聚对苯二甲酰对苯二胺浓硫酸溶液的相转变与剪切流变研究

赵鸣; 唐凯; 雒瑞银; 李京津; 马千里; 刘庚鑫; 滕翠青

doi:10.14028/j.cnki.1003-3726.2025.25.072

您当前的位置：

首页 >

文章列表页 >

聚对苯二甲酰对苯二胺浓硫酸溶液的相转变与剪切流变研究

流变学专辑特约研究论文 | 更新时间：2025-07-15

- 聚对苯二甲酰对苯二胺浓硫酸溶液的相转变与剪切流变研究
- Study on Phase Transition and Shear Rheology of Concentrated Sulfuric Acid Solution of Poly(p-phenylene terephthalamide)
- 高分子通报 2025年38卷第8期页码：1291-1298
- 作者机构：
  
  1.东华大学先进纤维材料全国重点实验室，先进低维材料中心，材料科学与工程学院，上海 201620
  2.宁夏泰和芳纶纤维有限责任公司，银川 750411
  3.泰和新材集团股份有限公司，烟台 264006
  4.东华大学先进纤维材料全国重点实验室，材料科学与工程学院，上海 201620
- 作者简介：
  
  lgx@dhu.edu.cn
  cqteng@dhu.edu.cn
- 基金信息：
  
  国家重点研发计划(2021YFB3700102);国家自然科学基金(22473025);上海市科技创新行动计划自然科学基金(22ZR1401300)
- DOI：10.14028/j.cnki.1003-3726.2025.25.072
  中图分类号：
- 收稿日期：2025-03-05，
  
  录用日期：2025-05-04，
  
  网络出版日期：2025-06-26，
  
  纸质出版日期：2025-08-20
- 稿件说明：
移动端阅览
赵鸣, 唐凯, 雒瑞银, 李京津, 马千里, 刘庚鑫, 滕翠青. 聚对苯二甲酰对苯二胺浓硫酸溶液的相转变与剪切流变研究. 高分子通报, 2025, 38(8), 1291–1298.

Zhao, M.; Tang, K.; Luo, R. Y.; Li, J. J.; Ma, Q, L.; Liu, G. X.; Teng, C. Q. Study on phase transition and shear rheology of concentrated sulfuric acid solution of poly(p-phenylene terephthalamide). Polym. Bull. (in Chinese), 2025, 38(8), 1291–1298.
赵鸣, 唐凯, 雒瑞银, 李京津, 马千里, 刘庚鑫, 滕翠青. 聚对苯二甲酰对苯二胺浓硫酸溶液的相转变与剪切流变研究. 高分子通报, 2025, 38(8), 1291–1298. DOI： 10.14028/j.cnki.1003-3726.2025.25.072.

Zhao, M.; Tang, K.; Luo, R. Y.; Li, J. J.; Ma, Q, L.; Liu, G. X.; Teng, C. Q. Study on phase transition and shear rheology of concentrated sulfuric acid solution of poly(p-phenylene terephthalamide). Polym. Bull. (in Chinese), 2025, 38(8), 1291–1298. DOI： 10.14028/j.cnki.1003-3726.2025.25.072.

摘要

聚对苯二甲酰对苯二胺(PPTA)能溶于浓硫酸(H

)，在一定的温度和浓度范围内呈现液晶相，可以经干喷湿法工艺纺丝制得对位芳纶。PPTA/H

溶液的相行为和流变行为是决定对位芳纶加工工艺和性能的关键因素，但是缺乏便捷的研究工具。本研究为旋转流变仪设计并制作了能够耐受浓硫酸的平行板夹具，揭示不同分子量PPTA/H

溶液的相转变和剪切流变行为。通过偏光显微镜观察PPTA/H

溶液的液晶织构，结合流变的线性黏弹性，确定相转变温度和边界。通过流变的振荡扫描以及稳态剪切，探索温度、质量分数和PPTA分子量与溶液的储能模量、松弛时间和黏度的关系。结果表明：更高浓度的PPTA/H

