纺织学报 ›› 2019, Vol. 40 ›› Issue (04): 7-14.doi: 10.13475/j.fzxb.20181103908

• 纤维材料 • 上一篇    下一篇

阻燃聚左旋乳酸及其纤维的制备与结构性能

张安莹1, 王照颖1, 王锐1(), 董振峰1, 魏丽菲2, 王德义3   

  1. 1.北京服装学院 材料科学与工程学院, 北京 100029
    2.四川大学 高分子科学与工程学院, 四川 成都 610065
    3.马德里高等材料研究院, 西班牙 马德里 28906
  • 收稿日期:2018-11-14 修回日期:2019-01-05 出版日期:2019-04-15 发布日期:2019-04-16
  • 通讯作者: 王锐
  • 作者简介:张安莹(1993—),女,硕士。主要研究方向为聚乳酸纤维的制备。
  • 基金资助:
    国家重点研究计划项目(2017YFB0309000)

Preparation and structural properties of flame retardant poly(L-lactic acid) and fiber thereof

ZHANG Anying1, WANG Zhaoying1, WANG Rui1(), DONG Zhenfeng1, WEI Lifei2, WANG Deyi3   

  1. 1. School of Materials Science & Engineering, Beijing Institute of Fashion Technology, Beijing 100029, China
    2. College of Polymer Science and Engineering, Sichuan University, Chengdu, Sichuan 610065, China
    3. IMDEA Materials Institute, Madrid 28906, Spain
  • Received:2018-11-14 Revised:2019-01-05 Online:2019-04-15 Published:2019-04-16
  • Contact: WANG Rui

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摘要：

为提高聚左旋乳酸(PLLA)的阻燃性及其可纺性,设计了环保[(6-氧-6H-二苯并-(c,e)(1,2)-氧磷杂己环-6-酮)-甲基]-丁二酸(DDP)阻燃PLLA体系,通过双螺杆熔融挤出方法制备了PLLA/DDP阻燃复合物,借助锥形量热仪、极限氧指数仪、垂直燃烧仪、扫描电子显微镜、差示扫描量热仪、热失重分析仪对复合物的结构与性能进行表征,研究了阻燃剂质量分数对PLLA阻燃性能的影响及其阻燃机制,并对阻燃剂最优添加量时的纺丝工艺及纤维性能进行分析。结果表明:当DDP质量分数为9%时,复合物的阻燃性能显著提高,其极限氧指数达到29%,垂直燃烧测试达到V-0级;复合物在800 ℃时的残炭量由10.7%增加到13.5%,且在该添加比例下具有优良的可纺性;将初生纤维3倍牵伸热定型后,其断裂强度为1.77 cN/dtex,断裂伸长率为44.9%。

关键词: 聚左旋乳酸, 无卤阻燃剂, 阻燃性能, 可纺性, 断裂强度

Abstract:

In order to study the flame retardancy and spinnability of poly(L-lactic acid) (PLLA), an environmentally [(6-oxo-6H-dibenzo-(c,e)(1,2)-oxaphosphorin-6-one)methyl] butanedioic acid (DDP) flame retardant PLLA system was designed. PLLA/DDP composites were prepared by twin-screw melt extrusion, and the structures and properties thereof were characterized by cone calorimetry, limiting oxygen index, vertical combustion, scanning electron microscopy, differential scanning calorimetry and thermogravimetric analysis. The effect of the flame retardant content on the flame retardant properties of PLLA and the flame retardant mechanism of DDP on PLLA were also investigated. The spinning process and fiber properties at the optimum flame retardant dosage were studied. The results show that when the mass content of DDP is 9%, the LOI of the composite reaches 29% and the UL-94 test reaches grade V-0. The amount of carbon residue of the composite at 800 ℃ increases from 10.7% to 13.5%, and the composite has excellent spinnability. After the nascent fiber is stretched and heat set by 3 times, the breaking strength is 1.77 cN/dtex, and the elongation at break is 44.9%.

Key words: poly(L-lactic acid), halogen-free flame retardant, flame retardancy, spinnability, breaking strength

中图分类号: 

  • TQ342.89

表1

复合物的配比"

样品编号 PLLA质量分数 DDP质量分数
1﹟ 100 0
2﹟ 97 3
3﹟ 95 5
4﹟ 93 7
5﹟ 91 9
6﹟ 89 11

表2

纺丝工艺参数"

样品
编号		 纺丝温度/℃ 卷绕速度/
(m·min-1)		 热定型温度/℃
Ⅰ区 Ⅱ区 Ⅲ区 Ⅳ区 管道 组件 上辊 下辊 热辊
1﹟ 160 185 180 180 180 180 500 60 75 85
5﹟ 165 195 210 210 210 210 500 75 80 90

图1

阻燃PLLA复合物的横截面扫描电镜照片(×500)"

图2

阻燃PLLA复合物的DSC曲线"

表3

阻燃PLLA复合物的DSC测试结果"

样品
编号		 θg θcc θm θmc θ0 θm-θ0
1﹟ 60 98 174 99 91 83
2﹟ 60 96 173 97 87 86
3﹟ 59 98 172 93 90 82
4﹟ 59 97 172 92 89 83
5﹟ 59 97 172 91 89 83
6﹟ 59 98 170 — 89 81

图3

PLLA、DDP及其复合物的热力学曲线"

图4

阻燃PLLA复合物的热稳定性曲线"

图5

阻燃PLLA复合物的锥形量热曲线"

表4

阻燃PLLA复合物的LOI和UL-94测试结果"

样品
编号		 LOI/
%		 UL-94测试结果 30 s内熔滴数
t1/s t2/s 等级
1﹟ 19 20.9 23.0 V-2 18
2﹟ 22 10.5 4.5 V-2 16
3﹟ 25 17.4 10.5 V-2 16
4﹟ 25 12.4 6.3 V-2 14
5﹟ 29 8.1 4.5 V-0 13(自熄)
6﹟ 27 9.5 4.3 V-0 13(自熄)

图6

PLLA及其复合物在不同温度的红外谱图"

图7

不同温度下样品热降解气体红外谱图"

图8

1#和5#样品在热降解条件下气相产物的三维图"

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