基于 PMMA 接枝的 α-磷酸锆纳米片的 PMMA 纳米复合材料,Macromolecules

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基于 PMMA 接枝的 α-磷酸锆纳米片的 PMMA 纳米复合材料
Macromolecules ( IF 5.1 ) Pub Date : 2022-02-08 , DOI: 10.1021/acs.macromol.1c02337
Zewen Zhu ₁ , Chia-Ying Tsai ₁ , Mingzhen Zhao ₁ , Joseph Baker ₁ , Hung-Jue Sue ₁

Affiliation

对于通过电子转移原子转移自由基聚合再生的表面引发活化剂，对含有溴引发剂的 α-磷酸锆 (ZrP) 纳米片进行双环氧化物改性，得到聚甲基丙烯酸甲酯接枝的 ZrP (ZrP- g -PMMA)用于 PMMA 基质中的分散。PMMA纳米复合材料的形态在_具有固定 PMMA 基体链长₍N m) 使用透射电子显微镜进行了研究。制备了各种类型的聚合物刷结构，包括蘑菇型、半稀聚合物刷和浓缩聚合物刷结构，它们对应于 PMMA 基质中 ZrP- g -PMMA 的润湿和去润湿现象。双环氧化物功能化有助于降低 ZrP 表面能并提高接枝聚合物链的构型熵，这导致基体 PMMA 链以低 σ = 0.07 链/nm ²渗透到接枝刷层中，即使在N _g /牛_米< 0.36。熔融状态下的流变学研究表明，PMMA 纳米复合材料的流动特性可以通过调节改变纳米片的负载或改变 ZrP 和 PMMA 基质之间界面的接枝特性。此外，发现含有二维 (2D) 纳米片的 PMMA/ZrP- g -PMMA 的流变行为与含有球形纳米颗粒的 PMMA /二氧化硅-PMMA 的流变行为显着不同。它们流变行为的这种巨大差异可能是由 PMMA 中二维纳米片的各向异性性质引起的。讨论了本研究对制备含有二维纳米片的热塑性纳米复合材料的意义。

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PMMA Nanocomposites Based on PMMA-Grafted α-Zirconium Phosphate Nanoplatelets

Dual-epoxide modification of α-zirconium phosphate (ZrP) nanoplatelets containing a bromine initiator was performed for surface-initiated activators regenerated by electron transfer atom transfer radical polymerization, resulting in poly(methyl methacrylate)-grafted ZrP (ZrP-g-PMMA) for dispersion in PMMA matrix. The morphology of the PMMA nanocomposites with variations in grafting density (σ) and grafted PMMA length (N_g) on ZrP-g-PMMA with a fixed PMMA matrix chain length (N_m) was investigated using transmission electron microscopy. Various types of polymer brush structures, including mushroom, semi-dilute polymer brush, and concentrated polymer brush structures, were prepared, which correspond to the wetting and dewetting phenomena of ZrP-g-PMMA in the PMMA matrices. The dual-epoxide functionalization helps decrease ZrP surface energy and improve the configurational entropy of grafted polymer chains, which results in the penetration of the matrix PMMA chains into the grafted brush layer at a low σ = 0.07 chain/nm² even when N_g/N_m < 0.36. The rheological study in the melt state reveals that the flow properties of the PMMA nanocomposites can be tuned via changing the loading of nanoplatelets or varying the grafting characteristics at the interface between ZrP and PMMA matrix. Furthermore, the rheological behavior of PMMA/ZrP-g-PMMA which contains two-dimensional (2D) nanoplatelets was found to be significantly different from that of the PMMA/silica-g-PMMA which contains spherical nanoparticles. This drastic discrepancy in their rheological behaviors is likely caused by the anisotropic nature of the 2D nanoplatelets in PMMA. The implication of the present study on the preparation of thermoplastic nanocomposites containing 2D nanoplatelets is discussed.

更新日期：2022-02-08

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