纺织学报 ›› 2023, Vol. 44 ›› Issue (02): 1-10.doi: 10.13475/j.fzxb.20220809410

• 纤维材料 •    下一篇

磷硅改性阻燃抑熔滴聚酯纤维的制备及其性能

任嘉玮1, 张圣明1, 吉鹏2(), 王朝生1, 王华平1   

  1. 1.东华大学 材料科学与工程学院, 上海 201620
    2.东华大学 纺织科技创新中心, 上海 201620
  • 收稿日期:2022-08-18 修回日期:2022-11-11 出版日期:2023-02-15 发布日期:2023-03-07
  • 通讯作者: 吉鹏(1988—),男,副研究员,博士。主要研究方向为功能聚酯、聚酰胺结构设计与制备。E-mail:jipeng@dhu.edu.cn。
  • 作者简介:任嘉玮(1997—),男,博士生。主要研究方向为阻燃聚酯纤维及织物。
  • 基金资助:
    中央高校基本科研业务费专项资金资助项目(2232022D-10)

Preparation and properties of phosphorus-silicon modified flame retardant and anti-dripping polyester fiber

REN Jiawei1, ZHANG Shengming1, JI Peng2(), WANG Chaosheng1, WANG Huaping1   

  1. 1. College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
    2. Innovation Center for Textile Science and Technology, Donghua University, Shanghai 201620, China
  • Received:2022-08-18 Revised:2022-11-11 Published:2023-02-15 Online:2023-03-07

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摘要：

针对聚酯 (PET)纤维易燃且燃烧时伴随着大量熔滴与烟气的问题,将二乙基次膦酸盐阻燃剂、大分子型有机硅与PET载体共混制备磷硅阻燃母粒。将磷硅阻燃母粒按照一定质量分数添加到常规PET切片中混合,经熔融纺丝制得阻燃抑熔滴PET纤维。借助扫描电子显微镜、复丝强度仪、差示扫描量热仪、热重分析仪、氧指数测试仪、拉曼光谱仪对阻燃PET的力学性能、热性能与阻燃性能等进行表征和分析。结果表明:二乙基次膦酸盐阻燃剂使PET表面脱水成炭,大分子型有机硅提升了炭层的石墨化程度,形成有序稳定的炭层,增强了阻燃PET纤维阻燃性能并抑制熔滴形成,且燃烧形成的烟气量下降;添加质量分数为3%的二乙基次膦酸盐阻燃剂与0.77%大分子型有机硅纺制的阻燃PET纤维,其极限氧指数达到31%以上,垂直燃烧测试等级达到 V-0 级;通过磷硅元素间的阻燃协效作用改善了阻燃PET纤维的可纺性,同时使其具有良好的阻燃与抑熔滴性能。

关键词: 聚酯纤维, 阻燃, 抑熔滴, 磷硅协同阻燃, 阻燃机制, 可纺性, 二乙基次膦酸盐, 大分子型有机硅

Abstract:

Objective Polyester fibers are flammable with a large number of molten droplets and smoke emission when burning. This research aims to improve the flame retardant properties of polyester fibers through the addition of phosphorus and silicon flame retardants, and to prepare polyester fibers with better flame retardant properties for fire safety in end uses.
Method The phosphorus-silicon flame retardant masterbatch was prepared by blending diethyl hypophosphite flame retardant, macromolecular silicone and polyester. Then, the phosphorus-silicon flame retardant masterbatch was added to the polyester according to an optimized mass fraction, and the flame retardant and anti-dripping polyester fiber was produced by melt spinning. The mechanical properties, thermal properties and flame retardant properties of the flame retardant polyester were characterized and analyzed by using scanning electron microscope, compound filament strength meter, differential scanning calorimeter, thermogravimetric analyzer, ultimate oxygen index meter and Raman spectroscopy.
Results The diethyl hypophosphite flame retardant selected in this work is found to be able to dehydrate the polyester surface into char, and the macromolecular silicone enhances the graphitization of the char layer, forms an orderly and stable char layer, enhances the flame retardant polyester flame retardant properties and inhibits the formation of molten droplets. Accordingly, the amount of smoke formed by combustion decreases, and the morphology of the char layer of the samples after combustion is shown in Fig. 5, and the results of the char layer structure stability study were shown in Fig. 6. It is discovered that macromolecular silicone mainly plays a role in the cohesive phase flame retardant process when polyester burns, forming a synergistic effect with phosphorus-containing flame retardant, generating an effective physical barrier, impeding the transfer of combustible gases, oxygen and heat, and inhibiting the occurrence of combustion reactions. The flame retardant polyester fiber spun by adding 3% diethyl hypophosphite flame retardant and 0.77% macromolecular silicone, the test results for the flame retardant properties of the modified samples are showed that the limiting oxygen index reached more than 31%, the vertical combustion test grade reached V-0 level, inhibiting the formation of molten droplets of polyester fiber during combustion, hence reducing the risk of secondary combustion brought about by the molten droplet phenome-non(Tab. 7).
Conclusion The flame retardant synergistic effect between phosphorus and silicon elements improved the spinnability of the flame retardant polyester fiber, and the modified polyester fiber has good flame retardant and anti-dripping properties. This work proved that the phosphorus-silicon element synergy is helpful to improve the flame retardant properties of polyester fibers, and provides ideas for the subsequent preparation of flame retardant polyester fibers by using different structural flame retardants from the viewpoint of conformational relationship and processing performance.

