Journal of Textile Research ›› 2023, Vol. 44 ›› Issue (02): 214-221.doi: 10.13475/j.fzxb.20220807408

• Dyeing and Finishing & Chemicals • Previous Articles     Next Articles

Preparation and application of flame retardant waterborne polyurethane by alcoholysis of waste polyethylene terephthalate fiber

PANG Mingke1,2,3, WANG Shuhua1,3(), SHI Sheng1,2,3, XUE Lizhong1,3, GUO Hong1,3, GAO Chengyong1,3, LU Jianjun1,3, ZHAO Xiaowan1,3, WANG Zihan1,3   

  1. 1. College of Textile Engineering, Taiyuan University of Technology, Jinzhong, Shanxi 030600, China
    2. Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering, Taiyuan, Shanxi 030024, China
    3. Key Laboratory of Waste Polyester Cotton Textiles for Cleaning and Regeneration in Textile Industry, Jinzhong, Shanxi 030600, China
  • Received:2022-08-17 Revised:2022-11-19 Online:2023-02-15 Published:2023-03-07

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Abstract:

Objective The increasing amount of waste polyethylene terephthalate (PET) textiles has resulted in a huge waste of energy and resources. Due to the limitation of recycling methods, the reuse of recycled products is also affected. In order to improve the yield of waste PET fabric and to reuse the recycled products, the aim of this research is to optimize the reaction conditions for depolymerization of waste PET fabric, to synthesize, using the depolymerized product as raw material, stable waterborne polyurethane (WPU), and to conduct flame retardant modification of the waterborne polyurethane for flame retardance.
Method Under the conditions of choline chloride and zinc acetate as catalysts, glycolysis was used to depolymerize waste PET fabric. The effects of reaction time, catalysts content and other influential factors were investigated on the product yields, and the products were characterized using Fourier transform infrared spectro-meter(FT-IR). Waterborne polyurethane was synthesized by the alcoholysis product ethylene terephtha-late(BHET) and isoflurone diisocyanate (IPDI) and so on, and tris(hydroxymethyl)phosphine (THPO) and SiO2 were used to improve its flame retardant property. The conditions were optimized for making stable waterborne polyurethane emulsion, and the effects of initial n(NCO)/n(OH), content of the flame retardants and SiO2 on the flame retardant property of WPU were systematically studied, and characterization was carried out using FT-IR and thermal gravity analysis. Flame retardant modified waterborne polyurethane on PET fabrics was studied with the assistance of scanning electron microscope (SEM).
Results The best depolymerization process took place when the mass ratio of EG and PET was set to be 4∶1, molar ratio of choline chloride to zinc acetate 1∶1, reaction temperature 185 ℃, and reaction time 4 h. The FT-IR results indicated that the depolymerized product was bis(hydroxyethyl) terephthalate (BHET), whose yield was up to 87.6%. When the THPO content was less than 24%, the SiO2 content less than 6%, and the n(NCO)/n(OH) was 3-7, the flame retardant modified waterborne polyurethane formed a uniform and stable emulsion. When the THPO content was 24%, SiO2 content was 4%, and n(NCO)/n(OH) was 6, the flame retardant modified PET fabric demonstrated promising flame retardant properties, with the residual carbon rate reaching up to 13.9%, which is 127% higher than original PET fabric, and the LOI value of the modified PET fabric reached up to 29.7%, which meets UL-94 V-0 level. The SEM results suggested that the PET fabric was uniformly coated by the flame retardant modified polyurethane emulsion after treatment, and the voids between the fabric and yarns were filled by the polyurethane, and the emulsion and the fabric were integrated together.
Conclusion This research has led to the following achievements: 1) waste PET fibers are depolymerized via alcoholysis; 2) the depolymerized product are successfully synthesized into flame retardant modified waterborne polyurethane; 3) the flame retardant modified waterborne polyurethane is used to treat PET fabrics which demonstrate promising flame retardant performance. The route can be applied to create general flame retardant fabrics.

