TMS/H_2O配比对丙烯腈/衣康酸共聚物制备及性能的影响The Preparation and Properties of Acrylonitrile/Itaconic Acid Copolymers Affected by the Solvent Ratios of TMS/H_2O
邵泽春,曾照坡,肖茹,吕永根
SHAO Ze-chun,ZENG Zhao-po,XIAO Ru,Lü Yong-gen
摘要(Abstract):
以环丁砜(TMS)和水(H_2O)为反应介质,制备丙烯腈/衣康酸共聚物。利用FTIR、SEM、WAXRD和DSC等方法研究不同溶剂配比对共聚物结构性能的影响。研究结果表明:随溶剂中TMS含量减少,共聚物的相对分子质量线性增加,转化率呈先增大后减小的趋势,在TMS/H_2O质量比30/70时,转化率存在最大值,达96%;随溶剂中TMS含量的增加,聚合物颗粒形貌由坚硬的细粒团簇状转变为蓬松多孔的大颗粒;溶剂配比对主要官能团的峰位置无显著影响,但随溶剂中TMS含量的增加,环化起始温度和放热速率明显降低,环化放热反应缓和。
The acrylonitrile/itaconic acid(AN/IA) copolymers were prepared with sulfolane/water as reactionmedium. The effects of solvent ratio on structure and properties were studied, the structure and performanceof the polyacrylonitrile were characterized by FTIR, SEM, WAXRD and DSC, respectively. The resultsshow that molecular weight linearly increases with the decrease of sulfolane content in the solvent, and theconversion rate firstly increases and then decreases, the highest polymerization conversion is obtained at aTMS/H2 O mass ratio of 30/70, conversion rate up to 96%. The morphology of the polymer particles changesfrom hard particles to fluffy porous large particles with the increase of the sulfolanecontent. The solvent ra-tio has no significant effect on the peak position of the main functional groups. However, the initial tempera-ture and the exothermic rate of cyclization decrease obviously, and the exothermic cyclization reaction mod-erates with the increase of TMS content in the solvent.
关键词(KeyWords):
聚丙烯腈;环丁砜;转化率;溶剂配比;性能
polyacrylonitrile;sulfolane;conversion rate;solvent ratio;property
基金项目(Foundation):
作者(Author):
邵泽春,曾照坡,肖茹,吕永根
SHAO Ze-chun,ZENG Zhao-po,XIAO Ru,Lü Yong-gen
DOI: 10.16090/j.cnki.hcxw.2018.03.002
参考文献(References):
- [1]林农,张爱丽,罗东,等.水相沉淀与溶液聚合法合成丙烯腈共聚物的对比[J].合成纤维,2009,38(9):25-28.
- [2]张旺玺,李木森,徐忠波,等.丙烯腈与衣康酸在DMSO/H2O中的聚合及聚合物性能表征[J].高分子学报,2003(1):83-87.
- [3]曾照坡,张珍珍,肖茹,等.聚合反应介质对丙烯腈/衣康酸共聚物结构与性能的影响[J].高分子学报,2016(9):1229-1237.
- [4]黄代忠,顾诗华.环丁砜的合成及其应用[J].四川化工,1991(3):40-43.
- [5]许国强.环丁砜及其广泛用途[J].辽宁化工,1986(5):33-37.
- [6]代永强.超高分子量聚丙烯腈混合溶剂沉淀聚合等理论研究及原丝制备工艺的探索[D].北京:北京化工大学,2013.
- [7]张旺玺.聚丙烯腈基碳纤维[M].上海:东华大学出版社,2005.
- [8]孙以实,冯新德.丙烯腈的共聚合及其竞聚率的研究[J].高分子学报,1966(2):59-67.
- [9]MUKESH K Jain,ABHIRAMAN A S.Conversion of acrylonitrilebased precursors to carbon fibres[J].Journal of Materials Science,1987,22(1):278-300.
- [10]HINRICHSEN G.Structural changes of drawn polyacrylonitrile during annealing[J].Journal of Polymer Science Polymer Symposia,1972,38(1):303-314.
- [11]GUPTA A K,SINGHAL R P.Effect of copolymerization and heat treatment on the structure and x-ray diffraction of polyacrylonitrile[J].Journal of Polymer Science Polymer Physics Edition,1983,21(11):2243-2262.
- [12]SHAARI Moghadam S H,HAJIR B S.Copolymerization of acrylonitrile-acrylic acid in DMF/H2O mixture[J].Iranian Polymer Journal,2005,14(12):1032-1041.
- [13]GUPTA A K,PALIWAL D K,Bajaj P.Effect of the nature and mole fraction of acidic comonomer on the stabilization of polyacrylonitrile[J].Journal of Applied Polymer Science,2015,59(12):1819-1826.