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含脂环结构聚酰胺66共聚物的合成及非等温结晶动力学

Synthesis and non-isothermal crystallization kinetics of polyamide 66 copolymers containing alicyclic structures.

作者信息

Lu Weijian, Wang Chunhua, Yi Yong, Liao Mingxi, Li Jianlin, Wang Wenzhi

机构信息

National and Local Joint Engineering Research Center of Advanced Packaging Material Research and Development Technology, School of Packaging and Materials Engineering, Hunan University of Technology Zhuzhou 412007 Hunan China

School of Life Sciences and Chemistry, Hunan University of Technology Zhuzhou 412007 China.

出版信息

RSC Adv. 2025 Jan 29;15(4):2900-2911. doi: 10.1039/d4ra08482a. eCollection 2025 Jan 23.

Abstract

To further improve the performance of PA66 and expand its applications, a new strategy was proposed to introduce an alicyclic structure into PA66 chain by the copolymerization method. Initially, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (MACM) was reacted with 1,6-adipic acid to form MACM6 salt, and then, it was copolymerized with PA66 salt to synthesize PA66/MACM6 copolymers with alicyclic structures. PA66/MACM6 copolymers exhibited good thermal stabilities, and the presence of alicyclic structure had no significant effect on their thermal stabilities. Notably, the crystallization temperature, crystallinity and melting point of the PA66/MACM6 copolymer decreased gradually with increasing MACM6 content, indicating that the addition of the MACM6 segment disrupted the regularity of the original PA66 chain. Moreover, as the melting point of the PA66/MACM6 copolymer was in between 223.9 °C and 254.8 °C, it could be processed in a wide temperature range to meet the requirements of different industrial applications. The non-isothermal crystallization kinetics of PA66/MACM6 copolymers were investigated using the Jeziorny and Mo methods, and the crystallization activation energy was calculated using the Kissinger method. The results indicated that the introduction of the MACM6 segment into the PA66 chain by copolymerization inhibited its crystallization and increased its crystallization activation energy, thereby reducing its crystallization rate. In addition, PA66/MACM6 copolymers exhibited improved toughness with a slight decrease in the strength. When the content of MACM6 reached 40 wt%, the elongation at break of PA66/MACM6-40 was about 760% higher than that of PA66, suggesting its high toughness.

摘要

为了进一步提高聚酰胺66(PA66)的性能并拓展其应用范围,提出了一种新策略,即通过共聚方法将脂环族结构引入PA66分子链中。首先,使3,3'-二甲基-4,4'-二氨基二环己基甲烷(MACM)与1,6-己二酸反应生成MACM6盐,然后将其与PA66盐进行共聚,以合成具有脂环族结构的PA66/MACM6共聚物。PA66/MACM6共聚物表现出良好的热稳定性,脂环族结构的存在对其热稳定性没有显著影响。值得注意的是,PA66/MACM6共聚物的结晶温度、结晶度和熔点随着MACM6含量的增加而逐渐降低,这表明MACM6链段的加入破坏了原始PA66分子链的规整性。此外,由于PA66/MACM6共聚物的熔点在223.9℃至254.8℃之间,它可以在较宽的温度范围内进行加工,以满足不同工业应用的需求。采用Jeziorny法和Mo法研究了PA66/MACM6共聚物的非等温结晶动力学,并使用Kissinger法计算了结晶活化能。结果表明,通过共聚将MACM6链段引入PA66分子链中会抑制其结晶并增加其结晶活化能,从而降低其结晶速率。此外,PA66/MACM6共聚物的韧性得到改善,强度略有下降。当MACM6的含量达到40 wt%时,PA66/MACM6-40的断裂伸长率比PA66高约760%,表明其具有高韧性。

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