溶液具有更宽的向列相(N)的温度范围，并且相转变临界温度也更高；模量、松弛时间和黏度随着浓度增加呈现非单调的变化；高浓度溶液在稳态剪切中表现出非线性流变行为。进一步理解PPTA/H

溶液的相转变条件以及剪切流变行为，将会对对位芳纶纺丝工艺参数的指导与改进有着重要意义。

Abstract

Poly(

-phenylene terephthalamide) (PPTA) can be dissolved in concentrated sulfuric acid (H

) and exhibits a liquid crystalline phase within a certain temperature and concentration range. It can be spun into para-aramid fibers through the dry-jet wet spinning process. The phase behavior and rheological behavior of PPTA/H

solutions are key factors determining the processing technology and performance of para-aramid fibers. However

there is a lack of convenient research tools. In this paper

a parallel plate fixture resistant to concentrated sulfuric acid was designed and fabricated for a rotational rheometer to reveal the phase transition and shear rheological behavior of PPTA/H

solutions with different molecular weights. The liquid crystalline texture of PPTA/H

solutions was observed by polarizing microscopy

and the phase transition temperature and boundaries were determined in combination with the linear viscoelasticity of rheology. The relationship between temperature

mass fraction

PPTA molecular weight and the storage modulus

relaxation time and viscosity of the solution was explored through rheological oscillation scanning and steady shear. The results show that higher concentration PPTA/H

solutions have a wider temperature range of the nematic phase (N) and a higher critical temperature for phase transition; the modulus

relaxation time and viscosity show non-monotonic changes with increasing concentration; high concentration solutions exhibit nonlinear rheological behavior in steady shear. A f

urther understanding of the phase transition conditions and shear rheological behavior of PPTA/H

solutions will be of great significance for guiding and improving the spinning process parameters of para-aramid fibers.

关键词

Keywords

references

李晔 . 对位芳纶的发展现状、技术分析及展望 . 合成纤维 , 2009 , 38 ( 9 ), 1 – 5 .

Kwolek, S. L . Mass and fibres or threads made from it. 1810426.2 . 1968 .

Wang, W. B. ; Qi, X. ; Guan, Y. ; Zhang, F. ; Zhang, J. ; Yan, C. ; Zhu, Y. D. ; Wan, X. H . Synthesis and properties of poly( p -phenylene terephthalamide) bearing both polar and unsaturated substituents introduced via claisen rearrangement reaction . J. Polym. Sci. Part A Polym. Chem. , 2016 , 54 ( 13 ), 2050 – 2059 .

Northolt, M. G. ; Sikkema, D. J . Lyotropic main chain liquid crystal polymers . Separation Techniques Thermodynamics Liquid Crystal Polymers . Berlin, Heidelberg : Springer , 1990 . 115 – 177 .

Shibaev, V. P. ; Platé, N. A . Thermotropic liquid-crystalline polymers with mesogenic side groups . Liquid Crystal Polymers Ⅱ/Ⅲ. Berlin, Heidelberg : Springer , 1984 . 173 – 252 .

Gordon, M. ; Platé, N. A. Dobb, M . G . Liquid Crystal Polymers Ⅱ/Ⅲ. Berlin, Heidelberg : Springer , 1984 .

Han, W. H. ; Zhao, T. Y. ; Wang, X. G . Study of first normal stress difference of poly( p -phenylene terephthalamide) in sulfuric acid . Polymer , 2015 , 57 , 150 – 156 .

Han, W. H. ; Zhao, T. Y. ; Wang, X. G . Steady shear viscosity and oscillatory complex viscosity of poly( p -phenylene terephthalamide) solutions in sulfuric acid . Rheol. Acta , 2016 , 55 ( 3 ), 257 – 266 .

