一维纳米结构稀土-聚氨酯阵列的构筑及光、热响应性能调控

The smart materials is a new generation of functional materials, but the responses to stimuli are only in the lower stage at present, multi sensitivity and its action principles are urgent problems.In the topic, the one dimensional nanoarrays of rare earth- polyurethane smart materials(TS&TSP-PUA@NA), which possesses temperature sensitivity- temperature sensitized photoluminescence(TS&TSP) and temperature perception - response – initiative fluorescent display, will be synthesized by the rare earth complex (REC) and poly(urethane-acrylate) macromonomer (PUAM) on the basis of the design and synthesis of temperature sensitive PUAM owning different temperature sensitivity (switch) temperature (Ts: the soft segment phase transition temperature) threshold. REC will be firstly prepared which have the different characteristic fluorescence emission intensity at different temperatures. Then pre-designed and fabricated functional REC as a temperature sensitive detection base load to the macromonomer PUAM polymerization system. Finally, a series of TS&TSP-PUA@NA will be synthesized by the radical polymerization of novel functional PUMA using 2, 2-azo-bis-iso-butyro-nitrile (AIBN) as catalyst in the nano-pores of anodic aluminum oxide (AAO) template. The novel TS&TSP-PUA@NA has performance of temperature Sensitivity & temperature Sensitized Photoluminescence, TS&TSP and can be used as multiple smart materials with "perception - response - fluorescent display “ in the field of self-detection temperature sensitive materials owning high stability and sensitivity. In the TS&TSP-PUA@NA system, the influence of sensitizing coordination effect between the REC and polymer matrix, nano-confined space, synthesis conditions on nanoarray structure (nanowires, nanotubes) and performance are studied. The structure and properties of the TS&TSP-PUA@NA can be regulated. Optical,thermal properties of TS&TSP-PUA@NA are extensively studied, Furthermore, structure-activity relationships and mechanism of action of structure and feature of target material TS&TSP-PUA@NA system are discussed such as the structure of rare earth complexes, nanoarray structure, bonding way between rare earth complexes and the polymer matrix and so on. The regulation of light and thermal response performance of TS&TSP-PUA@NA will be achieved, and a class of one-dimensional nano materials with controllable structure and multiple intelligence will be synthesized.

作为新一代功能材料，目前的智能材料对刺激的响应处于低级智能阶段，多重敏感性及其作用原理是亟待解决的难题。本课题以不同温敏开关温度阈值（Ts）的聚氨酯大单体（PUAM）和稀土配合物（REC）的设计合成为引导，利用REC荧光发射强度随温度变化的特性，将REC作为温敏探测基元加载到PUAM聚合体系中，PUAM在阳极氧化铝模板的纳米孔道内经自由基聚合，原位合成一类具有温敏－温敏发光（TS&TSP）特性，集对温度的“感知－响应－荧光显示”多重智能的一维纳米阵列（TS&TSP-PUA@NA）。深入研究目标材料体系中，聚氨酯基体PUA的温敏特性、REC的光致－温敏发光特性、PUA与REC间的敏化效应，及PUA与REC间温敏、温敏发光特性的匹配协同关系；探讨纳米阵列结构、REC结构、PUA结构等与目标材料光、热（温度）响应特性间的构效关系和作用机理，实现对TS&TSP-PUA@NA光、热响应性能的调控。

本项目按项目计划书的研究计划开展了深入的研究工作，主要研究内容有：①功能性稀土配合物REC的设计合成及表征；②不同结构聚氨酯大分子单体及其聚合物的设计合成；③一维结构稀土-聚氨酯纳米阵列的制备合成；④一维结构稀土-聚氨酯纳米阵列的光、热响应性能研究。. 本项目在设计合成不同结构的活性稀土配合物REC、温敏性聚氨酯大单体PUAM的基础上，合成制备了一系列对光、热响应灵敏、集对温度的“感知－响应－荧光显示”多重智能的一维聚氨酯纳米阵列（TS&TSP-PUA@NA）。在详细考察稀土配合物REC结构、纳米阵列结构、聚氨酯PUA结构对所制备的目标材料光、热响应特性的影响机制、温度与荧光强度间的作用规律等基础上，实现了一维结构聚氨酯纳米阵列、一维结构稀土-聚氨酯纳米阵列的光响应行为、热响应行为的可调可控。研究表明：所制备的聚合物纳米阵列具有良好的结构稳定性和尺寸均一性，且具有优异的热响应特性和储热性能，通过控制柔性链段（如PEG）的长度或通过改变AAO模板的孔径（调整纳米阵列的直径），可以实现对纳米阵列热响应行为的调控，该类纳米阵列在微器件储热及储能领域具有很大的应用潜力；所制备的一维结构稀土-聚氨酯纳米阵列具有优异的光致发光性能和光响应行为，通过改变AAO模板的孔径（调整纳米阵列的直径）或改变稀土配合物的添加量，可以实现对纳米阵列光响应行为的调控，该类纳米阵列在特殊光学和高端智能材料领域具有很大的应用潜力。