高清晰度激光标记高分子/无机复合水凝胶的构筑与性能

Laser marking is the ideal method for marking and decorating various polymeric materials with identifying characters, symbols, and patterns, due to its fast speed, excellent durability, high contrast, and environmental friendliness. However, the laser marking of highly swollen and soft hydrogels is difficult or impossible to perform due to the materials’ light color or transparency to laser beams, which limits the marking and identification applications of hydrogels. According to the laser marking technology of polymeric materials, in this project, the laser-sensitive inorganic oxide particles will be introduced into the hydrogel crosslinking network structure, and the laser process parameters will be optimized to prepare the polymer/inorganic composite hydrogel with excellent laser marking performance. It is proposed to use laser-sensitive inorganic oxide particles of different sizes, which will be further modified with physical absorption of polymers and the surface-initiated graft polymerization of monomers to form easy carbonization polymer layer with controlled thickness on their surface. At the same time, in order to attain the high-resolution and high-contrast markings on hydrogels, the laser marking performance of composite hydrogels can be regulated by the incorporation of the easy carbonization monomer units to the crosslinking networks, and the use of environmentally temperature and pH sensitivity of hydrogels. On the basis, the morphology, structure, composition and properties of the laser marked surface of the composite hydrogels will be analyzed to clarify the laser marking mechanism of the polymer/inorganic composite hydrogel, and a fast and efficient method for surface marking and patterning of the soft and wet materials by laser marking can be developed.

激光标记技术因其快速高效、标记持久、高对比度以及环境友好广泛用于高分子材料表面的文字符号标记和图案化修饰。高溶胀和柔软的水凝胶材料由于颜色较浅或透明难以进行激光标记，限制了水凝胶在识别标记领域的应用。本项目借鉴高分子材料激光标记技术，将激光敏感性无机氧化物颗粒引入水凝胶交联网络结构，优化激光工艺参数，制备具有优异激光标记性能的高分子/无机复合水凝胶。拟采用不同尺寸的无机氧化物颗粒，经物理包覆和表面引发接枝聚合在表面形成厚度可控的易成炭高分子层，同时在交联网络上引入易成炭的结构单元，利用水凝胶的环境温度和pH敏感性，调控水凝胶表面激光诱导变黑的标记性能，保证水凝胶高清晰度和高对比度标记。在此基础上，拟对复合水凝胶激光标记表面的形貌、结构、组成及性能等进行分析，阐明高分子/无机复合水凝胶的激光标记机理，为软物质和湿态材料的表面标记和图案修饰提供一种快速高效方法。

本项目借鉴高分子材料激光标记技术，将激光敏感性无机氧化物颗粒引入水凝胶交联网络结构，通过激光敏感性无机氧化物颗粒的表面改性与选择调控、复合水凝胶体系组分调控以及激光工艺参数的优化，制备获得了具有优异激光标记性能的聚丙烯酰胺/Bi2O3、聚丙烯酰胺/BiOCl、聚丙烯酰胺/PS@Bi2O3、聚丙烯酰胺/壳聚糖/Bi2O3、聚丙烯酰胺/海藻酸钠/Bi2O3以及聚丙烯酰胺/TiO2、聚丙烯酰胺/壳聚糖/Fe3O4、聚(N-异丙基丙烯酰胺-co-ATU)等多种体系复合水凝胶的制备方法，建立了复合水凝胶制备条件与高清晰度和对比度激光标记性能之间相互关系，建立了多种复合水凝胶的高清晰和对比度标记的控制方法，阐明了高分子/复合水凝胶激光诱导变色标记的机理，为水凝胶软物质和湿态材料的表面标记和图案修饰提供理论依据和制备方法，丰富水凝胶的性能并扩展应用领域；同时在可激光标记材料领域继续进行深入研究，设计与制备了多种可激光标记的高分子/无机复合材料体系。项目执行期内以第一或通讯作者在SCI/EI收录的国内外重要期刊发表文章13篇，授权发明专利4项。