纺织学报 ›› 2020, Vol. 41 ›› Issue (04): 174-180.doi: 10.13475/j.fzxb.20190308007

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自由基引发剂制备高相对分子质量聚丙烯腈研究进展

赵亚奇1(), 郭雯静2, 杜玲枝1, 赵振新1, 赵海鹏1   

  1. 1.河南城建学院 材料与化工学院, 河南 平顶山 467036
    2.郑州大学 化工与能源学院, 河南 郑州 450001
  • 收稿日期:2019-03-28 修回日期:2019-12-17 出版日期:2020-04-15 发布日期:2020-04-27
  • 作者简介:赵亚奇(1985—),男,副教授,博士。主要研究方向为聚丙烯腈的合成与表征。E-mail: zhyq5891@163.com。
  • 基金资助:
    国家自然科学基金青年基金项目(51803047);河南省科技厅项目(202102210035);河南省高等学校青年骨干教师培养计划项目(2019GGJS227);河南城建学院校级学术技术带头人项目(YCJXSJSDTR201909)

Research progress of high relative molecular weight polyacrylonitrile prepared by radical initiators

ZHAO Yaqi1(), GUO Wenjing2, DU Lingzhi1, ZHAO Zhenxin1, ZHAO Haipeng1   

  1. 1. School of Materials and Chemical Engineering, Henan University of Urban Construction,Pingdingshan, Henan 467036, China
    2. School of of Chemical Engineering and Energy,Zhengzhou University, Zhengzhou, Henan 450001, China
  • Received:2019-03-28 Revised:2019-12-17 Online:2020-04-15 Published:2020-04-27

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摘要：

为开发高品质聚丙烯腈(PAN)共聚物用于PAN基碳纤维生产,针对水相悬浮聚合、水相沉淀聚合和混合溶剂沉淀(悬浮)聚合等自由基聚合工艺的优缺点,结合其反应特征,综述了近几年来自由基引发剂制备高相对分子质量PAN共聚物的研究进展,探讨了油溶性或水溶性引发剂的选择机制,并对制备高相对分子质量PAN共聚物的理论与实验进行分析。根据单一引发剂制备PAN共聚物的实验结果发现:采用纯水相聚合体系可制得高转化率和高相对分子质量的PAN共聚物;采用混合溶剂沉淀(悬浮)聚合反应体系,可在不降低聚合反应产率的前提下,对PAN共聚物的平均相对分子质量进行合理调节。

关键词: 自由基引发剂, 高相对分子质量聚丙烯腈, 水相体系, 混合溶剂, 引发剂选择, 高品质碳纤维原丝

Abstract:

To develop high quality polyacrylonitrile(PAN) copolymer for PAN-based carbon fiber production,in view of the advantages and disadvantages of different polymerization processes, such as aqueous suspension polymerization, aqueous precipitation polymerization and mixed-solvent precipita-tion (suspension) polymerization, and combined with its reaction characteristics, the research progress of high relative molecular weight PAN copolymer prepared by radical initiator in recent years was reviewed. The research contents include the choice of oil-soluble or water-soluble initiator,theoretical and experimental analysis of the preparation of high molecular weight PAN polymer. From the experiment results of PAN copolymers synthesized by a single initiator, it is understood that PAN copolymers with high conversion and high molecular weight can be obtained by using the water phase polymerization system. On the premise of not reducing the polymerization reaction yield, average molecular weights of PAN copolymers can be reasonably adjusted by using the mixed-solvent precipitated (suspension) polymerization.

Key words: radical initiator, high relative molecular weight polyacrylonitrile, aqueous medium, mixed-solvent, initiator selection, high quality carbon fiber precursor

中图分类号: 

  • TQ342

表1

不同聚合方法制备PAN均聚物的理论计算结果"

聚合方法 极限相对分子质量
均相溶液聚合 2.43×105
水相沉淀/悬浮聚合 17.67×105
混合溶剂沉淀(悬浮)聚合 2.43×105~17.67×105

表2

不同聚合方法制备PAN共聚物的实验结果"

实验
序号		 聚合方法 共聚单体
质量配比		 单体质
量分
数/%		 引发剂 引发剂
质量分
数/%		 反应时
间/h		 其他反应条件 转化
率/%		 PAN黏均
分子量/
105		 参考
文献
1 均相溶液
聚合		 m(AN):
m(AA)=98:2		 25 [AIBN] 1 2 反应温度为60 ℃ 75.1 0.8 [34]
2 水相悬浮
聚合		 m (AN):
m (MA)=95:5		 25 [AIBN] 1 4 反应温度为60 ℃,引入质量分数为0.5%的PVA 39.5 7.59 [18]
3 水相悬浮
聚合		 m (AN):
m (IA)=98:2		 17 [AIBN] 0.6 2 反应温度为60 ℃,引入质量分数为0.15%的PVA 52.9 7.5 [19]
4 水相沉淀
聚合		 m (AN):
m (IA)=99:1		 22 [APS] a:0.8
b:1.2		 2 a:无相对分子质量调节剂
b:引入质量分数为0.5%的
n-DDM		 a:75.2
b:72.5		 a:12.02
b:2.00		 [22]
5 水相沉淀
聚合		 m (AN):
m (MA)=98:2		 22 [APS] 1 3 反应温度为65 ℃ 91.6 7.15 [35]
6 混合溶剂
沉淀聚合		 m (AN):
m (IA)=98:2		 22 [APS] 0.6 2 反应温度为60 ℃,DMSO和H2O质量比为50:50 86.0 9.23 [36]
7 混合溶剂
沉淀聚合		 m (AN):
m (MA)=99:1		 20 [AIBN] 0.6 2 反应温度为60 ℃
DMSO和H2O质量比为20:80		 48.2 5.6 [11]
8 混合溶剂
悬浮聚合		 m (AN):
m (AA)=98:2		 25 [AIBN] 1 2 反应温度为60 ℃,引入质量分数为0.1%的PVA,DMF和H2O体积比为10:90 35.7 3.39 [34]
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