Journal of Textile Research ›› 2023, Vol. 44 ›› Issue (02): 1-10.doi: 10.13475/j.fzxb.20220809410

• Fiber Materials •     Next Articles

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 Online:2023-02-15 Published:2023-03-07

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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

CLC Number: 

  • TQ342.21

Tab.1

Formula of FR1 and FR2 masterbatches%"

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

Tab.2

Formula of flame retardant PET blends%"

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

Tab.3

Section temperature of molten spinning℃"

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

Fig.1

SEM images of cross-sections and surfaces for flame retardant PET fiber"

Fig.2

DSC curves of FR1/PET (a) and FR2/PET (b) blends"

Tab.4

Thermal performance parameters of different component flame retardant modified PET blends℃"

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

Tab.5

Strength,elongation at break and corresponding CV values of flame retardant modified PET fibers with different draw ratios"

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

Tab.6

TG data of different component flame retardant modified PET blends in N2"

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

Fig.3

Thermogravimetric curves of FR1/PET (a) and FR2/PET (b) blends in N2"

Fig.4

Vertical burning test results of different component flame retardant modified PET blends"

Tab.7

Vertical burning test results and LOI values of different component flame retardant modified PET blends"

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

Fig.5

Surface SEM images of char residue for different component flame retardant modified PET blends after burned(×100)"

Fig.6

Raman spectra of char residue for different component flame retardant modified PET blends"

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