丙烯腈溶液共聚过程体系黏度变化的动态测定与理论分析

doi:10.3969/j.issn.0438-1157.2013.02.046

化工学报 ›› 2013, Vol. 64 ›› Issue (2): 742-748.DOI: 10.3969/j.issn.0438-1157.2013.02.046

• 材料化学工程与纳米技术 • 上一篇下一篇

丙烯腈溶液共聚过程体系黏度变化的动态测定与理论分析

缪金根¹, 王世栋¹, 程振民¹, 周美华², 潘鼎²

1. 华东理工大学,化学工程联合国家重点实验室,上海 200237;
2. 东华大学高性能纤维及制品教育部重点实验室,上海 201620

收稿日期:2012-07-18 修回日期:2012-08-20 出版日期:2013-02-05 发布日期:2013-02-05
通讯作者: 程振民
作者简介:缪金根(1982—),男,博士研究生。
基金资助:
上海市科委资助项目(07DJ14002,09DZ1100203)。

Viscosity behavior of solution copolymerization of acrylonitrile and itaconic acid:on-line determination and theoretical analysis

MIAO Jingen¹, WANG Shidong¹, CHENG Zhenmin¹, ZHOU Meihua², PAN Ding²

1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China;
2. Key Laboratory of High Performance Fibers & Products, Ministry of Education, Donghua University, Shanghai 201620, China

Received:2012-07-18 Revised:2012-08-20 Online:2013-02-05 Published:2013-02-05
Supported by:
supported by the Science and Technology Committee of Shanghai Municipal Government(07DJ14002, 09DZ1100203).

摘要/Abstract

摘要： 通过BrookField DV-Ⅲ Ultra可编程旋转流变仪实时测定了以偶氮二异丁腈为引发剂,二甲基亚砜为溶剂,丙烯腈-衣康酸二元溶液共聚合体系的零剪切黏度变化。同时设计相同条件的封管实验测定转化率,并利用Arrhenius-Frenkel-Eyring方程导出了适合描述丙烯腈溶液共聚合体系的零剪切黏度随固含量、温度及黏均分子量变化的经验关联式。结果表明,各工艺条件对体系黏度都有显著影响,原料配比细微的差别将导致最终原液黏度相差数百帕秒以上,调控黏度时需综合考虑。值得注意的是,所有实验条件下反应2～3 h后,体系黏度激增1000倍以上,即从约2 mPa·s的初始黏度迅速增加至2～3 Pa·s;而当总单体含量达到28%时体系产生凝胶效应,反应一定时间后黏度急剧增长。另外发现,当体系达到某一临界固含量时,溶液中大分子发生链缠结,固含量微小的增量就会导致体系黏度剧增。

关键词: 黏度, 聚丙烯腈, 分子量, 溶液聚合, 碳纤维

Abstract: A programmable torque rheometer was used for on-line determination of zero shear viscosity of solution copolymerization of acrylonitrile and itaconic acid in dimethylsulfoxide.The Arrhenius- Frenkel-Eyring equation was extended to identify the dependence of zero shear viscosity on polymer content, temperature and viscosity-average molecular weight of polyacrylonitrile.It was observed that under all of these process conditions, small differences in feed composition would give rise to a large variation on zero shear viscosity and ultimate viscosity to more than 100 Pa·s, so the control strategy for viscosity should be considered critically.The changes of reaction temperature seemed to be more effective than other methods.The viscosity increased quickly from about 2 mPa·s to 2—3 Pa·s in the first three hours under all experiment conditions which would greatly depress heat exchange and mixing efficiency.It was also found that viscosity increased dramatically as a result of gel effect when total overall monomer mass fraction was beyond 28% in feed.In addition, a small increase of polymer content could give rise to a great increase in viscosity when polymer content reached some critical values, which indicated that macromolecules were entangled severely in copolymerization solution.

Key words: viscosity, polyacrylonitrile, molecular weight, solution polymerization, carbon fiber

中图分类号:

TQ342⁺.31

缪金根, 王世栋, 程振民, 周美华, 潘鼎. 丙烯腈溶液共聚过程体系黏度变化的动态测定与理论分析[J]. 化工学报, 2013, 64(2): 742-748.

