纺织学报 ›› 2021, Vol. 42 ›› Issue (10): 15-21.doi: 10.13475/j.fzxb.20210701107

• 纺织科技新见解学术沙龙专栏: 纤维原液着色关键技术及其产品 • 上一篇    下一篇

原位法连续聚合聚酯/炭黑体系的结构与性能

邱志成, 李鑫(), 李志勇, 王颖, 金剑, 武术方   

  1. 中国纺织科学研究院有限公司 生物源纤维制造技术国家重点实验室, 北京 100025
  • 收稿日期:2021-07-02 修回日期:2021-07-21 出版日期:2021-10-15 发布日期:2021-10-29
  • 通讯作者: 李鑫
  • 作者简介:邱志成(1984—),男,正高级工程师,博士。主要研究方向为功能聚酯合成及其工程化技术开发。
  • 基金资助:
    国家重点研发计划项目(2020YFB0311400)

Structure and properties of polyester/carbon black system prepared by in-situ continuous polymerization

QIU Zhicheng, LI Xin(), LI Zhiyong, WANG Ying, JIN Jian, WU Shufang   

  1. State Key Laboratory of Biobased Fiber Manufacturing Technology, China Textile Academy, Beijing 100025, China
  • Received:2021-07-02 Revised:2021-07-21 Published:2021-10-15 Online:2021-10-29
  • Contact: LI Xin

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摘要：

为开发高黑度的细原液着色聚酯纤维,采用原位法连续聚合制备出炭黑质量分数为2%~3%的聚酯/炭黑(简称原位法PET/炭黑)体系,对其流变行为、结晶行为和炭黑分散形态等进行了表征,并制备了高速纺长丝。结果表明:原位法连续聚合使炭黑以直径小于1 μm的粒子簇团形式均匀分散在聚酯基体中;炭黑含量较低时的流变行为与PET相似,当炭黑质量分数达到3%时,原位法PET/炭黑熔体的表观黏度随剪切速率增大而快速降低;熔融结晶过程中,炭黑作为高效异相成核剂,显著加快了聚酯结晶速率,同时,聚酯与炭黑的良好相互作用,导致有更多的结晶缺陷,与PET相比,出现了熔融双峰,且高温熔融峰峰顶温、结晶度均降低,这与母粒法PET/炭黑体系明显不同。因为原位法保证了良好的炭黑分散性,原位法PET/炭黑可以稳定制备出炭黑质量分数为3%、单丝线密度为0.52 dtex、断裂强度≥3.31 cN/dtex的长丝。

关键词: 原位聚合, 原液着色, 聚酯纤维, 炭黑, 结晶行为, 流变行为

Abstract:

In order to develop dope-dyed polyester fiber with high blackness and fine denier, polyester (PET)/carbon black system with carbon black content of 2% to 3% was prepared by in-situ continuous polymerization. The rheology behavior, crystallization behavior and carbon black dispersion morphology of the in-situ polymerized PET/carbon black system were characterized, and polymerized PET/carbon black filaments were prepared by high speed spinning. The results show that carbon black is uniformly dispersed in polyester matrix in the form of particle clusters less than 1 μm in diameter. The rheological behavior of the in-situ polymerized PET/carbon black with low carbon black content is similar to that of PET. When the carbon black content reaches 3%, the apparent viscosity of in-situ polymerized PET/carbon black melt decreases rapidly with the increase of shear rate. During melt crystallization of the polymerized PET/carbon black, carbon black, as a high efficient heterogeneous nucleating agent, significantly speeds up the crystallization rate of polyester, at the same time, and the good interaction between polyester and carbon black leads to more crystallization defects. These results lead to the double melting peaks of the polymerized PET/carbon black system, and the crystallinity and the peak temperature of the melting peak of polymerized PET/carbon black are lower than that of PET, which is obviously different from that of PET/carbon black prepared by masterbatch method. Due to the good dispersion of carbon black, the polymerized PET/carbon black with 3% carbon black content can be successfully spun into filaments, with the monofilament size 0.52 dtex and breaking strength higher than 3.3 cN/dtex.

