阻燃、抗熔滴一体化CNSs-BA/PET复合材料的制备及性能

肖云超; 杨雅茹; 陈建航; 曹红; 付建勋; 孔文龙

阻燃、抗熔滴一体化CNSs-BA/PET复合材料的制备及性能

肖云超^{1, 2},
杨雅茹^{1, 2, 3, ,},
陈建航¹,
曹红²,
付建勋³,
孔文龙⁴

1.
嘉兴大学　材料与纺织工程学院, 嘉兴 314001
2.
嘉兴大学　G60科创走廊产业与创新研究院, 嘉兴 314001
3.
上海大学　材料科学与工程学院, 上海 200444
4.
国望高科纤维(宿迁)有限公司, 宿迁 223800)

基金项目: 浙江省自然科学基金(LQ22C100002)；嘉兴市科技计划项目-青年科技人才专项(2023AY40034)；嘉兴大学SRT计划项目(8517231012)。

详细信息

通讯作者:
杨雅茹，博士，讲师，硕士生导师，研究方向为阻燃材料　E-mail: yyr0515@zjxu.edu.cn

中图分类号: TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2024-04-29
- 修回日期: 2024-05-24
- 录用日期: 2024-05-28
- 网络出版日期: 2024-06-18

Preparation and properties of CNSs-BA/PET composites integrated with flame retardancy and melt-drop resistance

XIAO Yunchao^{1, 2},
YANG Yaru^{1, 2, 3
, ,},
CHENG Jianhang¹,
CAO hong²,
FU Jianxun³,
KONG Wenlong⁴

1.
School of Materials and Textile Engineering, Jiaxing University, Jiaxing 314001, China
2.
G60 STl Valley Industry & Innovation Institute, Jiaxing University, Jiaxing 314001, China
3.
School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
4.
Guowang Hi-Tech Fiber (Suqian) Limited Company, Suqian 223800, China)

Funds: Natural Science Foundation of Zhejiang Province (No. LQ22C100002); Jiaxing Science and Technology Program Project-Young Science and Technology Talents Special Project (No. 2023AY40034); Jiaxing University SRT Program Project (No. 8517231012)

摘要

摘要: 聚对苯二甲酸乙二醇酯(PET)的易燃问题极大地威胁着人们的生命和财产安全，但通用阻燃剂无法兼顾其阻燃和抗熔滴需求。为同时改善PET的阻燃性和抗熔滴性，在碳纳米球(CNSs)表面接枝芳香席夫碱(BA)制备了一种新型的纳米碳基复合阻燃剂CNSs-BA，并将其通过熔融共混法引入PET中制备了复合材料。对CNSs-BA阻燃剂的形貌结构和热稳定性进行了表征，并研究了CNSs-BA/PET复合材料的阻燃性及其阻燃机制。结果表明：CNSs-BA为粒径50 nm左右的球状颗粒，热稳定性良好。当CNSs-BA添加量仅为2.0wt.%时，CNSs-BA/PET的LOI从PET的21.0%提高至28.1%，阻燃等级达到UL-94 V-0级，峰值热释放速率降低了46.3%。阻燃机制研究表明：CNSs-BA/PET表现出典型的凝聚相阻燃机制，CNSs-BA的引入可显著提高PET的成炭性，CNSs-BA/PET的高温残炭量较纯PET提高了55.4%，且其成炭量的实际值大于理论值。与纯PET相比，CNSs-BA阻燃剂的引入使PET熔融之后发生了高温交联，使得CNSs-BA/PET燃烧生成的炭层致密性、连续性和热稳定性均显著提高。
- 碳纳米球 /
- 聚对苯二甲酸乙二醇酯 /
- 复合材料 /
- 阻燃 /
- 抗熔滴
Abstract: The inherent flammability of polyethylene terephthalate (PET) poses a considerable THReat to human lives and property, yet conventional flame retardants fail to adequately address both flame resistance and melt-drop concerns. To effectively enhance both the flame retardancy and melt-drop resistance of PET, a novel nanocarbon- method. The morphology structure and thermal stability of CNSs-BA were characterized. The flame retardancy of based composite flame retardant, CNSs-BA, was prepared by grafting aromatic Schiff bases (BA) on the surface of carbon nanospheres (CNSs), and the composite was prepared by introducing CNSs-BA into PET via melt blending CNSs-BA/PET composites and its flame retardant mechanism were investigated. The results show that the CNSs-BA with the addition of just 2.0wt.% of CNSs-BA, the limiting oxygen index (LOI) of the CNSs-BA/PET composite increased significantly from 21.0% to 28.1%, achieving a UL-94 V-0 flame retardant grade. Furthermore, the peak heat exhibit a spherical shape with a particle size approximating 50 nm and possess remarkable thermal stability. Notably, release rate was reduced by an impressive 46.3%. The investigation into the flame retardant mechanism revealed that the CNSs-BA/PET composite exhibits a typical condensed-phase flame retardant behavior. The introduction of CNSs-BA greatly enhances the char formation of PET, with the high-temperature char residual of the composite increasing by 55.4% compared to pure PET, and the actual value of char formation exceeds the theoretical value. Moreover, the addition of CNSs-BA flame retardant triggers high-temperature crosslinking in PET after melting, leading to a substantial improvement in the density, continuity and thermal stability of the char layer formed during the combustion of the CNSs-BA/PET composite.
- carbon nanospheres /
- PET /
- composites /
- flame retardancy /
- melt-drop resistance