MIAO Jingen, WANG Shidong, CHENG Zhenmin, ZHOU Meihua, PAN Ding. Viscosity behavior of solution copolymerization of acrylonitrile and itaconic acid:on-line determination and theoretical analysis[J]. CIESC Journal, 2013, 64(2): 742-748.

参考文献 19

[1]	Sen S, Bahrami S H, Bajaj P.High-performance acrylic fibers[J].J.Macromol.Sci., Polym.Rev., 1996, 36(1):1-76
[2]	Deng W, Lobovsky A, Iacono S T, et al.Poly(acrylonitrile-co-1-vinylimidazole):a new melt processable carbon fiber precursor[J].Polymer, 2011, 52(3):622-628
[3]	Chen Hou(陈厚), Zhang Wangxi(张旺玺), Wang Chengguo(王成国), Cai Huasu(蔡华甦).Comparative study of acrylonitrile copolymer prepared by suspension and solution polymerization[J].Synthetic Fiber(合成纤维), 2002, 31(3):10-13
[4]	Zhao Y, Wang C, Wang Y, et al.Aqueous deposited copolymerization of acrylonitrile and itaconic acid[J].J.Appl.Polym.Sci., 2009, 111(6):3163-3169
[5]	Cheng Lu(程璐), Wang Haojing(王浩静).Study on factors affecting viscosity during polymerization of acrylonitrile[J].New Chemical Materials(化工新型材料), 2010, 38(7):97-99
[6]	Mahdavian A R, Abdollahi M.Kinetic study of radical polymerization(Ⅶ):Investigation into the solution copolymerization of acrylonitrile and itaconic acid by real-time 1H NMR spectroscopy[J].J.Appl.Polym.Sci., 2007, 103:3253-3260
[7]	Takenaka M, Johnson A F, Kamide K.Aspects of high-conversion free-radically initiated polymerizations(Ⅰ):Initiator efficiency in the homopolymerization of acrylonitrile and methyl acrylate in dimethylsulfoxide with azobisisobutyronitrile as initiator[J].Polymer, 1994, 35(18):3899-3907
[8]	Tan L J, Wan A J, Pan D.Viscoelasticity of concentrated polyacrylonitrile solutions:effects of solution composition and temperature[J].Polym.Int., 2011, 60(7):1047-1052
[9]	Tan L J, Pan J P, Wan A J.Shear and extensional rheology of polyacrylonitrile solution:effect of ultrahigh molecular weight polyacrylonitrile[J].Colloid.Polym.Sci., 2012, 290(4):289-295
[10]	Devasia R, Nair C P R, Ninan K N.Temperature and shear dependencies of rheology of polyacrylonitrile co itaconic acid)dope in DMF[J].Polym.Adv.Technol., 2008, 19(12):1771-1778
[11]	Devasia R, Nair C P R, Ninan K N.Rheological behavior of dope solutions of poly(acrylonitrile-co-itaconic acid)in N,N-dimethylformamide:effect of polymer molar mass[J].J.Macromol.Sci., Pure Appl.Chem., 2008, 45(3):248-254
[12]	Bridgman P W. The thermal conductivity of liquids under pressure[J].Proceedings of the American Academy of Arts and Sciences, 1923,59(7):141-169
[13]	Nieto-Draghi C, Avalos J B, Rousseau B. Transport properties of dimethyl sulfoxide aqueous solutions[J].J.Chem.Phy., 2003,119(9):4782-4789
[14]	Brandrup J, Immergut E H, Grulke E A.Polymer Handbook[M].4th ed.New York:John Wiley & Sons Inc., 1998:V/64
[15]	Athawale V D, Desai V M.Studies in concentrated solution properties of 1,4-cis-polybutadiene, polystyrene, and polychloroprene using viscometry as a tool[J].J.Polym.Mater., 2001, 18(4):423-432
[16]	Zhang Wangxi(张旺玺), Jiang Qingli(姜庆利), Liu Jianjun(刘建军), Wang Yanzhi(王艳芝), Cao Huaihua(曹怀华), Cai Huasu(蔡华苏).Study on AN-IA copolymerization in DMSO solution[J].Journal of Shandong University of Technology(山东工业大学学报), 1998, 28(5):401-406
[17]	Devasia R, Nair C P R, Ninan K N.Solvent and kinetic penultimate unit effects in the copolymerization of acrylonitrile with itaconic acid[J].Eur.Polym.J., 2002, 38(10):2003-2010
[18]	Buback M, Egorov M, Gilbert R G, Kaminsky V, Olaj O F, Russell G T, Vana P, Zifferer G. Critically evaluated termination rate coefficients for free-fadical polymerization(Ⅰ):The current situation[J].Macromol.Chem.Phy., 2002, 203(18):2570-2582
[19]	O'Neil G A, Torkelson J M.Modeling insight into the diffusion-limited cause of the gel effect in free radical polymerization[J].Macromolecules, 1999,32(2):411-422

