碳化钛-二氧化锰/热塑性聚氨酯纳米复合材料的制备及阻燃性能

施永乾; 马苏宁; 杨晔; 刘川; 叶娅婷

doi:10.13801/j.cnki.fhclxb.20211012.001

碳化钛-二氧化锰/热塑性聚氨酯纳米复合材料的制备及阻燃性能

doi: 10.13801/j.cnki.fhclxb.20211012.001

福州大学　环境与安全工程学院，福州 350108

基金项目: 国家自然科学基金(52173070)

详细信息

通讯作者:
施永乾，博士，副教授，硕士生导师，研究方向为阻燃高分子复合材料设计与应用　E-mail：shiyq1986@fzu.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2021-08-19
- 修回日期: 2021-09-22
- 录用日期: 2021-09-25
- 网络出版日期: 2021-10-12
- 刊出日期: 2022-08-22

Preparation and flame retardancy of titanium carbide-manganese dioxide/thermoplastic polyurethane nanocomposites

School of Environment and Safety Engineering, Fuzhou University, Fuzhou 350108, China

摘要

摘要: 热塑性聚氨酯(TPU)具有优良的性能，现已广泛应用于生产生活的各个领域。但该材料是一种有机高分子材料，具有高度易燃性，且燃烧时会发生熔融滴落现象，同时产生大量CO、CO₂、NO_x等有毒、窒息性气体，限制了TPU的应用。将层状碳化钛(Ti₃C₂T_x)与二氧化锰(MnO₂)通过界面调控技术制备为MXene(一类二维无机化合物，碳化钛是其中的一种)基杂化阻燃剂(Ti₃C₂T_x-MnO₂)，然后再引入TPU材料形成MXene/TPU基杂化物纳米复合材料(Ti₃C₂T_x-MnO₂/TPU)，利用TGA、XRD、SEM等进行检测。结果显示，在Ti₃C₂T_x-MnO₂/TPU纳米复合材料中，700℃时炭渣含量最大程度提高91.89%，总热释放量(THR)、总烟释放量(TSR)、CO释放总量(CO TY)和CO₂释放总量(CO₂ TY)相较于纯TPU分别最大程度降低了28.62%、33.41%、34.12%和29.77%。通过分析，MXene基杂化阻燃剂中Ti₃C₂T_x氧化为TiO₂，并与MnO₂协同催化成炭，大幅度提高纳米复合材料燃烧后炭层连续性和致密性，阻隔热量、阻挡氧气进入并抑制烟气释放。
- 热塑性聚氨酯 /
- 碳化钛 /
- 二氧化锰 /
- 界面修饰 /
- 阻燃 /
- 抑烟减毒
Abstract: Thermoplastic polyurethane elastomer (TPU) was equipped with excellent properties, which was widely used in various fields of industry and living. However, the application scope of TPU was limited because the material was a kind of organic polymer material with high inflammability. Moreover, a large amount of CO, CO₂, NO_x and other toxic asphyxiating gases from TPU material were released during combustion. The design of MXene-based hybrid flame retardant based on layered titanium carbide (Ti₃C₂T_x) and manganese dioxide (MnO₂) was proposed for preparation of MXene-based hybrid/TPU nanocomposites. The mechanisms of flame retardancy, smoke suppression and toxicity reduction of the TPU nanocomposites were studied by means of TGA, XRD, SEM and other techniques. In the case of Ti₃C₂T_x-MnO₂/TPU systems, the total heat release (THR), the total smoke release (TSR), the total CO yield (CO TY) and the total CO₂ yield (CO₂ TY) of the TPU nanocomposite were maximally decreased by 28.62%, 33.41%, 34.12% and 29.77% respectively compared to those of TPU, besides 91.89% increase in residual char at 700℃. According to the analysis, Ti₃C₂T_x in MXene-based hybrid flame retardant was oxidized to TiO₂ and co-catalyzed with MnO₂ to form carbon, which not only improved the continuity and compactness of carbon layer after combustion of nanocomposite materials, but also blocked the entry of heat and oxygen and inhibit the release of flue gas.
- thermoplastic polyurethane /
- titanium carbide /
- manganese dioxide /
- interface decoration /
- flame retardancy /
- smoke suppression