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图 1 碳纳米球(CNSs)-芳香席夫碱(BA)制备示意图

Figure 1. Schematic diagram of the preparation of carbon nanospheres (CNSs)- Schiff bases (BA)

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图 2 CNSs(a)和CNSs-BA(b)的SEM图和EDS能谱图

Figure 2. SEM and EDS images of CNSs (a) and CNSs-BA (b)

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图 3 CNSs和CNSs-BA的红外光谱

Figure 3. Infrared spectra of CNSs和CNSs-BA

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图 4 CNSs和CNSs-BA的TG(a)和DTG(b)曲线

Figure 4. TG(a) and DTG(b) curves of CNSs and CNSs-BA

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图 5 CNSs-BA/PET的热释放速率(a)和总热释放(b)曲线

Figure 5. Curves of heat release rate (HRR) and total heat release (THR) of CNSs-BA/PET

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图 6 CNSs、CNSs-BA以及PET、CNSs/PET、CNSs-BA/PET的TG(a)和DTG(b)曲线

Figure 6. TG (a) and DTG (b) curves of CNSs, CNSs-BA, PET, CNSs/PET and CNSs-BA/PET

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图 7 PET(a)、CNSs/PET(b)和CNSs-BA/PET(c)残炭的SEM图

Figure 7. SEM images of the char residues of PET(a), CNSs/PET(b)和CNSs-BA/PET(c)

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图 8 残炭的TG曲线

Figure 8. TG curves of the char residues

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图 9 PET、CNSs/PET和CNSs-BA/PET的TG-DSC曲线

Figure 9. TG-DSC curves of PET, CNSs/PET, and CNSs-BA/PET

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图 10 PET复合材料的抗拉强度(a)和断裂伸长率(b)

Figure 10. Tensile strength (a) and elongation at break (b) of PET composites

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表 1 LOI和UL 94垂直燃烧测试结果

Table 1. LOI and UL 94 vertical burning test results

Samples	Flame retardant content/wt.%	LOI /%	UL 94 Vertical combustion test results
Samples	Flame retardant content/wt.%	LOI /%	t₁ /s	t₂ /s	t₃ /s	Ignite cotton?	Rate
PET	—	21.0	Burn out	—	—	Yes	NR
CNSs/PET	0.5	23.2	2.6	2.5	0	Yes	V-2
	1.0	25.0	2.4	2.4	0	Yes	V-2
	2.0	26.2	2.4	2.8	0	Yes	V-2
	3.0	24.6	3.1	2.2	0	Yes	V-2
CNSs-BA/PET	0.5	24.0	1.5	2.3	0	Yes	V-2
	1.0	26.9	1.2	2.1	0	Yes	V-2
	2.0	28.1	0.5	2.2	0	No	V-0
	3.0	27.5	0.6	1.9	0	No	V-0
Notes: t₁-Afterglow time after the first application of flame, t₂-Afterglow time after the second application of flame, t₃-Afterglow time.

