纺织学报 ›› 2020, Vol. 41 ›› Issue (06): 1-7.doi: 10.13475/j.fzxb.20190705607

• 纤维材料 •    下一篇

生物基聚对苯二甲酸丙二醇酯低聚物的提取及其热性能

王晶晶1, 陈咏1, 王朝生1, 王华平1,2, 边树昌3, 乌婧2()   

  1. 1.东华大学 材料科学与工程学院, 上海 201620
    2.东华大学 纺织产业关键技术协同创新中心,上海 201620
    3.江苏国望高科纤维有限公司, 江苏 苏州 215000
  • 收稿日期:2019-07-19 修回日期:2020-03-11 出版日期:2020-06-15 发布日期:2020-06-28
  • 通讯作者: 乌婧
  • 作者简介:王晶晶(1994—),女,硕士生。主要研究方向为高分子材料合成。
  • 基金资助:
    国家重点研发计划项目(2017YFB0309400)

Extraction of oligomers from bio-based propylene terephthalate polyester and its thermal properties

WANG Jingjing1, CHEN Yong1, WANG Chaosheng1, WANG Huaping1,2, BIAN Shuchang3, WU Jing2()   

  1. 1. School of Materials Science and Engineering, Donghua University, Shanghai 201620, China
    2. Key Technology Collaborative Innovation Center of Textile Industry, Donghua University, Shanghai 201620, China
    3. Jiangsu Guowang High-Tech Fiber Co., Ltd., Suzhou, Jiangsu 215000, China
  • Received:2019-07-19 Revised:2020-03-11 Online:2020-06-15 Published:2020-06-28
  • Contact: WU Jing

摘要:

针对目前生物基聚对苯二甲酸丙二醇酯(PTT)产业化过程中,大量环状低聚物的形成易对后续加工造成不良影响的问题,通过索氏提取法和溶解沉淀法对生物基PTT切片、纤维及粉末样品中提取的环状低聚物进行表征与分析。结果表明:从PTT纤维中提取的环状低聚物的质量分数为3.6%,比PTT切片中的高约1%;低聚物的主要组分为环状二聚体,其质量分数约占低聚物总量的85%~90%;同时检测出低质量分数的环状三聚体、环状四聚体、环状五聚体及环状七聚体,几种组分占低聚物总量的10%~15%;环状低聚物的热稳定性远低于生物基PTT高聚物且具有比高聚物更高的熔融温度,可充当成核剂,促进高聚物的结晶。

关键词: 聚合物, 生物基聚对苯二甲酸丙二醇酯, 环状低聚物, 溶剂萃取, 热性能

Abstract:

Aiming at the problem that the formation of a large number of cyclic oligomers in the industrialization process of current bio-based propylene terephthalate (bio-based PTT) is likely to adversely affect subsequent processing, the Soxhlet extraction method and the dissolution-precipitation method were used to characterize and analyze cyclic oligomers extracted from PTT slices, fibers and powder samples. It is reported from this research that the content of cyclic oligomers extracted from the fiber sample was 3.6%, which is about 1% higher than the slice. The main component of the oligomer is cyclic dimer, and its mass fraction is 85%-90% of the total of oligomers. Low levels of cyclic trimer, cyclic tetramer, cyclic pentamer, and cyclic heptamer are detected at the same time, and the total content of these components is about 10%-15%. The thermal stability of cyclic oligomers is found much lower than that of bio-based PTT polymers and higher than polymers in melting point, showing function of nucleating agent and could promote the crystallization of polymers.

Key words: polymer, bio-based propylene terephthalate, cyclic oligomer, solvent extraction, thermal property

中图分类号: 

  • TQ342.29

表1

生物基PTT物理性能参数"

样品
编号
数均
分子量
重均
分子量
分子量
分散度
特性黏度/
(dL·g-1)
PTT-1 17 400 42 300 2.4 1.01
PTT-2 19 500 47 700 2.4 0.99
PTT-3 19 500 43 600 2.2 0.97

表2

生物基PTT切片和纤维样品通过溶解-沉淀法所得提取物含量"

样品编号 切片低聚物提取量 纤维低聚物提取量
PTT-1 2.60 3.23
PTT-2 2.39 2.79
PTT-3 3.01 3.55

图1

不同溶剂萃取PTT切片、粉末及纤维提取物的质量分数与时间的关系"

图2

索氏提取前后生物基PTT-2纤维表面形貌扫描电镜照片"

图3

生物基PTT-2切片经溶解-沉淀法和索氏萃取法获得提取物的HPLC图"

图4

生物基PTT切片提取物6种组分比例图"

图5

生物基PTT切片提取物的核磁氢谱图"

图6

生物基PTT-2切片索氏萃取法提取物的红外谱图"

图7

生物基PTT-2切片索氏提取物的MALDI-TOF图"

图8

热重分析曲线"

图9

生物基PTT-2索氏提取物的DSC曲线图"

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