Key words: waste polyethylene terephthalate, alcoholysis, waterborne polyurethane, flame retardant modification, finishing technology, recycling

CLC Number: 

  • TS102.9

Tab.1

Effect of alcohololysis experimental conditions on BHET yield"

序号 n(醋酸锌)∶n(氯化胆碱) 时间/h BHET产率/%
1 2:1 2 63.2
2 2:1 3 82.8
3 2:1 4 85.4
4 1:1 2 78.8
5 1:1 3 82.4
6 1:1 4 87.6
7 1:2 2 71.4
8 1:2 3 77.8
9 1:2 4 83.3

Fig.1

Infrared spectra of alcoholysis products"

Tab.2

Effect of different n(NCO)/n(OH) value on waterborne polyurethane emulsion"

样品编号 n(NCO)/n(OH) 乳液状态 稳定性
IPDI-1 3 乳液 稳定
IPDI-2 4 乳液 稳定
IPDI-3 5 乳液 稳定
IPDI-4 6 乳液 稳定
IPDI-5 7 悬浊液 沉淀
IPDI-6 8 悬浊液 少量沉淀

Tab.3

Effect of different THPO contents on waterborne polyurethane emulsion"

样品编号 THPO质量分数/% 乳液状态 稳定性
THPO-0 0 乳液 稳定
THPO-1 6 乳液 稳定
THPO-2 9 乳液 稳定
THPO-3 12 乳液 稳定
THPO-4 15 乳液 稳定
THPO-5 18 乳液 稳定
THPO-6 21 乳液 稳定
THPO-7 24 乳液 稳定

Tab.4

Effect of different SiO2 contents on waterborne polyurethane emulsion"

样品编号 SiO2质量分数/% 乳液状态 稳定性
SiO2-0 0 乳液 稳定
SiO2-1 2 乳液 稳定
SiO2-2 4 乳液 稳定
SiO2-3 6 乳液 稳定
SiO2-4 8 悬浊液 极少沉淀
SiO2-5 10 悬浊液 沉淀

Tab.5

Flame retardant properties of PET modified by different content of THPO"

样品编号 LOI值/% UL-94测试结果
t1/s t2/s 是否引燃棉球 等级
THPO-1 23.1 3.4 2.9 否 V-1
THPO-2 24.3 2.8 2.5 否 V-1
THPO-3 25.0 2.8 2.4 否 V-1
THPO-4 26.0 2.4 1.8 否 V-1
THPO-5 27.2 2.3 1.9 否 V-0
THPO-6 28.6 1.9 0.8 否 V-0
THPO-7 29.7 2.0 0.7 否 V-0

Tab.6

Flame retardant properties of PET modified by different contents of SiO2"

样品
编号		 LOI值/
%		 UL-94测试结果
t1/s t2/s 是否引燃棉球 等级
SiO2-0 21.3 12.6 11.3 否 V-1
SiO2-1 24.2 7.0 5.8 否 V-0
SiO2-2 26.0 4.6 4.5 否 V-0
SiO2-3 28.5 2.2 1.8 否 V-0
SiO2-4 25.2 2.4 1.5 否 V-0
SiO2-5 24.0 1.8 1.1 否 V-0

Tab.7

Effect of n(NCO)/n(OH) value on flame retardant properties of PET"

样品
编号		 LOI值/
%		 UL-94测试结果
t1/s t2/s 是否引燃棉球 等级
IPDI-1 20.7 14.3 19.3 否 V-1
IPDI-2 23.9 13.5 11.3 否 V-1
IPDI-3 28.5 5.2 4.8 否 V-0
IPDI-4 29.7 4.9 4.6 否 V-0
IPDI-5 20.0 11.9 10.8 否 V-1
IPDI-6 18.6 13.1 12.7 是 V-2

Fig.2

TG (a) and DTG (b) curves of phosphorus-silicon flame retardant modified PET fabric"

Fig.3

DSC heating (a) and cooling(b) curves of flame retardant modified PET fabric"

Fig.4

Infrared spectrum of flame retardant modified PET fabric"

Fig.5

SEM images of flame retardant modified PET fabric(×200). (a) PET fabric; (b) PET/polyurethanes fabric; (c) PET/THPO modified polyurethanes fabric; (d) Flame retardant modified PET fabric"

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