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表 2 锥形量热仪测试数据

Table 2. Data of cone calorimeter test

Samples	FR content/wt.%	TTI/s	Time to pk-HRR/s	pk-HRR/(kW·m⁻²)	THR/(MJ·m⁻²)
PET	0	47	104	810.45	150.27
CNSs/PET	0.5	44	34	528.96	151.64
	1	34	34	503.44	148.03
	2	40	41	470.72	146.06
	3	30	29	501.49	143.19
CNSs-BA/PET	0.5	35	39	485.54	146.54
	1	31	55	469.98	156.04
	2	34	39	433.90	146.54
	3	30	39	466.05	156.69
Notes: TTI- Time to ignition, pk-HRR- Peak heat release rate, THR- Total heat release.

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表 3 CNSs、CNSs-BA以及PET、CNSs/PET、CNSs-BA/PET在氮气气氛下的TG-DTG数据

Table 3. TG-DTG data of CNSs, CNSs-BA, PET, CNSs/PET and CNSs-BA/PET under nitrogen atmosphere

Samples	T_onset /℃	T_max /℃	C_R500℃ /%	∆C_R500℃/%^c
Samples	T_onset /℃	T_max /℃	exp.^a/cal.^b	∆C_R500℃/%^c
CNSs	＞800℃	-	96.88/-	-
CNSs-BA	476.4	-	94.92/-	-
PET	379.1	419.1	10.09/-	-
CNSs/PET	380.1	421.4	13.97/11.52	2.45
CNSs-BA/PET	382.0	420.1	15.68/11.79	3.89
Note: ^a C_{R500℃, exp.} is the experimental value of char residue; ^b C_{R500℃, cal.} is the calculated value of char residue; ^c ∆C_R500℃ = C_{R500℃, exp.} - C_{R500℃, cal.}

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表 4 PET、CNSs/PET和CNSs-BA/PET在空气气氛下的TG-DTG数据

Table 4. TG-DTG data of PET, CNSs/PET and CNSs-BA/PET under air atmosphere

Samples	T_onset/℃	T_max-1/℃	T_max-2/℃
PET	397.3	433.4	585.1
CNSs/PET	359.1	438.4	567.5
CNSs-BA/PET	391.0	439.7	563.3
Notes: T_onset - initial weightlessness temperature, T_max-1- Maximum weightlessness temperature in the first stage, T_max-2- Maximum weightlessness temperature of the second stage.

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表 5 PET、CNSs/PET和CNSs-BA/PET裂解产物