Key words: in-situ polymerization fiber, dope-dyed, polyester fiber, carbon black, crystallization behavior, rheological behavior

中图分类号: 

  • TQ342.21

图1

过滤器的压差变化趋势"

图2

原位法PET/炭黑淬断面的SEM照片(×5 000)"

图3

PET和原位法PET/炭黑熔体在290 ℃时的流动曲线"

图4

PET和原位法PET/炭黑的DSC曲线"

表1

PET和原位法PET/炭黑的DSC曲线的相关参数"

样品 Tmc/
℃		 ΔHmc/
(J·g-1)		 Tm1/
℃		 Tm2/
℃		 ΔHm/
(J·g-1)		 Xc/
%
PET 162.5 25.7 / 250.0 35.2 29.9
PET-CB-2.0 191.0 38.0 239.8 248.5 33.0 28.6
PET-CB-3.0 188.4 36.8 235.7 244.5 31.6 27.7

图5

PET和母粒法PET/炭黑的DSC曲线"

表2

PET和母粒法PET/炭黑的DSC曲线的相关参数"

样品 Tmc/
℃		 ΔHmc/
(J·g-1)		 Tm1/
℃		 Tm2/
℃		 ΔHm/
(J·g-1)		 Xc/
%
PET 162.5 25.7 / 250.0 35.2 29.9
PET-CB-2.0-MB 196.9 39.0 / 250.3 37.2 32.3
PET-CB-3.0-MB 198.0 38.4 / 250.4 37.1 32.5

表3

不同纺丝速度下制备的PET和原位法PET/炭黑POY的力学性能和取向度"

样品 纺丝
速度/
(m·min-1)		 复丝线
密度/
dtex		 单丝线
密度/
dtex		 断裂
强度/
(cN·dtex-1)		 断裂伸
长率/
%		 声速取
向因子
fs
PET 2 800 134.1 1.86 2.13 147.6 —
91.3 1.27 2.32 142.5 0.401
67.3 0.93 2.34 132.4 —
3 000 92.2 1.28 2.42 134.4 0.452
3 200 92.0 1.28 2.51 112.2 0.490
3 400 92.2 1.28 2.65 108.7 0.551
PET-CB-
2.0		 2 800 135.6 1.88 2.03 151.8 —
92.6 1.29 2.06 146.0 0.390
67.8 0.94 2.17 147.8 —
3 000 92.0 1.28 2.11 130.8 0.430
3 200 92.7 1.29 2.15 127.5 0.473
3 400 91.5 1.27 2.18 122.1 0.527
PET-CB-
3.0		 2 800 136.1 1.89 1.79 170.3 —
92.9 1.29 1.79 158.3 0.390
67.7 0.94 1.79 153.8 —
3 000 90.8 1.26 1.83 155.6 0.427
3 200 91.6 1.27 1.84 152.2 0.445
3 400 90.9 1.26 1.79 143.7 0.463

表4

PET和原位法PET/炭黑POY经1.8倍牵伸制备拉伸丝(DY)力学性能"

样品 POY 纺
丝速度/
(m·min-1)		 复丝线
密度/
dtex		 单丝线
密度/
dtex		 断裂
强度/
(cN·dtex-1)		 断裂
伸长/
%
PET 2 800 74.1 1.03 4.17 32.4
51.0 0.71 4.58 28.5
37.1 0.52 4.64 18.7
3 000 51.2 0.71 4.58 22.5
3 200 51.9 0.72 4.86 15.6
3 400 51.2 0.71 5.45 12.4
PET-CB-
2.0		 2 800 75.3 1.05 3.72 33.5
51.0 0.71 4.05 28.6
37.0 0.51 4.03 26.4
3 000 51.4 0.71 3.90 22.1
3 200 51.9 0.72 4.04 24.1
3 400 51.0 0.71 4.23 22.1
PET-CB-
3.0		 2 800 75.6 1.05 3.13 38.5
51.8 0.72 3.31 40.4
37.4 0.52 3.31 35.7
3 000 51.9 0.72 3.19 32.5
3 200 51.7 0.72 3.57 39.2
3 400 51.8 0.72 3.38 28.2
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