Journal of Textile Research ›› 2024, Vol. 45 ›› Issue (06): 1-10.doi: 10.13475/j.fzxb.20221101501

• Fiber Materials •     Next Articles

Preparation and properties of flame retardant modified polyethylene terephthalate by in-situ polymerization

WU Yuhang1, WEI Jianfei1,2, GU Weiwen1, WANG Yuping3, ZHANG Anying1, WANG Rui1()   

  1. 1. School of Materials Design and Engineering, Beijing Institute of Fashion Technology, Beijing 100029, China
    2. Beijing Key Laboratory of Clothing Materials R&D and Assessment, Beijing Institute of Fashion Technology, Beijing 100029, China
    3. New Vision Advanced Functional Fiber Innovation Center Co., Ltd., Suzhou, Jiangsu 215228, China
  • Received:2022-11-04 Revised:2023-04-11 Online:2024-06-15 Published:2024-06-15

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Abstract:

Objective Polyethylene terephthalate (PET) is widely used because of its excellent comprehensive properties, but PET has poor flame retardancy, which greatly limits its application. Traditional halogenated flame retardants have great impact on the environment during combustion and cause damage to people's eye sight. Hence, the research of new halogen-free flame retardants is imperative.

Method In this study, flame retardant polyester (DDP-gCDs-PET) was prepared with [(6-oxo-6H-dibenzo[c,e][1,2]oxahex-6-yl)methyl]succinic acid (DDP) and gelatin-based carbon dots (gCDs) as flame retardant by in-situ polymerization. To explore the flame retardant properties of PET, a study was conducted using limiting oxygen index (LOI), vertical combustion (UL-94) and cone calorimetry to assess the influence of gCDs with varying mass fractions.

Results gCDs are quasi-spherical in structure, with an average particle size of about 3.34 nm and good dispersion. FT-IR spectra demonstrated the presence of amino groups and carboxyl groups on the surface of gCDs. In addition, FT-IR spectra also demonstrated the successful introduction of gCDs, DDP into PET molecular chains. When DDP was 8% and gCDs were 1.0% (named DDP-1.0gCDs-PET), the glass transition temperature of DDP-1.0gCDs-PET was increased by 9.33% compared with that of pure PET. The temperature at which ester mass decreases by 5% of DDP-1.0gCDs-PET was increased by 10.32 ℃ compared to that of DDP-PET. Compared with PET, the peak heat release rate of DDP-1.0gCDs-PET was reduced by 39.77%, the total heat release was reduced by 25.00%, and the time to ignition was delayed by 25 s compared with that of PET. UL-94 and LOI studies show that DDP-1.0gCDs-PET had a LOI of up to 35%, and UL-94 was upgraded from V-2 to V-0. After the combustion of flame-retardant polyester, a continuous dense carbon layer was formed, which effectively hinders the spread of heat and gas and improves the flame retardant performance of the matrix. It is evident that DDP promoted the decomposition of the matrix and played the role of quenching free radicals when the matrix was burned. The addition of gCDs significantly reduced the concentration of CO2 and CO in meteorological products and improved the quality of the carbon layer.

Conclusion Compared with pure PET, the flame retardant effect of DDP-gCDs-PET is significantly improved. The flame retardant mechanism of DPP and gCDs in PET system is understood. During the combustion process, gCDs absorb heat to form a heat conduction network, so that the heat diffuses rapidly and evenly in the matrix and delays the combustion of the matrix. DDP promotes decomposition of the matrix, while producing P=O to quench free radicals in the gas phase and dilute combustible groups in the gas. gCDs promote the retention of P in DDP in the carbon layer, forming a large number of dense and continuous high-quality carbon layers in the solidified phase to achieve the purpose of flame retardancy.

Key words: polyethylene terephthalate, gelatin-based carbon dot, phosphorus-based flame retardant, in situ polymerization method, compound flame retardant, flame retardant mechanism

CLC Number: 

  • TQ323.4

Tab.1

Formulations of sample preparation"

样品名称 PTA质
量/g		 EG质
量/g		 gCDs
质量分
数/%		 DDP
质量分
数/%
PET 700 314 0 0
DDP-PET 700 314 0 8
DDP-0.5gCDs-PET 700 314 0.5 8
DDP-1.0gCDs-PET 700 314 1.0 8
DDP-1.5gCDs-PET 700 314 1.5 8

Fig.1

TEM image(a) and size distribution image (b) of gCDs"

Fig.2

FT-IR spectra of gCDs"

Fig.3

FT-IR spectra of PET before and after flame retardant modification"

Fig.4

DSC curves of PET before and after flame retardant modification. (a) Heating curves; (b) Cooling curves"

Tab.2

DSC data for PET before and after flame retardant modification ℃"

样品名称 Tg Tcc Tm Tmc ΔTmc
PET 69.0 118.3 249.2 213.1 36.1
DDP-PET 75.3 142.2 238.6 177.4 61.2
DDP-0.5gCDs-PET 73.4 138.6 237.1 180.7 56.4
DDP-1.0gCDs-PET 76.1 135.3 240.5 184.5 56.0
DDP-1.5gCDs-PET 75.9 135.1 238.9 179.2 59.7

Fig.5

Thermogravimetric curves of PET before and after flame retardant modification"

Tab.3

Thermogravimetric data for PET before and after flame retardant modification"

样品名称 T5%/℃ Tmax/℃ 700 ℃残炭
量/%
PET 395.70 434.64 10.57
DDP-PET 371.77 447.39 3.93
DDP-0.5gCDs-PET 377.93 445.94 8.14
DDP-1.0gCDs-PET 382.09 446.96 4.63
DDP-1.5gCDs-PET 384.09 447.08 4.09

Fig.6

Cone calorimetry curves of PET before and after flame retardant modification"

Tab.4

Cone calorimetry parameters of PET before and after flame retardant modification"

样品名称 引燃时间/
s		 热释放速率峰值/
(kW·m-2)		 总释放热/
(MJ·m-2)
PET 59 808.48 74.72
DDP-PET 52 430.48 55.93
DDP-0.5gCDs-PET 75 765.61 52.59
DDP-1.0gCDs-PET 84 486.92 56.04
DDP-1.5gCDs-PET 69 437.71 56.78

Tab.5

LOI and UL-94 test results of PET before and after flame retardant modification"

样品名称 LOI值/
%		 垂直燃烧测试
t1/s t2/s 等级
PET 21 15.0 16.0 NR
DDP-PET 26 1.7 1.5 V-2
DDP-0.5gCDs-PET 30 1.9 1.8 V-2
DDP-1.0gCDs-PET 35 1.8 2.0 V-0
DDP-1.5gCDs-PET 33 1.2 0.8 V-0

Fig.7

Macro morphology and SEM images of residual carbon after cone calorimetry test. (a) Height of residual carbon after combustion; (b) Surface topography of residual carbon and SEM image (×100)"

Fig.8

FT-IR spectra of residual carbon after cone calorimetry test"

Fig.9

Three-dimensional FT-IR spectra of PET before and after flame retardant modification"

Fig.10

FT-IR spectra of thermal decomposition product of PET before and after flame retardant modification at different temperatures"

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