共缩聚法制备含芴大侧基无色透明聚酰亚胺薄膜及其性能

韩龙; 李静静; 窦垚; 奚桢浩; 郭旭虹; 王杰

doi:10.14133/j.cnki.1008-9357.20210901001

共缩聚法制备含芴大侧基无色透明聚酰亚胺薄膜及其性能

doi: 10.14133/j.cnki.1008-9357.20210901001

韩龙^1,,
李静静²,
窦垚¹,
奚桢浩¹,
郭旭虹¹,
王杰^1, ,

1.
华东理工大学化工学院, 化学工程联合国家重点实验室, 上海 200237
2.
中国石油化工股份有限公司茂名分公司研究院, 广东茂名 525000

基金项目: 国家自然科学基金（51403062）

详细信息

作者简介:
韩龙：韩龙 (1995—)，男，硕士研究生，主要从事无色聚酰亚胺薄膜材料的研究。E-mail: 215313062@qq.com

通讯作者:
王杰，E-mail: jiewang2010@ecust.edu.cn

中图分类号: TQ323.7
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- 被引次数: 0
出版历程
- 收稿日期: 2021-09-01
- 录用日期: 2022-02-28
- 网络出版日期: 2022-03-07
- 刊出日期: 2022-08-01

Colorless and Transparent Polyimide Film with Fluorene-Containing Large Side Groups Prepared by Copolycondensation Method

1.
State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
2.
Maoming Branch R&D Institute, SINOPEC, Maoming 525000, Guangdong, China

摘要

摘要: 以4,4′-二氨基二苯醚（ODA）和含芴大侧基的9,9-双（3-氟-4-氨基苯基）芴（FFDA）为二胺单体，4,4′-联苯醚二酐（ODPA）为二酐单体，经常温下溶液共缩聚反应得到含FFDA的聚酰胺酸（PAA）溶液，再经化学亚胺化得到无色透明聚酰亚胺（PI）薄膜。使用傅里叶红外光谱（FT-IR）、差示扫描量热（DSC）、热重分析（TGA）、X射线衍射（XRD）分析、紫外-可见分光光度计（UV-Vis）、万能材料试验机等对PI进行了结构及性能表征。结果表明：随着n（FFDA）∶n（ODPA）的投料比增加，PI的热性能和力学性能均相应提高，当该比例达到50%时，PI的可见光透过率达到85%，且室温下在常见极性溶剂中的溶解性较好。
- 聚酰亚胺 /
- 共缩聚 /
- 化学亚胺化 /
- 无色透明薄膜
Abstract: A colorless and transparent polyimide (PI) film with excellent comprehensive properties was synthesized via chemical imidization process by using 4,4'-diaminodiphenyl ether (ODA) and 9,9-bis(3-fluoro-4-aminophenyl)fluorene (FFDA) as diamine monomers, 4,4'-oxydiphthalic anhydride (ODPA) as a dianhydride monomer in dimethylformamide (DMF). The relationship between the content of FFDA and the performance of PI was studied. The optical properties, heat resistance, mechanical properties and solubilities of PI were characterized by ultraviolet-visible spectrophotometer (UV-Vis), differential scanning calorimeter (DSC), thermogravimetric analyzer (TGA), universal material testing machine, etc. The addition of diamine monomer with asymmetric large side group can increase the degree of distortion of the molecular chain to a certain extent, increase the free volume between molecules, reduce the stacking of molecular chains, and reduce the interaction among molecular chains, which weakening the charge transfer complexing effect and improving the optical transparency of the PI film. The addition of ether bonds can increase the flexibility of PI molecular chains and improve the solubility. The fluorine-containing group of the diamine part has a strong electron withdrawing effect, which significantly reduces the electron donating effect of the diamine monomer, thereby inhibiting the charge transfer complexing (CTC) effect and improving the optical performance of PI film. The results show that the PI sample with n(FFDA):n(ODPA) of 50% exhibits excellent solubility and the film presents good optical property. At ambient temperature, PI is soluble in many strong polar solvents such as N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), dimethyl acetamide (DMAc) and dimethyl sulfoxide (DMSO), which also has good solubility in weak polar solvents such as tetrahydrofuran (THF). The transmittance of PI film at 500 nm attains 85%, and its UV cutoff wavelength is as low as 365 nm. Meanwhile, the PI film has excellent thermal stability and mechanical properties.
- polyimide /
- copolycondensation /
- chemical imidization /
- colorless and transparent film

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图 1 PI的合成路线

Figure 1. Synthetic route of PI

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图 2 PI薄膜的红外光谱

Figure 2. FT-IR spectra of PI films

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图 3 PI薄膜的TGA曲线

Figure 3. TGA curves of PI films

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图 4 PI薄膜的DSC曲线

Figure 4. DSC curves of PI films

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图 5 PI薄膜的XRD谱图

Figure 5. XRD patterns of PI films

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图 6 PI薄膜的紫外-可见光谱

Figure 6. UV-Vis spectra of PI films

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图 7 PI薄膜光学透过性对比

Figure 7. Comparison of optical transmittance of PI films

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表 1 PI的单体投料比

Table 1. Monomer feed ratio of PI

Sample	n (ODA) ∶n (FFDA) ∶n (ODPA)	n(FFDA)∶n(ODPA)/%
PI	n (ODA) ∶n (ODPA)=1∶1	0
PI-30%	7∶3∶10	30
PI-50%	5∶5∶10	50
PI-70%	3∶7∶10	70

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表 2 PAA溶液的黏度

Table 2. Viscosities of PAA solutions

Sample	t₀/s	t/s	η_r/(dL·g⁻¹)	η_sp/(dL·g⁻¹)	[η]/(dL·g^-1)
PI	138.24	258.51	1.87	0.87	1.41
PI-30%	138.24	236.16	1.71	0.71	1.18
PI-50%	138.24	210.73	1.52	0.52	0.90
PI-70%	138.24	196.67	1.42	0.42	0.75
t₀：The outflow time of solvent; t：The outflow time of solution

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表 3 PI的溶解性能

Table 3. Solubilities of PI

Sample	DMAc	DMF	NMP	DMSO	DCM	THF
PI	+−	+−	+−	+	−	−
PI-30%	++	++	++	++	++	++
PI-50%	++	++	++	++	++	++
PI-70%	++	+	++	++	++	+−
++：Soluble at RT; +：Partially soluble at RT; +−：Soluble after heating; −：Partially soluble after heating

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表 4 PI薄膜的力学性能

Table 4. Mechanical properties of PI films

Sample	Tensile strength/MPa	Tensile modulus/GPa	Elongation at break/%
PI	112.4	2.2	7.8
PI-30%	123.1	2.4	8.1
PI-50%	131.6	2.9	10.6
PI-70%	143.4	3.3	12.3

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