Key words: polyester fiber, flame retardant, anti-dripping, phosphorus-silicon synergy, flame retardant mechanism, spinnability, diethyl hypophosphite, macromolecular silicone

中图分类号: 

  • TQ342.21

表1

FR1、FR2阻燃母粒物料配方"

样品编号 二乙基次膦酸盐 大分子型有机硅 PET
FR1 20.0 0.0 80.0
FR2 17.4 4.5 78.1

表2

阻燃PET共混物物料配方"

样品
编号		 配方 磷元素质
量分数
FR1阻燃
母粒		 FR2阻燃
母粒		 PET
PET 0 0 100.00 0.0
FR1-1 5 0 95.00 0.2
FR1-2 10 0 90.00 0.4
FR1-3 15 0 85.00 0.6
FR2-1 0 5.75 94.25 0.2
FR2-2 0 11.50 88.50 0.4
FR2-3 0 17.25 82.75 0.6

表3

熔融纺丝各区间温度"

样品编号 Ⅰ区 Ⅱ区 Ⅲ区 Ⅳ区 机头
PET 280 288 293 295 295
FR1-1 280 288 293 296 295
FR1-2 280 290 295 296 296
FR1-3 280 290 295 296 298
FR2-1 280 288 293 293 295
FR2-2 280 288 293 293 290
FR2-3 280 288 293 293 288

图1

阻燃PET纤维的截面和表面SEM照片"

图2

FR1/PET和FR2/PET共混物的DSC曲线"

表4

不同组分阻燃改性PET共混物的热性能参数"

样品编号 玻璃化转变温度 熔点 结晶温度
PET 81.59 253.79 180.30
FR1-1 80.69 254.44 203.96
FR1-2 79.65 254.38 203.37
FR1-3 80.95 253.61 201.33
FR2-1 79.61 252.69 221.78
FR2-2 80.12 253.77 210.13
FR2-3 78.54 253.51 207.62

表5

不同牵伸倍率下阻燃改性PET纤维的断裂强度、断裂伸长率及其CV值"

样品
编号		 断裂强度/(cN·dtex-1) 断裂强度CV值/% 断裂伸长率/% 断裂伸长率CV值/%
5.5倍 6.0倍 6.5倍 5.5倍 6.0倍 6.5倍 5.5倍 6.0倍 6.5倍 5.5倍 6.0倍 6.5倍
PET 2.00 2.10 2.15 6.30 7.50 5.10 54.20 60.50 62.90 11.60 13.20 13.30
FR1-1 1.28 1.46 1.58 11.30 6.06 7.25 49.40 65.50 45.40 16.40 16.90 15.22
FR1-2 1.77 2.06 2.28 1.00 2.70 5.90 57.10 25.60 25.20 17.50 13.70 15.30
FR1-3 1.61 1.96 2.13 5.81 3.40 2.50 38.40 38.80 28.50 14.10 12.90 8.80
FR2-1 1.20 1.27 1.50 8.90 9.70 1.00 50.70 57.50 45.00 24.80 27.70 7.10
FR2-2 1.24 1.43 1.67 4.30 3.40 4.30 64.00 55.30 40.30 17.30 11.50 8.20
FR2-3 1.25 1.49 1.63 6.10 4.90 5.40 60.70 59.50 31.60 8.50 8.50 7.80

表6

不同组分阻燃改性PET共混物氮气氛围的TG数据"

样品编号 初始分解
温度/℃		 最大质量
损失温度/℃		 700 ℃时
残炭量/%
PET 399.9 437.1 10.88
FR1-1 390.4 434.8 12.59
FR1-2 392.8 437.7 14.05
FR1-3 393.0 434.9 14.25
FR2-1 397.1 432.3 14.68
FR2-2 397.6 434.3 15.34
FR2-3 394.9 432.4 15.10

图3

FR1/PET和FR2/PET共混物在氮气氛围下的热重曲线"

图4

不同组分阻燃改性PET共混物垂直燃烧测试结果"

表7

不同组分阻燃改性PET共混物垂直燃烧与极限氧指数测试结果"

样品编号 LOI值/% 垂直燃烧测试结果
是否引燃
脱脂棉		 熔滴数 UL-94 等级
PET 21.0 是 1 V-2
FR1-1 26.8 是 1 V-2
FR1-2 27.8 是 1 V-2
FR1-3 29.4 否 1 V-0
FR2-1 27.4 是 1 V-2
FR2-2 28.4 是 1 V-2
FR2-3 31.4 否 1 V-0

图5

不同组分阻燃改性PET共混物燃烧后炭层表面的扫描电镜照片(×100)"

图6

不同组分阻燃改性PET共混物燃烧后炭层拉曼光谱图"

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