面向3D打印的β成核剂改性聚丙烯的制备与成型质量研究

随着3D打印技术的快速发展，适用于3D打印的高性能聚合物有望推动聚合物工件迈入快速成型与智能制造的新局面。热塑性高分子聚合物与3D打印技术兼容性很高，但绝大多数属于半结晶性材料。受聚合物结晶过程的影响，在3D打印过程中，打印件容易产生残余应力与翘曲变形，极大地限制了3D打印聚丙烯工件的工业运用。在工业应用，聚丙烯是最重要的半结晶性聚合物之一，其自然结晶的情况下仅产生α晶体，造成打印件翘曲变形。本文考虑其同质多晶的性质，利用β成核剂对聚丙烯进行改性，制备了β成核剂改性聚丙烯，诱导聚丙烯向β晶体进行结晶，并探究了其对3D打印件翘曲变形与成型质量的影响。

本文经过对材料性能、成本等综合考虑，选择无规共聚聚丙烯PPR-4220与稀土配位化合物WBG-II β成核剂为原料，通过物理共混制备β成核剂改性聚丙烯。通过系统性实验，确定了改性聚丙烯的制备工艺，根据WBG-II添加量的不同制备了4种改性聚丙烯PP0、PP1、PP2、PP3（对应添加量为0%、0.1%、0.2%、0.3%），并对其热力学性质、结晶过程等相关性质进行了表征。测试结果表明在3种加入WBG-II成核剂的改性聚丙烯中，PP3在25℃~70℃的温度范围内具有最小的热膨胀系数（160.1ppm/℃）；此外在相同温度下PP3具有最大的熔融指数（230℃时1.8g/10min）与最小的表观黏度（230℃时1.21´10⁴mPa·s），即具有最好的流动性；PP3中β结晶的诱导效率最高。以上性能的变化均有利于提高3D打印件的成型质量，降低其翘曲变形。

将4种改性聚丙烯通过3D打印制备了3种打印件，对3D打印改性聚丙烯拉伸标准件进行了DSC测试并计算了其结晶度、α与β晶体相对含量。此外，对改性聚丙烯3D打印件翘曲变形、成型质量与性能进行了测试。结果表明PP0中仅存在α晶体，含量为100%，PP3中β晶体结晶诱导效率最高，结晶度也最高，β晶体相对含量达到80.8%，同时其力学性能得到提升。对于打印件的翘曲变形、收缩变形、打印质量的测试结果发现，PP3对于改善打印件的成型质量、降低翘曲变形（拉伸标准件：58%，方框：87%，方管：72%）与收缩变形（拉伸标准件：27%，方框：46%，方管：33%）的效果最佳。本文关于β成核剂改性聚丙烯的研究为半结晶聚合物的高质量、低翘曲3D打印成型提供了新途径。

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