耐超高温双酮酐型聚酰亚胺的合成及性能

doi:10.11944/j.issn.1000-0518.2019.06.180352

摘要/Abstract

摘要：

以4,4'-对苯二甲酰二邻苯二甲酸酐(TDPA)为芳二酐单体,对苯二胺(PPD)为芳二胺单体,经低温溶液缩聚制得成膜性能优良的高相对分子质量聚酰胺酸(PAA),再经过热亚胺化制备双酮酐型聚酰亚胺(PI)薄膜。采用傅里叶变换红外光谱仪(FT-IR)、广角X射线衍射(WAXD)、差示扫描量热仪(DSC)、动态热机械分析仪(DMA)、热重分析仪(TGA)、紫外-可见分光光度计(UV-Vis)及力学性能等技术手段表征了聚酰亚胺膜的结构和性能,考察了不同亚胺化温度对合成的双酮酐型聚酰亚胺膜性能的影响。结果表明,经程序升温至320 ℃能使PAA热亚胺化基本趋于完成。 PI薄膜为部分有序聚集态结构,玻璃化转变温度(T_g)为298 ℃,具有优异的热性能,热失重温度(T_5%)为523 ℃。拉伸强度达到130 MPa,弹性模量为5.77 GPa。 PI薄膜紫外光透过截止波长为375 nm,在可见光区具有良好的透光性能及耐溶剂性能。

关键词: 双酮酐型聚酰亚胺, 热性能, 透光性能

Abstract:

A novel diketone anhydride polyimide was synthesized by introducing p-phenylenediamine(PPD) to 4,4'-terephthaloyldiphthalic anhydride through the traditional two-step method in dimethylacetamide(DMAc). The properties of the polyimide were characterized by Fourier transform infrared spectrometer(FT-IR), wide-angle X-ray diffraction(WAXD), differential scanning calorimetric(DSC), dynamic thermomechanical analyzer(DMA), thermal gravimetric analysis(TGA), tensile test and ultraviolet-visible spectrophotometry(UV-Vis). The relationship between different thermal imidization temperature and the properties of the diketone polyimide was studied. The results showed that PAA formed the imide ring structure completely at 320 ℃. The polyimide had good film-forming performance and partially ordered aggregate structure. The polyimide had excellent thermal properties: the glass transition temperature(T_g) was 298 ℃ and the thermal decomposition temperature(T_5%) was 523 ℃. The film had a tensile strength of 130 MPa and tensile modulus of 5.77 GPa at 320 ℃. The cutoff wavelength of the film was 375 nm and the film had good transmittance in visible region.

Key words: diketone anhydride polyimide, thermal properties, transmittance

刘勇军, 周丽云, 盛寿日, 宋琤, 侯豪情, 宋才生. 耐超高温双酮酐型聚酰亚胺的合成及性能[J]. 应用化学, 2019, 36(6): 658-663.

LIU Yongjun, ZHOU Liyun, SHENG Shouri, SONG Cheng, HOU Haoqing, SONG Caisheng. Synthesis and Properties of Super-high Temperature Diketone Anhydride Polyimides[J]. Chinese Journal of Applied Chemistry, 2019, 36(6): 658-663.

参考文献

[1]	WANG Jiaming.Technology Advances and Market Prospects of Polyimide Film[J]. Synth Technol Appl,2012,37(3):24-29(in Chinese). 汪家铭. 聚酰亚胺薄膜技术进展与市场前景[J]. 合成技术及应用,2012,37(3):24-29.
[2]	Min C Y,Liu D D,He Z B,et al. Preparation of Novel Polyimide Nanocomposites with High Mechanical and Tribological Performance Using Covalent Modified Carbon Nanotubes via Friedel-Crafts Reaction[J]. Polymer,2018,150:223-231.
[3]	Cheng Y,Dong J,Yang C R,et al. Synthesis of Poly(benzobisoxazole-co-imide) and Fabrication of High-Performance Fibers[J]. Polymer,2017,133:50-59.
[4]	Chen D,Zhu H,Liu T.In Situ Thermal Preparation of Polyimide Nanocomposite Films Containing Functionalized Graphene Sheets[J]. ACS Appl Mater Interfaces,2010,2(12):3702-3708.
[5]	YANG Shiyong.Progress in High Temperature Polyimide Resin[J]. Polym Bull,2014,(12):23-28(in Chinese). 杨士勇. 耐高温聚酰亚胺树脂研究[J]. 高分子通报,2014,(12):23-28.
[6]	Pratt J R,Blackwell D A, Clair T L S,et al. 4,4'-Isophthaloyldiphthalic Anhydride Polyimides[J]. Polym Prepr,1988,29(1):128-129.
[7]	Pratt J R,Blackwell D A, St.clair T L,et al. 4,4'-Isophthaloyidiphthalic anhydride Polyimides[J]. Polym Eng Sci,1989,29(1):63-68.
[8]	Pratt J R,St.clair T L, Progar D J. Processable Polyimide Adhesive and Matrix Composite Resin:US, 4937317 A[P].1990-06-26.
[9]	SONG Cheng,SONG Caisheng. A Preparation Method of 4, 4'-Terephthaloyldiphthalic and Its Products and Uses:CN201310384452[P].2013-08-29(in Chinese). 宋琤,宋才生. 一种聚合级4, 4'-对苯二甲酰二邻苯二甲酸酐的制法及其产品和用途:CN201310384452[P].2013-08-29.
[10]	ZHAN Meidong,HONG Huiming,WANG Liyun,et al. Synthesis and Properties of Organosolubile Dikentone Anhydride Copolymides[J]. Polym Mater Sci Eng,2016,32(8):16-20(in Chinese). 詹美栋,洪慧铭,王利云,等. 一种可溶性双酮酐型共聚酰亚胺的合成及性能[J]. 高分子材料科学与工程,2016,32(8):16-20.
[11]	HU Shuncheng,CHEN Zhiqiang,HONG Huiming,et al. The Synthesis and Characterization of Novel Thermoplastic Polyimide Based on Diketone Anhydride[J]. J Jiangxi Norm Univ(Nat Sci),2016,40(4):415-419(in Chinese). 胡顺成,陈志强,洪慧铭,等. 新型热塑性的双酮酐型聚酰亚胺的合成与性能研究[J]. 江西师范大学学报(自然科学版),2016,40(4):415-419.
[12]	Seo Y,Lee S M,Kim D Y.Kinetic Study of the Imidization of a Poly(ester amic acid) by FT-Raman Spectroscopy[J]. Macromolecules,1997,30(13):3747-3753.
[13]	SONG Cheng,CHEN Zhiqiang,JIANG Yangcheng,et al. Synthesis and Properties of 4,4'-Terephthaloyldiphthalic/PMDA Anhydride Copolyimide[J]. Polym Mater Sci Eng,2015,12:27-31(in Chinese). 宋琤,陈志强,江杨诚,等. 4,4'-对苯二甲酰二邻苯二甲酸酐和均苯四甲酸酐共聚酰亚胺的合成与性能[J]. 高分子材料科学与工程,2015,31(12):27-31.
[14]	Vanherck K,Koeckelberghs G,Vankelecom I.Crosslinking Polyimides for Membrane Applications:A Review[J]. Prog Polym Sci,2013,38:874-896.
[15]	Liaw D J,Wang K L,Huang Y C,et al. Advanced Polyimide Materials:Syntheses, Physical Properties, and Applications[J]. Prog Polym Sci,2012,37:907-974