低聚聚酰亚胺<strong>(SPI)</strong>改性的聚酰亚胺<strong>(PI)</strong>固化物的制备和性能

doi:10.11901/1005.3093.2024.276

材料研究学报

2025, Vol. 39

Issue (2): 103-112 DOI: 10.11901/1005.3093.2024.276

研究论文

本期目录 | 过刊浏览

低聚聚酰亚胺(SPI)改性的聚酰亚胺(PI)固化物的制备和性能

朱国豪, 陈平(

), 徐计雷, 孙慧敏

大连理工大学化工学院精细化工全国重点实验室大连 116024

Preparation and Properties of Curd Polyimide Modified by Oligomeric Polyimide

ZHU Guohao, CHEN Ping(

), XU Jilei, SUN Huimin

State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China

引用本文:

朱国豪, 陈平, 徐计雷, 孙慧敏. 低聚聚酰亚胺(SPI)改性的聚酰亚胺(PI)固化物的制备和性能[J]. 材料研究学报, 2025, 39(2): 103-112.
Guohao ZHU, Ping CHEN, Jilei XU, Huimin SUN. Preparation and Properties of Curd Polyimide Modified by Oligomeric Polyimide[J]. Chinese Journal of Materials Research, 2025, 39(2): 103-112.

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摘要:

设计并合成一种具有Cardo结构、柔性硅氧烷和苯乙炔封端的低聚聚酰亚胺(SPI)，将其以不同比例混入聚酰亚胺(PI)中制备出低聚聚酰亚胺(SPI)改性的聚酰亚胺(PI)。将SPI改性的PI固化，制备出SPI改性的PI固化物，其玻璃化转变温度(T_g)从PI基体的382 ℃提高到459 ℃；拉伸强度从96.25 MPa提高到128.96 MPa，拉伸模量从1.83 GPa提高到2.41 GPa。改性 PI固化物的热稳定性和力学性能优异，因为在改性固化的热交联过程中形成的半互穿聚合物网络结构(semi-IPNs)和硅氧烷结构间产生了协同效应。

关键词 ：有机高分子材料, 聚酰亚胺, 热交联, semi-IPNs结构, 热稳定性, 力学性能

Abstract：

A novel oligomeric polyimide (SPI) incorporated with Cardo structures, flexible siloxane bonds, and phenylethynyl terminations was designed and synthesized. Then, the prepared SPI was blended with polyimide (PI) matrix in different proportions to produced SPI modified PI polymer. Upon curing, the SPI modified PI polymer exhibited significant improvements in thermal and mechanical properties. The glass transition temperature (T_g) of the cured blends increased from 382 ^oC for the PI matrix to 459 ^oC. Correspondingly, the tensile strength and tensile modulus were improved from 96.25 MPa and 1.83 GPa to 128.96 MPa and 2.41 GPa respectively. The enhanced thermal stability and mechanical performance of the modified PI may be attributed to the synergistic effects between the siloxane structures with the semi-interpenetrating polymer network (semi-IPNs) formed during the thermal crosslinking process.

Key words： organic polymer materials polyimide thermal -crosslinking semi-IPNs thermal stability mechanical property

收稿日期: 2024-06-15

ZTFLH:

TB324

基金资助:兴辽英才计划(XLYC1802085);国家自然科学基金(51873109);大连市科技创新基金重大项目(2019J11CY007)

通讯作者: 陈平，教授，pchen@dlut.edu.cn，研究方向为高性能高分子材料与先进聚合物基复合材料与功能一体化设计与制备

Corresponding author: CHEN Ping, Tel: (0411)84986100, E-mail: pchen@dlut.edu.cn

作者简介: 朱国豪，男，1999年生，硕士

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https://www.cjmr.org/CN/10.11901/1005.3093.2024.276 或 https://www.cjmr.org/CN/Y2025/V39/I2/103

图1 SPI、PI的合成路线和固化SPI改性PI聚合物薄膜的照片

图2 二硝基化合物BNFPS和二胺基化合物APFPS的红外光谱和APFPS的核磁谱

图3 SPI的红外谱和1H NMR谱

图4 未固化SPI改性PI聚合物薄膜的红外谱、2100~2300 cm-1范围苯乙炔基团的红外谱和固化后SPI改性PI聚合物薄膜的红外谱

图5 SPI、未固化和固化的SPI改性PI聚合物薄膜的广角X射线衍射谱

图6 未固化SPI改性PI聚合物薄膜的DSC曲线和Tg与组成的关系

表1 未固化的SPI改性PI聚合物薄膜的Tg测试值与理论计算结果

图7 热固化过程

图8 固化SPI改性PI聚合物薄膜的DSC、DMA、TGA和DTG曲线

表2 固化后SPI改性PI聚合物薄膜的热性能

表3 SPI改性PI固化聚合物薄膜的力学性能

图9 固化SPI改性PI聚合物薄膜的SEM照片

图10 固化SPI改性PI聚合物薄膜的水接触角

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