Effect of three distinctive crosslinking agents on the dielectric properties of as-prepared polyimide aerogels prepared from super-critical fluid technique

IF 4.8 3区材料科学 Q1 CHEMISTRY, APPLIED

Microporous and Mesoporous Materials Pub Date : 2024-11-08 DOI:10.1016/j.micromeso.2024.113406

Ming-Jaan Ho , Kuan-Ying Chen , Minsi Yan , Yun-Ting Chen , Wei-Syuan Jhuang , Ho-Hsiu Chou , Jui-Ming Yeh

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Abstract

In this study, the impact of three distinct cross-linking agents—1,3,5-benzene tricarbonyl trichloride (BTC), tris(4-aminophenyl)amine (TAPA), and 3-aminopropyltrimethoxysilane (APTMS)—on the dielectric and thermal properties of polyimide aerogels was investigated. Poly(amic acid) (PAA) was synthesized by reacting diamine ODA with dianhydride BPDA in NMP, followed by cross-linker introduction in acetic anhydride and pyridine. The analysis reveals that BTC and TAPA, both organic cross-linkers with varying aromatic content, influence the dielectric properties differently. APTMS, an organosilane, introduces inorganic siloxane linkages, enhancing the thermal stability of the aerogels.

Key findings include that BTC-crosslinked aerogels achieved the lowest dielectric constant, 1.215, and dielectric loss, 0.025, making them particularly effective for high-frequency applications. In contrast, TAPA and APTMS-crosslinked aerogels displayed higher dielectric constants and losses. Differential Scanning Calorimetry (DSC) revealed that PI-APTMS exhibited the highest glass transition temperature (T_g), followed closely by PI-TAPA, both significantly higher than the non-crosslinked polyimide aerogel (NAPI), indicating excellent thermal properties. The melting points (T_m) of PI-APTMS and PI-BTC were similar, around 294 °C, attributed to the density of structural stacking. At the same time, PI-TAPA exhibited a lower T_m, likely due to its superior network structure.

Thermogravimetric analysis (TGA) further indicated that PI-TAPA had the highest thermal decomposition temperature (T_5d), with all aerogels remaining stable above 420 °C. These results underscore the potential of BTC-crosslinked polyimide aerogels for applications requiring minimal dielectric loss and low constants. We also highlight the influence of organic versus inorganic cross-linkers on thermal and dielectric performance, advancing the field of high-speed communication materials.

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三种不同交联剂对超临界流体技术制备的聚酰亚胺气凝胶介电性能的影响

本研究调查了三种不同的交联剂--1,3,5-苯三羰基三氯化物（BTC）、三（4-氨基苯基）胺（TAPA）和 3-氨基丙基三甲氧基硅烷（APTMS）--对聚酰亚胺气凝胶介电性能和热性能的影响。聚酰胺（PAA）是通过二胺 ODA 与二酐 BPDA 在 NMP 中反应，然后在乙酸酐和吡啶中引入交联剂合成的。分析表明，BTC 和 TAPA 这两种具有不同芳香族含量的有机交联剂对介电性能的影响各不相同。主要发现包括：BTC 交联气凝胶的介电常数（1.215）和介电损耗（0.025）最低，因此特别适用于高频应用。相比之下，TAPA 和 APTMS 交联气凝胶的介电常数和介电损耗较高。差示扫描量热法（DSC）显示，PI-APTMS 显示出最高的玻璃化转变温度（Tg），紧随其后的是 PI-TAPA，两者均明显高于非交联聚酰亚胺气凝胶（NAPI），表明其具有优异的热性能。PI-APTMS 和 PI-BTC 的熔点（Tm）相似，都在 294 °C 左右，这归因于结构堆叠的密度。热重分析（TGA）进一步表明，PI-TAPA 的热分解温度（T5d）最高，所有气凝胶在 420 ℃ 以上仍保持稳定。这些结果凸显了 BTC 交联聚酰亚胺气凝胶在要求最小介电损耗和低常数的应用中的潜力。我们还强调了有机交联剂和无机交联剂对热性能和介电性能的影响，从而推动了高速通信材料领域的发展。

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来源期刊

Microporous and Mesoporous Materials 化学-材料科学：综合

CiteScore

10.70

自引率

5.80%

发文量

649

审稿时长

26 days

期刊介绍： Microporous and Mesoporous Materials covers novel and significant aspects of porous solids classified as either microporous (pore size up to 2 nm) or mesoporous (pore size 2 to 50 nm). The porosity should have a specific impact on the material properties or application. Typical examples are zeolites and zeolite-like materials, pillared materials, clathrasils and clathrates, carbon molecular sieves, ordered mesoporous materials, organic/inorganic porous hybrid materials, or porous metal oxides. Both natural and synthetic porous materials are within the scope of the journal. Topics which are particularly of interest include: All aspects of natural microporous and mesoporous solids The synthesis of crystalline or amorphous porous materials The physico-chemical characterization of microporous and mesoporous solids, especially spectroscopic and microscopic The modification of microporous and mesoporous solids, for example by ion exchange or solid-state reactions All topics related to diffusion of mobile species in the pores of microporous and mesoporous materials Adsorption (and other separation techniques) using microporous or mesoporous adsorbents Catalysis by microporous and mesoporous materials Host/guest interactions Theoretical chemistry and modelling of host/guest interactions All topics related to the application of microporous and mesoporous materials in industrial catalysis, separation technology, environmental protection, electrochemistry, membranes, sensors, optical devices, etc.