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图 1 阻燃剂层状碳化钛(Ti₃C₂T_x)-MnO₂及其热塑性聚氨酯(TPU)纳米复合材料的制备路线图

Figure 1. Preparation route of layered titanium carbide (Ti₃C₂T_x)-MnO₂ flame retardant and thermoplastic polyurethane (TPU) nanocomposites

NPs—Nanoparticles

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图 2 阻燃剂Ti₃AlC₂、Ti₃C₂T_x、MnO₂和Ti₃C₂T_x-MnO₂的XRD图谱

Figure 2. XRD patterns of Ti₃AlC₂, Ti₃C₂T_x, MnO₂ and Ti₃C₂T_x-MnO₂ flame retardants

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图 3 TPU纳米复合材料N₂氛围下的热重曲线 (a) 和热重微分曲线 (c)，以及空气氛围下的热重曲线 (b) 和热重微分曲线 (d)

Figure 3. Thermogravimetric (a) and thermogravimetric differential (c) curves in N₂, as well as thermogravimetric (b) and thermogravimetric differential (d) curves in air of TPU nanocomposites

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图 4 TPU纳米复合材料的热释放速率 (a)、总热释放量 (b)、烟释放速率 (c) 和总烟释放量 (d) 曲线

Figure 4. Heat release rate (a), total heat release (b), smoke production rate (c), and total smoke release (d) curves of TPU nanocomposites

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图 5 TPU纳米复合材料的CO释放速率 (a)、总CO释放量 (b)、CO₂释放速率 (c) 和总CO₂释放量 (d) 曲线

Figure 5. CO production rate (a), total yield of CO (b), CO₂ production rate (c) and total yield of CO₂ (d) curves of TPU nanocomposites

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图 6 锥形量热仪测试后样品炭渣的数码照片：(a) TPU；(b) MnO₂/TPU；(c) Ti₃C₂T_x/TPU；(d) Ti₃C₂T_x-MnO₂-0.5/TPU；(e) Ti₃C₂T_x-MnO₂-1.0/TPU；(f) Ti₃C₂T_x-MnO₂-2.0/TPU

Figure 6. Digital photo of carbon residues of samples after cone calorimeter test: (a) TPU; (b) MnO₂/TPU; (c) Ti₃C₂T_x/TPU; (d) Ti₃C₂T_x-MnO₂-0.5/TPU; (e) Ti₃C₂T_x-MnO₂-1.0/TPU; (f) Ti₃C₂T_x-MnO₂-2.0/TPU

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图 7 锥形量热仪测试(CCT)后TPU纳米复合材料炭渣的XRD图谱

Figure 7. XRD patterns of carbon residues of TPU nanocomposites after cone calorimeter test (CCT)

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图 8 锥形量热仪测试后TPU纳米复合材料炭渣的SEM图像：((a1), (a2)) TPU；((b1), ( b2)) MnO₂/TPU；((c1), (c2)) Ti₃C₂T_x/TPU；((d1), (d2)) Ti₃C₂T_x-MnO₂-0.5/TPU；((e1), (e2)) Ti₃C₂T_x-MnO₂-1.0/TPU；((f1), (f2)) Ti₃C₂T_x-MnO₂-2.0/TPU

Figure 8. SEM images of carbon residues of TPU nanocomposites after CCT: ((a1), (a2)) TPU; ((b1), (b2)) MnO₂/TPU; ((c1), (c2)) Ti₃C₂T_x/TPU; ((d1), (d2)) Ti₃C₂T_x-MnO₂-0.5/TPU; ((e1), (e2)) Ti₃C₂T_x-MnO₂-1.0/TPU; ((f1), (f2)) Ti₃C₂T_x-MnO₂-2.0/TPU