Table 5. Pyrolysis products of PET, CNSs/PET and CNSs-BA/PET

Pyrolysis products which found only in PET	Tetrahydropyran, 2,2-dimethylpropanal, 4,8,12-trimethyl-tridecanoic acid methyl ester, 2,2-dimethoxybutane, 2-methyl-1,5-hexadien-3-yne, 1,6-heptadiyne, p-xylene, decane, methyl benzoate, dodecylethyl ketone, 1-(3-methylphenyl), benzyl, (2-methyl-1-methylenepropylidene), 4-methylphenyl-1-pentyn-3 -ol phenol, dimethyl 1,3-benzenedicarboxylate, vinylmethyl terephthalate, diphenylacetylene, biphenyl-4-ylacetophenone, 1-(5,5-dimethyl-1,3-dioxocyclohexan-2-ylidene)-2-(N-ethylbenzothiazol-2-ylidene)-ethanes, phthalic acid, 4-formylphenyl ester, o-tertiaryl tricyclic [8.2.2.2(4,7)]hexadeca- 2,4,6,8,10,12,13,15-octene, 4-(diethylaminomethyl)-2,5-dimethylphenol
Pyrolysis products which found only in CNSs/PET	Phenol, 1,2-dihydro-indene, 1-(4-methylphenyl)-ethanone, stilbene, 1 H-cyclopropyl[l]phenanthrene, dihydro-p-terphenyl, 1-naphthol, fluorene-9-methanol, 2-ethyl-1,1'-biphenyl, 1,1-diphenylethene, 4-(2-benzoyl-5-phenyl-3-thienyl)-1,2-dihydrophenanthrene 2-phenylnaphthalenyl benzoate, 1,1-dihydro-2-phenylnaphthalenyl benzoate, 3-chlorobenzylnononyl, 1-(2,5-dimethylphenyl)ethanone, 1-(2,5-dimethylphenyl)ethanone, 1-(2,5-dimethylphenyl)ethanone, 1-(2,5-dimethylphenethyl) ethanone, 3-chlorobenzylnonyl, 1-(2,5-dimethylphenyl) acetone dimethyl-1 H-indene, diethylmalonic acid, 3-chlorobenzylnonyl ester, 1-(2,5-dimethylphenyl) ethanone
Pyrolysis products which found only in CNSs-BA/PET	1,5-Hexadiyne, dimethylamine, nitrous oxide, 1,1'-(1,4-phenylene)bis-acetophenone, 2-methylindene, azobenzene, benzene, (1-methyl-2-cyclopropen-1-yl)-2-methylindene, stilbene, ethylketone, 1-(3,4-dimethylphenyl), ethylketone, 1-(4-methylphenyl), 1-ethenyl-4-methylbenzene, dibenzofuran, 2-naphthol, 4-hydroxy-1,2,3,4-tetrahydrophenanthrene, 9,10-dihydrophenanthrene, benzopropiophenone, fluorene, 4-vinylbiphenyl, 1,2,3,4-tetrahydrofil, 9,10-dihydrofil, fluorene, 4-vinylbiphenyl, 1,4-vinylbiphenyl. hydroxy-1,2,3,4-tetrahydrophenanthrene, 9,10-dihydrophenanthrene, phenylacetone, fluorene, 4-vinylbiphenyl, 1,3,5-cycloheptatriene, 2-phenylnaphthalene, 1-acrylbenzene, 2-methylnaphthalene, 4-(2-benzoyl-5-phenyl-3-thienyl)-methylbenzoic acid, 1,3-dimethyl-1 H-indene, tricyclohexen-8-ol, hexaethylcyclohexane, 9- phenyl-9-fluorenol, ethylene oxide, methoxyphenyltricyclohexadecen-5-ylmethanol, 4-benzylbiphenyl, tritylbenzene, 9-phenylanthracene, 3-(1-phenylethoxy)-3 H-isobenzofuran-1-one, 4-phenyl-3,4-dihydroisoquinoline, oxetane,-2-phenyl,-3-phenylethynyl, tetraphenyl, 1-[4-(2-phenylethenyl)phenyl]-ethanone, acenaphthene, 1,2 ,3,5-tetraisopropyl-cyclohexane, 6,9-dimethoxy-phenazine-1-carboxylic acid, [1,1'-biphenyl]-4-yl-phenylmethanone, 1,1':4',1''-3'-methyltriphenylene
Pyrolysis products which found both in PET and CNSs/PET	Acetophenone, benzoic acid, biphenyl, 2-methyl-1,1'-biphenyl, 1,1'-(1,4-phenylene)bisacetophenone, p-terphenyl
Pyrolysis products which found both in PET and CNSs-BA/PET	Styrene, acetophenone, benzoic acid, biphenyl, 2-ethyl-1,1'-biphenyl, benzophenone, 9 H-fluoren-9-one, p-terphenyl
Pyrolysis products which found both in CNSs/PET and CNSs-BA/PET	Benzene, biphenyl, acetophenone, naphthalene, toluene, phenanthrene, indene, 6,6-diphenylfulvene, p-terphenyl, methylstyrene, biphenylacetophenone, 4-ethylbiphenyl, diphenylmethane
Pyrolysis products found in PET, CNS/PET and CNSs-BA/PET	Acetophenone, benzoic acid, biphenyl, p-terphenyl

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