聚对苯二甲酸乙二醇酯基碳点热解法制备及其在阻燃改性中的应用

doi:10.13475/j.fzxb.20230708301

纺织学报 ›› 2024, Vol. 45 ›› Issue (10): 1-8.doi: 10.13475/j.fzxb.20230708301

• 纤维材料 • 下一篇

聚对苯二甲酸乙二醇酯基碳点热解法制备及其在阻燃改性中的应用

邴琳涵¹, 王锐¹^,², 吴雨航¹, 刘博同¹, 黄寒江¹, 魏建斐¹^,²()

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

收稿日期:2023-10-19 修回日期:2024-07-13 出版日期:2024-10-15 发布日期:2024-10-22
通讯作者: 魏建斐(1986—),男,副教授,博士。主要研究方向为纺织废弃物的高值利用及功能化纤维材料制备。E-mail:weijianfei@bift.edu.cn。
作者简介:邴琳涵(2001—),女,硕士生。主要研究方向为阻燃聚酯材料制备。
基金资助:
北京市自然科学基金面上项目(2222054);北京市教委科技计划一般项目(KM202110012007);北京服装学院高水平教师队伍建设专项资金(BIFTXJ202225);北京学者项目(RCQJ20303)

Preparation of PET-based carbon dots by pyrolysis and its application in PET flame retardancy

BING Linhan¹, WANG Rui¹^,², WU Yuhang¹, LIU Botong¹, HUANG Hanjiang¹, WEI Jianfei¹^,²()

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

Received:2023-10-19 Revised:2024-07-13 Published:2024-10-15 Online:2024-10-22

摘要/Abstract

摘要：

为提高聚对苯二甲酸乙二醇酯(PET)阻燃性能,以PET废弃物为前驱体,采用热解法制备了PET基碳点(PET-CDs),并采用熔融共混法将其与PET混合制备PET复合物(PET-CDs-PET)。借助透射电子显微镜、X射线光电子能谱、傅里叶红外光谱对PET-CDs进行结构分析,借助荧光光谱仪、紫外分析仪研究了PET-CDs的光学性能,通过极限氧指数、垂直燃烧及锥形量热探究了不同添加量下PET-CDs对PET阻燃性能的影响,并采用材料强力测试仪研究了PET-CDs-PET的力学性能。结果表明:所制备的PET-CDs的荧光为激发波长依赖型,最佳激发波长和最佳发射波长分别为320 nm和420 nm,荧光量子产率为25.73%;当PET-CDs的添加质量分数为1%时,LOI值达30%,UL-94等级达到V-2级,总热释放量及总烟释放量略有降低,CO释放峰值下降42%,CO₂释放峰值下降35.9%。

关键词: 聚对苯二甲酸乙二醇酯, 碳点, 热解, 阻燃改性, 共混, 聚酯回收利用

Abstract:

Objective In order to improve the flame retardant properties of polyethylene terephthalate (PET), PET-based carbon dots (PET-CDs) were prepared by pyrolysis using PET waste as a precursor, and PET com-plexes (PET-CDs-PET) were prepared by mixing them with PET using physical blending method. The transformation from PET waste to flame-retardant PET was achieved. PET oligomers were prepared by microwave method, and then PET-CDs were prepared by pyrolysis reaction of PET oligomers with ethylenediaminetetraacetic acid. PET-CDs of different qualities were crushed in a pulveriser together with PET slices to obtain four kinds of PET-CDs-PETs with different contents of PET-CDs.

Method Transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier infrared spectroscopy were used to analyse the structure of PET-CDs, and the optical properties of PET-CDs were investigated with the help of fluorescence spectrometer and UV analyser. The effects of different additive amounts of PET-CDs on the flame retardancy of PET were investigated by the limiting oxygen index (LOI), vertical combustion (UL-94), and cone calorimetry. The effect of PET-CDs on the flame retardancy of PET with different additions was also investigated by using a material. The mechanical properties of PET-CDs-PET were investigated by a material strength tester.

