Preparation and properties of polyamic acid-polyurethane block copolymers and thermoimide elastomers

doi:10.16085/j.issn.1000-6613.2023-2285

Abstract

Abstract:

The polyamic acid (PAA) was synthesized by pyromellitic dianhydride (PMDA) and 4,4'-diaminodiphenyl ether (ODA), followed by polymerization with a polyurethane prepolymer constructed by isophorone diisocyanate (IPDI), polytetramethylene tetramethylene ether glycol (PTMG) and 1,4'-butanediol (BDO) to prepare a block copolymer poly(amide-urethane) (PAA-PU). Subsequently, the PAA-PU evolved to final poly(imide-urethane) (PI-PU) by thermal imidization by a plate vulcanizer. The chemical structure and performance of aforementioned copolymers were characterized by infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), mechanical property testing, dynamic thermomechanical analysis (DMA), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). As a result, the tensile strength was enhanced to 63.7MPa for PAA-PU and 86.4MPa for PI-PU, compared to 28.3MPa for polyurethane (PU). Besides, the temperature of maximum degradation rate of copolymer reached to 352.6℃ and the residual retention was increased. In addition, the glass transformation temperature of copolymer was improved from 37.2℃ to 91.6℃ as polyimide segments incorporated and further elevated to 128.5℃ due to additional content of polyimide segments. Meanwhile, the increases of storage modulus, reduction of loss modulus and widened rubber platform of PI-PU copolymer were also displayed in respect to PU.

Key words: polyurethane, polyimide, block copolymerization, elastomer, mechanical properties

摘要：

以均苯四甲酸酐（PMDA）、4,4'-二氨基二苯醚（ODA）为原料，合成聚酰胺酸齐聚物（PAA），后与异佛尔酮二异氰酸酯（IPDI）、聚四氢呋喃醚二醇（PTMG）和1,4'-丁二醇（BDO）合成的聚氨酯预聚体进行嵌段，合成聚酰胺酸聚氨酯嵌段共聚物（PAA-PU），通过平板硫化仪热亚胺化，制备聚酰亚胺-聚氨酯嵌段共聚物（PI-PU）弹性体。采用红外光谱（FTIR）、核磁共振波谱（NMR）、热重分析（TGA）、X射线光电子能谱（XPS）、力学性能测试、动态热机械分析（DMA）、差示扫描量热分析（DSC）、凝胶渗透色谱（GPC）对齐聚物PAA、嵌段聚合物PAA-PU、PI-PU及PU进行结构表征和性能测试。结果表明，相较于拉伸强度23.8MPa的PU，引入PAA的嵌段聚合物拉伸强度提高到63.7MPa，亚胺化后的聚合物拉伸强度进一步提高到86.4MPa，聚合物最大热分解温度提高到352.6℃，残留质量上升。DMA测试结果表明，随着PI的嵌段引入，嵌段聚合物T_g由37.2℃提升至91.6℃，随着PI含量增加，T_g进一步提升至128.5℃。此外，嵌段聚合物的储能模量增大，损耗模量降低，橡胶平台变宽。

关键词: 聚氨酯, 聚酰亚胺, 嵌段共聚, 弹性体, 力学性能

CLC Number:

TQ334

WAN Lixiang, CUI Jinfeng, GUO Junhong, BAO Xuemei, YANG Baoping. Preparation and properties of polyamic acid-polyurethane block copolymers and thermoimide elastomers[J]. Chemical Industry and Engineering Progress, 2025, 44(1): 398-406.

万立祥, 崔锦峰, 郭军红, 包雪梅, 杨保平. 聚酰胺酸-聚氨酯嵌段共聚物及其热亚胺化弹性体的制备与性能[J]. 化工进展, 2025, 44(1): 398-406.

Figures/Tables 15

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样品编号	PMDA/g	ODA/g	nPMDA/nODA	NMP/g
PAA-1	2.18	4.00	1∶2	14.42
PAA-2	6.54	8.01	3∶4	33.95

样品编号	PMDA/g	ODA/g	nPMDA/nODA	NMP/g
PAA-1	2.18	4.00	1∶2	14.42
PAA-2	6.54	8.01	3∶4	33.95

样品	PTMG/g	BDO/g	IPDI/g	PAA-1/g	PAA-2/g	DMF/g
PAA-PU-1	10.24	1.26	8.89	5.77	—	61.04
PAA-PU-2	10.24	1.26	8.89	—	12.56	79.28
PU	10.24	2.1	8.89	—	—	49.54

样品	PTMG/g	BDO/g	IPDI/g	PAA-1/g	PAA-2/g	DMF/g
PAA-PU-1	10.24	1.26	8.89	5.77	—	61.04
PAA-PU-2	10.24	1.26	8.89	—	12.56	79.28
PU	10.24	2.1	8.89	—	—	49.54

样品	数均分子量/g·mol^-1	重均分子量/g·mol^-1	分子量峰值/g·mol^-1	多分散系数
PU	146632	295532	246779	2.02
PAA-PU-1	150049	284241	233710	1.89
PAA-PU-2	114014	199543	201451	1.75