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表 1 TPU纳米复合材料配方表

Table 1. Recipe list of TPU nanocomposites

No.	Sample	TPU/g	Ti₃C₂T_x-MnO₂/g	Ti₃C₂T_x/g	MnO₂/g
1^#	TPU	60.000	0.000	0.000	0.000
2^#	Ti₃C₂T_x-2.0/TPU	58.800	0.000	1.200	0.000
3^#	MnO₂-2.0/TPU	58.800	0.000	0.000	1.200
4^#	Ti₃C₂T_x-MnO₂-2.0/TPU	58.800	1.200	0.000	0.000
5^#	Ti₃C₂T_x-MnO₂-1.0/TPU	59.400	0.600	0.000	0.000
6^#	Ti₃C₂T_x-MnO₂-0.5/TPU	59.700	0.300	0.000	0.000

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表 2 TPU纳米复合材料的热降解行为

Table 2. Thermal degradation behavior of TPU nanocomposites

Sample	T_−5%/℃	T_−50%/℃	T_max/℃		Residual yield/wt%
Sample	T_−5%/℃	T_−50%/℃	Step1	Step2	Residual yield/wt%
TPU	319.9	392.4	340.3	404.8	5.92
Ti₃C₂T_x-2.0/TPU	305.9	400.4	329.9	409.6	7.80
MnO₂-2.0/TPU	257.1	310.6	275.7	311.6	9.04
Ti₃C₂T_x-MnO₂-2.0/TPU	295.3	376.1	396.0	349.3	11.36
Ti₃C₂T_x-MnO₂-1.0/TPU	296.2	373.2	323.1	378.7	10.51
Ti₃C₂T_x-MnO₂-0.5/TPU	310.1	392.4	344.9	405.5	4.47
Notes: T_−5%—Corresponding temperature at 5wt% weight loss; T_−50%—Corresponding temperature when the material is reduced to 50wt%; T_max—Temperature corresponding to the maximum mass loss rate.

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表 3 TPU纳米复合材料在热流密度为35 kW/m²的情况下锥形量热仪测试数据

Table 3. Conical calorimeter test data of the TPU nanocomposites under the heat flux of 35 kW/m²

Sample	TTI/ s	PHRR/ (kW·m⁻²)	THR/ (MJ·m⁻²)	PSPR/ (m²·s⁻¹)	TSR/ (m²·m⁻²)	PCOPR/ (g·s⁻¹)	PCO₂PR/ (g·s⁻¹)	CO TY/ (kg·kg⁻¹)	CO₂ TY/ (kg·kg⁻¹)
TPU	63	920	85.6	0.63	9108.4	0.0085	0.50	0.85	49.38
(Error)	±5	±65	±9.4	±0.04	±1073.6	±0.0005	±0.03	±0.07	±5.62
Ti₃C₂T_x-2.0/TPU	55	883	69.1	0.78	7528.6	0.0076	0.48	0.92	39.60
MnO₂-2.0/TPU	29	940	66.3	0.95	7447.3	0.0103	0.53	0.53	39.14
Ti₃C₂T_x-MnO₂-0.5/TPU	47	764	61.1	0.45	6576.8	0.0056	0.42	0.56	37.90
Ti₃C₂T_x-MnO₂-1.0/TPU	38	891	68.1	0.44	6065.6	0.0071	0.49	0.61	35.17
Ti₃C₂T_x-MnO₂-2.0/TPU	39	955	61.1	0.39	6285.8	0.0070	0.51	0.66	34.68
Notes: TTI—Time to ignite; PHRR—Peak of heat release rate; THR—Total heat release; PSPR—Peak of smoke production rate; TSR—Total smoke release; PCOPR—Peak of carbon monoxide production rate; PCO₂PR—Peak of carbon dioxide production rate; CO TY—Total yield of carbon monoxide; CO₂ TY—Total yield of carbon dioxide.

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