点问题。项目基于此，拟合成无规-嵌段型两亲性端ω-乙烯基聚甲基丙烯酸类大分子用于分散有机颜料粒子，并作为可逆加成-断裂链转移（RAFT）大分子试剂用于调控有机硅大单体等疏水性单体的原位RAFT无皂乳液共聚，获得无硫无皂的聚合物-有机颜料杂化乳胶。通过无硫无皂RAFT乳液聚合反应规律的研究，实现有机颜料微细粒子的有效分散与微结构调控，获得无规-嵌段型两亲性RAFT试剂与有机颜料粒子发生吸附分散的条件和规律，并阐述其分散模型，揭示聚合物基团结构、组成结构、序列结构与有机颜料分散稳定性能之间的构效关系，为制备环境友好、应用性能优异的新型聚合物-颜料杂化乳胶提供科学依据。

基于有机颜料墨水的纺织品数码喷墨印花是一种环境友好的清洁着色新技术。然而，由于有机颜料微细粒子易团聚、水分散稳定性差，有机颜料微细粒子的有效包覆、分散稳定并用于数码印花墨水的制备仍是目前纺织品数码喷墨印花领域的一个热点与难点问题。项目基于此，合成了两亲性端ω-乙烯基聚甲基丙烯酸类大分子用于分散有机颜料粒子，并作为可逆加成-断裂链转移（RAFT）大分子试剂用于调控丙烯酯类疏水性单体的原位RAFT无皂乳液共聚，获得无硫无皂的聚合物-有机颜料杂化乳胶。. 首先，合成得到一系列不同组成的无硫端ω-乙烯基聚甲基丙烯酸类大分子RAFT试剂，系统性地考察了在水溶液中对有机颜料粒子的吸附分散规律，实现了有机颜料微细粒子在水相介质中的稳定分散，获得了不同结构RAFT试剂对有机颜料的吸附曲线和模型。其次，通过对两亲性无硫大分子RAFT试剂调控丙烯酸酯类单体在有机颜料微细粒子表面的原位无硫RAFT(SF-RAFT)自由基乳液共聚反应动力学的系统研究，实现了包覆层聚合物基团结构、组成结构、序列结构的调控，获得了包覆率高、分散稳定的聚合物-有机颜料杂化乳胶。最后，为了制备手感良好、透气、服用性能优良的印花织物，本项目扩大了研究范围，通过双原位聚合法进行了有机硅改性聚合物（丙烯酸酯、聚氨酯丙烯酸酯、醇酸树脂等）-有机颜料杂化胶粒的合成与性能研究，发现通过双原位聚合法可实现有机硅/聚合物分子层面杂化，有效控制有机硅相与聚合物相的微相分离行为，并得到具有良好疏水和手感的杂化乳胶印花织物。此外，通过双原位聚合体系研究，还发现以染料皮克林乳液制备树莓结构有机-无机复合粒子能精准控制复合粒子的形貌结构和微相杂化结构，这些双原位聚合体系还具有低成本、绿色制造特点，在有机/无机杂化材料制备与利用具有重要价值。

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