Results As far as the structure is concerned, the prepared PET-CDs are quasi-spherical, with uniform particle distribution and no agglomeration. The particle size ranged from 0.44 nm to 4.39 nm, the average particle size was 1.85 nm, the lattice spacing was 0.25 nm, and the surface contained hydroxyl, carboxyl, and amine functional groups. In terms of optical properties, the prepared PET-CDs ethanol solutions showed dark brown colour under indoor natural light and blue fluorescence in UV analyser when irradiated by UV lamp with wavelength of 365 nm. The fluorescence of PET-CDs ethanol solutions was typical excitation wavelength-dependent, with the optimal excitation wavelengths and emission wavelengths of 320 nm and 420 nm, respectively. The absolute fluorescence quantum yield reached 25.73% under the light excitation at 320 nm, and the UV-visible absorption spectrum had an obvious absorption peak at 293 nm. In terms of flame retardant properties, the thermal stability of PET-CDs met the requirements of blending with PET, and the residual carbon of PET was increased by adding PET-CDs into PET. The LOI values of PET-CDs was increased and then decreased after the addition of PET-CDs with different contents, but all of them were higher than that of pure PET. The UL-94 fire ratings were all V-2 with different additions of PET-CDs. The LOI value of PET-CDs 1%-PET was 30%, and there was no significant decrease in the mechanical properties of PET at this additive amount, so the optimal additive amount of PET-CDs was 1%. The total heat release of PET-CDs 1%-PET was decreased by 1.5%, the total smoke release by 8.1%, the peak value of CO by 42%, the peak value of CO₂ by 35.9%.

Conclusion The preparation of CDs from PET waste as raw material can provide a new method for the reuse of waste, and the PET waste can be used in the flame retardant modification of PET materials after the preparation of CDs, forming a green and benign cycle. At the same time, the application of CDs in the flame retardant field not only broadens the scope of its application, but also provides a new flame retardant in this field.

Key words: polyethylene terephthalate, carbon dots, pyrolysis, flame retardant modification, co-mixing, polyester recycling and utilization

中图分类号:

TQ317.9

邴琳涵, 王锐, 吴雨航, 刘博同, 黄寒江, 魏建斐. 聚对苯二甲酸乙二醇酯基碳点热解法制备及其在阻燃改性中的应用[J]. 纺织学报, 2024, 45(10): 1-8.

BING Linhan, WANG Rui, WU Yuhang, LIU Botong, HUANG Hanjiang, WEI Jianfei. Preparation of PET-based carbon dots by pyrolysis and its application in PET flame retardancy[J]. Journal of Textile Research, 2024, 45(10): 1-8.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20230708301

http://www.fzxb.org.cn/CN/Y2024/V45/I10/1

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样品	PET-CDs质量	PET切片质量
纯PET	0	500
PET-CDs 1%-PET	5	495
PET-CDs 3%-PET	15	485
PET-CDs 5%-PET	25	475

样品	T_g	T_cc	T_m	T_mc	ΔT_mc
纯PET	72	134	245	208	37
PET-CDs 1%-PET	71	121	247	202	45
PET-CDs 3%-PET	70	118	245	201	44
PET-CDs 5%-PET	69	116	243	200	43

样品	T_5%/℃	T_max/℃	残炭量(700 ℃)/%
纯PET	403.33	445.39	8.48
PET-CDs 1%-PET	401.51	445.97	11.52
PET-CDs 3%-PET	398.65	445.07	11.72
PET-CDs 5%-PET	391.99	440.67	8.64

样品	t₁/s	t₂/s	是否熔滴	是否引燃脱脂棉	UL-94 等级
纯PET	42.0±10.7	8.7±6.9	是	是	—
PET-CDs 1%-PET	7.7± 1.8	2.8±2.0	是	是	V-2
PET-CDs 3%-PET	2.5± 0.3	1.3±0.3	是	是	V-2
PET-CDs 5%-PET	1.9± 0.5	2.5±0.7	是	是	V-2

样品	TTI/s	PHRR/(kW·m^-2)	THR/(MJ·m²)	CO峰值/(kg·kg^-1)	CO₂峰值/(kg·kg^-1)	TSR/m²
纯PET	48	892.87	80.1	21.7	196.3	1 995
PET-CDs 1%-PET	60	702.98	78.9	12.6	125.8	1 834
PET-CDs 3%-PET	59	691.34	72.3	6.7	60.1	1 834
PET-CDs 5%-PET	67	677.78	65.7	4.6	58.6	1 710

聚对苯二甲酸乙二醇酯基碳点热解法制备及其在阻燃改性中的应用

Preparation of PET-based carbon dots by pyrolysis and its application in PET flame retardancy

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样品	拉伸强度/MPa	弹性模量/MPa	断裂伸长率/%
纯PET	60.0±1.4	1 079.4±21.4	507.6±27.7
PET-CDs 1%-PET	49.7±1.0	1 045.2±20.3	480.0±11.2
PET-CDs 3%-PET	45.8±1.3	965.7±36.7	41.3±13.8
PET-CDs 5%-PET	8.8±1.0	921.1±63.2	2.8± 0.1

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