Han, W. H. ; Zhao, T. Y. ; Wang, X. G . Dynamic viscoelastic relaxations of nematic solutions of poly( p -phenylene terephthamide) in sulfuric acid after cessation of shearing . Polymer , 2015 , 67 , 72 – 79 .

Zhou, S. ; Li, C. S. ; Fan, X. H. ; Shen, Z. H . Effect of hydrogen bonding on the liquid crystalline behavior of poly( p -phenylene terephthamide) in sulfuric acid . Polymer , 2018 , 143 , 316 – 323 .

Arpin, M. ; Strazielle, C . Characterization and conformation of aromatic polyamides: poly(1, 4-phenylene terephthalamide) and poly( p -benzamide) in sulphuric acid . Polymer , 1977 , 18 ( 6 ), 591 – 598 .

杨拯 , 吴清基 , 顾锦江 . PPTA低温硫酸溶解工艺研究 . 高科技纤维与应用 , 2010 , 35 ( 2 ), 6 – 9 .

张光耀 . PPTA聚合体低温溶解工艺的探究 . 硕士学位论文 , 上海 : 东华大学 , 2023 .

Teng, C. Q. ; Li, H. ; Liu, J. ; Gu, H. ; Kong, H. J. ; Yu, M. H . Effect of high molecular weight PPTA on liquid crystalline phase and spinning process of aramid fibers . Polymers , 2020 , 12 ( 5 ), 1206 .

Rommel, H. ; Foerster, G . Topology of the ternary phase system poly( p -phenyleneterephthalamide)-sulfuric acid-water . Macromolecules , 1994 , 27 ( 16 ), 4570 – 4576 .

Gardner, K. H. ; Matheson, R. R. ; Avakian, P. ; Chia, Y. T. ; Gierke, T. D . A partial phase diagram and crystal solvate for the poly( p -phenyleneterephthalamide)/sulfuric acid system . J.Am.Chem.Soc. , 1984 , 91 – 102 .

王芳 , 刘娜 , 王腾飞 . PPTA硫酸溶液流变性能及纺丝工艺的研究 . 合成技术及应用 , 2022 , 37 ( 1 ), 24 – 29 .

Nesrullajev, A . Texture transformations and thermo-optical properties of nematic mesogen at nematic–isotropic liquid phase transition . J. Mol. Liq. , 2014 , 196 , 217 – 222 .

Zhou, M. ; Han, C. D . Rheology of a combined main-chain/side-chain liquid-crystalline polymer in the thermotropic and lyotropic states . Macromolecules , 2006 , 39 ( 1 ), 232 – 242 .

Cox, W. P. ; Merz, E. H . Correlation of dynamic and steady flow viscosities . J. Polym. Sci. , 1958 , 28 ( 118 ), 619 – 622 .

Gleissle, W. ; Hochstein, B . Validity of the Cox-Merz rule for concentrated suspensions . J. Rheol. , 2003 , 47 ( 4 ), 897 – 910 .

Kanso, M. A. ; Pak, M. C. ; Giacomin, A. J . Cox-Merz rules from general rigid bead-rod theory . Phys. Fluids , 2023 , 35 ( 9 ), 093112 .

Liu, F. ; Huang, S. Y. ; Tang, J. ; Chen, Q . Elongational flow-induced crystallization of poly( L -lactic acid) telechelic ionomers . Chinese J. Polym. Sci. , 2024 , 42 ( 12 ), 1957 – 1965 .

刘双 , 黄茜 , 陈全 , 黄险波 . 流变技术在高分子表征中的应用: 拉伸流变测试 . 高分子学报 , 2023 , 54 ( 2 ), 286 – 302 .

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

基于聚(N,N-二乙基丙烯酰胺)温度响应型接枝共聚物的制备与表征

炭黑/硅橡胶介电弹性体复合材料的制备研究

温敏支化聚合物的合成及其双重相转变行为

铁电性液晶高分子的研究进展