含酰胺结构超低膨胀聚酰亚胺薄膜的热膨胀行为

doi:10.7503/cjcu20190563

摘要/Abstract

摘要：

采用联苯二酐与3种含酰胺结构二胺制备了具有不同取代基团的聚酰胺-酰亚胺薄膜, 考察了酰胺结构对薄膜力学、耐热及尺寸稳定性的影响, 研究了聚集态结构与薄膜热膨胀行为的关系和规律. 该系列薄膜具有超高强度和优异的耐热性能, 拉伸强度高达280.5 MPa, 玻璃化转变温度在389~409 ℃, 并在30~300 ℃温度范围内表现出超低负膨胀, 热膨胀系数(CTE, ppm/℃, 即10 ⁶ cm·cm ^-1·℃ ^-1)在-3.05~-1.74 ppm/℃之间. 聚集态分析结果表明, 酰胺结构使分子链间形成了强氢键相互作用, 分子链在薄膜面内方向高度有序取向, 并在膜厚方向堆积更为紧密, 使薄膜表现出热收缩现象. 通过不同体积大小的取代基团进一步调控分子链间相互作用及排列堆积, 可实现薄膜在高温下近乎零尺寸形变, 为设计制备超低膨胀聚合物基板材料提供了新思路.

关键词: 聚酰亚胺, 氢键作用, 聚集态结构, 热膨胀行为

Abstract:

A series of amide-containing polyimide i. e. poly(amide-imide) films was prepared from biphenyl tetracarboxylic dianhydride and three diamines comprising diamide groups via two-step thermal imidization method. The effect of amide structure and different substituents on mechanical properties, water absorption, thermal properties and thermal expansion behavior of poly(amide-imide) films were investigated. The results showed that these films exhibited ultrahigh tensile strength up to 280.5 MPa and excellen theat resistance with T_g above 389 ℃. Moreover, these films showed ultralow thermal expansion coefficient(CTE) from -3.05 to -1.74 ppm/℃ in the wide temperature range of 30—300 ℃. The correlation of their thermal expansion behavior with aggregation structures including molecular chain interactions, orientation and packing was systematically studied. It was found that the molecular chains of poly(amide-imide)s were highly oriented along the in-plane direction while densely packed in the out-of-plane direction, because of the hydrogen bonding interactions between amide structures and the rigid linear backbone. That was the main reason for the thermal contraction of films and contributed to their outstanding dimensional stabilities. The aggregation structures of poly(amide-imide)s could be further affected by the substituents in the backbones with different volume and steric effect, resulting in the regulation of CTE values close to zero. It provids a new design thought for the heat-resistant polymer substrates with ultralow CTE for optoelectronic application.

Key words: Polyimide, Hydrogen bonding interaction, Aggregation structure, Thermal expansion behavior

中图分类号:

O631

TrendMD:

白兰, 翟磊, 王畅鸥, 何民辉, 莫松, 范琳. 含酰胺结构超低膨胀聚酰亚胺薄膜的热膨胀行为. 高等学校化学学报, 2020, 41(4): 795.

BAI Lan, ZHAI Lei, WANG Changou, HE Minhui, MO Song, FAN Lin. Thermal Expansion Behavior of Amide-containing Polyimide Films with Ultralow Thermal Expansion Coefficient ^†. Chem. J. Chinese Universities, 2020, 41(4): 795.

图/表 11

Scheme 1 Synthetic routes of PAI-1, PAI-2 and PAI-3 APTA and PAI-1(s-BPDA/APTA): R=H; AFPTA and PAI-2(s-BPDA/AFPTA): R=F; AMPTA and PAI-3(s-BPDA/AMPTA): R=CH3

Fig.1 ATR-FTIR spectra of PAI-1(a), PAI-2(b) and PAI-3(c)

Fig.2 Water absorption, water contact angle and amide content of PAI-1, PAI-2 and PAI-3

Table 1 Tensile strength, modulus and elongation at break of PAI-1, PAI-2 and PAI-3 films

Film	Tensile strength/MPa	Modulus/GPa	Elongation at break(%)
PAI-1	280.5±9.9	9.3±0.1	8.6±1.1
PAI-2	242.1±4.0	10.2±0.2	5.2±0.2
PAI-3	244.6±19.5	11.6±0.3	2.7±0.4

Fig.3 DMA(A) and TGA(B) curves of PAI-1, PAI-2 and PAI-3 films

Table 2 Thermal properties of PAI-1, PAI-2 and PAI-3 films*

Film	T_g/℃	T_d/℃	T_5%/℃	R_w(%)	CTE/(ppm·℃^-1)		[(ΔL-L₀)/L₀](%)
Film	T_g/℃	T_d/℃	T_5%/℃	R_w(%)	30—300 ℃	30—350 ℃	30—300 ℃	30—350 ℃
PAI-1	406	530	534	58.4	-3.05	-3.93	-0.082	-0.12
PAI-2	389	486	488	63.3	-2.62	-4.96	-0.071	0.17
PAI-3	409	499	510	61.3	-1.74	-5.31	-0.047	-0.16

Fig.4 TMA curves of PAI-1, PAI-2 and PAI-3 films

Table 3 Refractive indices and XRD data of PAI-1, PAI-2 and PAI-3 films*

Film	n_TE	n_TM	n_av	Δn	d-spacing/nm	d(ch-pack)/nm
PAI-1	1.8542	1.6241	1.7808	0.2301	0.4312	0.4939
PAI-2	1.8471	1.6195	1.7713	0.2276	0.4323	0.4996
PAI-3	1.8291	1.6051	1.7544	0.2238	0.5092	0.5011
Ref-PI	1.7451	1.6682	1.7199	0.0769	0.4908	0.4937

Fig.5 Effects of birefringence(a) and averagere fractive(b) on the CTE of PAI-1, PAI-2 and PAI-3

Fig.6 Reflection(A) and transmission(B) WAXD patterns of PAI-1, PAI-2 and PAI-3 films

Fig.7 Effects of d-spacing and d(ch-pack) on the CTE of PAI-1, PAI-2 and PAI-3 films

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