<br>高分子结构对 3D 打印材料相分离状态的影响,Macromolecular Rapid Communications

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高分子结构对 3D 打印材料相分离状态的影响
Macromolecular Rapid Communications ( IF 4.2 ) Pub Date : 2023-06-08 , DOI: 10.1002/marc.202300236
Yuan Xiu _{1,

2} , Valentin A Bobrin _{1,

2} , Nathaniel Corrigan _{1,

2} , Jin Zhang ₃ , Cyrille Boyer _{1,

2}

Affiliation

在这项研究中，展示了通过光诱导 3D 打印，使用聚合诱导微相分离 (PIMS) 来制造具有受控相分离的 3D 打印聚合物材料。虽然影响 PIMS 过程中纳米结构的许多参数已被广泛研究，但大分子链转移剂 (macroCTA) 的链转移剂 (CTA) 端基（即 Z 基团）的影响仍不清楚，因为之前的研究专门使用三硫代碳酸酯作为纳米结构。 CTA端基。在此，探讨了含有四种不同Z基团的macroCTA对3D打印材料纳米结构形成的影响。结果表明，不同的 Z 基团会导致树脂之间形成不同的网络和相分离行为，从而影响 3D 打印过程和所得材料的性能。具体而言，对丙烯酸自由基加成反应性较低的大CTA，例如O-烷基黄原酸酯和N-烷基-N-芳基二硫代氨基甲酸酯，会产生具有宏观相分离形态的半透明脆性材料。相比之下，反应性更强的大CTA（例如S-烷基三硫代碳酸酯和4-氯-3,5-二甲基吡唑二硫代氨基甲酸酯）可产生具有纳米级形态的透明且刚性的材料。这项研究的结果提供了一种操纵 3D 打印 PIMS 材料的纳米结构和性能的新方法，这对材料科学和工程具有重要意义。

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Effect of Macromolecular Structure on Phase Separation Regime in 3D Printed Materials

In this study, the fabrication of 3D-printed polymer materials with controlled phase separation using polymerization induced microphase separation (PIMS) via photoinduced 3D printing is demonstrated. While many parameters affecting the nanostructuration in PIMS processes are extensively investigated, the influence of the chain transfer agent (CTA) end group, i.e., Z-group, of macromolecular chain transfer agent (macroCTA) remains unclear as previous research has exclusively employed trithiocarbonate as the CTA end group. Herein, the effect of macroCTAs containing four different Z-groups on the formation of nanostructure of 3D printed materials is explored. The results show that the different Z-groups lead to distinct network formation and phase separation behaviors between the resins, influencing both the 3D printing process and the resulting material properties. Specifically, less reactive macroCTAs toward acrylic radical addition, such as O-alkyl xanthate and N-alkyl-N-aryl dithiocarbamate, result in translucent and brittle materials with macrophase separation morphology. In contrast, more reactive macroCTAs such as S-alkyl trithiocarbonate and 4-chloro-3,5-dimethylpyrazo dithiocarbamate produce transparent and rigid materials with nano-scale morphology. Findings of this study provide a novel approach to manipulate the nanostructure and properties of 3D printed PIMS materials, which can have important implications for materials science and engineering.

更新日期：2023-06-08

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