喷雾干燥结合紫外交联制备甲基丙烯酸缩水甘油酯改性丝胶中空微球及其性能
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河南省自然科学基金项目(242300421470);河南省重点研发与推广专项(232102230155);中原工学院研究生科研创新计划(YKY2023ZK06);中原工学院“学科青年硕导培育计划”项目(SD202219)


Preparation and Properties of GMA-Modified Sericin Hollow Particles by Spray Drying Combined with Ultraviolet Cross-Linking
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    摘要:

    为了制备高耐水性光固化丝胶蛋白(SS)微球,采用喷雾干燥与紫外交联相结合的方法,以丝胶为原料制备了甲基丙烯酸缩水甘油酯(GMA)交联SS中空微球(GMA-g-SS),该法赋予了其良好的耐水稳定性和紫外光固化性能。优化的喷雾干燥工艺参数包括:SS浓度、进风温度及进液速度;研究了GMA浓度、二苯甲酮(BP)用量及紫外辐照时间对接枝率的影响。借助扫描电镜、红外光谱及热分析对微球表面形貌结构及稳定性进行了表征与分析。结果表明,喷雾干燥SS 微球呈单分散空心结构,直径约5~20 μm;GMA-g-SS 微球红外光谱在1152 cm-1和764 cm-1处出现环氧基的吸收峰,表明GMA与SS 交联成功。交联后微球呈黏连聚集状态,具有较高的紫外光固化性能且耐水稳定性大幅提升,溶失率仅为17.1%。所制备的GMA-g-SS 微球具有可调的耐水稳定性和紫外光固化性,是一种有潜力的光固化3D打印生物材料。

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    In order to fabricate highly water- resistant and light- curing silk sericin (SS) particles, spraying drying and ultraviolet cross- linking technology were combined to prepare glycidyl methacrylate (GMA) crosslinked sericin hollow particles (GMA-g-SS) from silk sericin materials, conferring good water- resistant stability and UV curing properties. Spray drying process parameters such as SS concentration, inlet air temperature, and liquid feed rate were optimized. The effects of GMA concentration, benzophenone (BP) dosage and UV irradiation time on the grafting rate were investigated. The surface morphology, structure, and stability of as- fabricated microspheres were characterized through scanning electron microscopy, infrared spectroscopy and thermogravimetry. The results reveal that the spray- dried SS microspheres are hollow and monodispersed (diameters ranging from 5 μm to 20 μm) . The infrared spectra of GMA-g-SS microspheres show new adsorption peaks of epoxy group at 1152 cm-1 and 764 cm-1, suggesting the GMA and SS were successfully cross-linked. After crosslinking, the SS microspheres are in an adherent state, with high UV curing performance and greatly improved water stability (mass-loss ratio is only 17.1%). The prepared GMA-g-SS microspheres have tunable water stability and UV curing performance, making them a potential biomaterial for UV-curing 3D printing.

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谭宇浩,杜姗,韩璐,张祎,李勇,周金利,周伟涛.喷雾干燥结合紫外交联制备甲基丙烯酸缩水甘油酯改性丝胶中空微球及其性能[J].高分子材料科学与工程,2024,40(3):30-38. Yuhao Tan, Shan Du, Lu Han, Yi Zhang, Yong Li, Jinli Zhou, Weitao Zhou. Preparation and Properties of GMA-Modified Sericin Hollow Particles by Spray Drying Combined with Ultraviolet Cross-Linking[J]. Polymer Materials Science & Engineering,2024,40(3):30-38.

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