丙烯腈溶液共聚过程体系黏度变化的动态测定与理论分析

Viscosity behavior of solution copolymerization of acrylonitrile and itaconic acid:on-line determination and theoretical analysis

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献 19

相关文章 15

编辑推荐

Metrics

本文评价

[1]	刘爽, 张霖宙, 许志明, 赵锁奇. 渣油及其组分黏度的分子层次组成关联研究[J]. 化工学报, 2023, 74(8): 3226-3241.
[2]	李靖, 沈聪浩, 郭大亮, 李静, 沙力争, 童欣. 木质素基碳纤维复合材料在储能元件中的应用研究进展[J]. 化工学报, 2023, 74(6): 2322-2334.
[3]	雷博雯, 吴建华, 吴启航. R290低压比热泵高补气过热度循环研究[J]. 化工学报, 2023, 74(5): 1875-1883.
[4]	周必茂, 许世森, 王肖肖, 刘刚, 李小宇, 任永强, 谭厚章. 烧嘴偏转角度对气化炉渣层分布特性的影响[J]. 化工学报, 2023, 74(5): 1939-1949.
[5]	尹驰, 张正国, 凌子夜, 方晓明. 含石蜡@二氧化硅纳米胶囊和碳纤维的相变热界面材料及其散热性能[J]. 化工学报, 2023, 74(4): 1795-1804.
[6]	张永泉, 玄伟伟. 碱金属/（FeO+CaO+MgO）对硅酸盐灰熔渣结构和黏度的影响机理[J]. 化工学报, 2023, 74(4): 1764-1771.
[7]	张雪婷, 胡激江, 赵晶, 李伯耿. 高分子量聚丙二醇在微通道反应器中的制备[J]. 化工学报, 2023, 74(3): 1343-1351.
[8]	靳志远, 单国荣, 潘鹏举. AM/AMPS/SSS三元共聚物的制备及耐温耐盐性能[J]. 化工学报, 2023, 74(2): 916-923.
[9]	张家庆, 蒋榕培, 史伟康, 武博翔, 杨超, 刘朝晖. 煤基/石油基火箭煤油高参数黏温特性与组分特性研究[J]. 化工学报, 2023, 74(2): 653-665.
[10]	姚翰林, 辛忠. 液相沉淀反应在管式微通道反应器中的流动行为研究[J]. 化工学报, 2022, 73(8): 3518-3528.
[11]	王江丽, 薛敏, 赵承科, 岳凤霞. 木质素分级对其应用性能的影响[J]. 化工学报, 2022, 73(5): 1894-1907.
[12]	王利霞, 毕肇杰, 史淼磊, 王晨, 王东方, 李倩. UHMWPE/PEG共混方式及配比对UHMWPE缠结行为及性能的影响[J]. 化工学报, 2022, 73(2): 933-940.
[13]	朱晨阳, 刘向阳, 何茂刚, 陈光进. 基于Eyring绝对速率理论的流体混合物黏度推算[J]. 化工学报, 2022, 73(11): 4826-4837.
[14]	张家庆, 刘朝晖, 李宇, 宋晨阳. 碳氢燃料JP-10高温液态黏度测量和推算模型构建方法研究[J]. 化工学报, 2022, 73(1): 153-161.
[15]	罗伟莉, 王雯雯, 潘权稳, 葛天舒, 王如竹. 基于活性碳纤维毡复合吸附剂的储热性能[J]. 化工学报, 2021, 72(S1): 554-559.