纺织学报 ›› 2024, Vol. 45 ›› Issue (06): 1-10.doi: 10.13475/j.fzxb.20221101501

• 纤维材料 •    下一篇

共聚阻燃改性聚对苯二甲酸乙二醇酯的制备及其性能

吴雨航1, 魏建斐1,2, 顾伟文1, 王玉萍3, 张安莹1, 王锐1()   

  1. 1.北京服装学院 材料设计与工程学院, 北京 100029
    2.北京服装学院 服装材料研究开发与评价北京市重点实验室, 北京 100029
    3.江苏新视界先进功能纤维创新中心有限公司, 江苏 苏州 215228
  • 收稿日期:2022-11-04 修回日期:2023-04-11 出版日期:2024-06-15 发布日期:2024-06-15
  • 通讯作者: 王锐(1963—),女,教授,博士。主要研究方向为高分子材料的高性能化与功能化。E-mail:clywangrui@bift.edu.cn。
  • 作者简介:吴雨航(1999—),女,硕士。主要研究方向为碳点及功能纤维的制备与应用。
  • 基金资助:
    北京学者计划(RCQJ20303);北京市自然科学基金项目(2222054号);北京市教委科技计划项目(KM202110012007)

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 Published:2024-06-15 Online:2024-06-15

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摘要：

针对聚对苯二甲酸乙二醇酯(PET)阻燃性较差的问题,以[(6-氧代-6H-二苯并[c,e][1,2]氧磷杂己环-6-基)甲基]丁二酸(DDP)和明胶基碳点(gCDs)构建复合阻燃体系,采用原位聚合法制备了阻燃DDP-gCDs-PET,借助扫描电子显微镜、傅里叶变换红外光谱仪对其结构进行分析,通过极限氧指数(LOI)、垂直燃烧(UL-94)及锥形量热指标研究了不同质量分数的gCDs与DDP复配后对PET阻燃性能的影响,并利用热重-傅里叶变换红外光谱分析探究了阻燃PET在气相中的热分解产物,提出了DDP、gCDs对PET的阻燃机制。结果表明:当添加DDP质量分数为8%、gCDs质量分数为1.0%时,DDP-gCDs-PET的UL-94等级提升至V-0级,LOI值可达到35%;相较于纯PET,DDP-gCDs-PET的热释放速率峰值降低39.77%,总热释放量降低25.00%,引燃时间延长25 s,阻燃效果显著改善;在燃烧过程中DDP促进了PET基体分解并在气相中淬灭自由基,gCDs使热量迅速扩散,提升了PET基体的热稳定性能,且gCDs在凝聚相促进成炭使DDP中的P留存于炭层中,二者共同作用提升了PET的阻燃性能。

关键词: 聚对苯二甲酸乙二醇酯, 明胶基碳点, 磷系阻燃剂, 原位聚合法, 复配阻燃, 阻燃机制

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

中图分类号: 

  • TQ323.4

表1

样品的制备配比"

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

图1

gCDs的透射电子显微镜照片和粒径分布图"

图2

gCDs的傅里叶变换红外光谱图"

图3

阻燃改性前后PET的傅里叶变换红外光谱图"

图4

阻燃改性前后PET的DSC曲线"

表2

阻燃改性前后PET的DSC数据"

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

图5

阻燃改性前后PET的热重曲线"

表3

阻燃改性前后PET热重数据"

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

图6

阻燃改性前后PET的锥形量热曲线"

表4

阻燃改性前后PET的锥形量热参数"

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

表5

阻燃改性前后PET的极限氧指数和垂直燃烧测试结果"

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

图7

锥形量热实验后残炭的宏观形貌以及SEM照片"

图8

锥形量热测试后炭层的傅里叶变换红外光谱图"

图9

阻燃改性前后PET的三维傅里叶变换红外光谱图"

图10

阻燃改性前后PET在不同温度下热分解产物的傅里叶变换红外光谱图"

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