三聚氰胺植酸/硬质聚氨酯泡沫复合材料的制备及其热解动力学特性

张冰; 杨素洁; 杨亚东; 刘新亮; 刘梦茹; 唐刚; 刘秀玉

doi:10.13801/j.cnki.fhclxb.20201110.002

三聚氰胺植酸/硬质聚氨酯泡沫复合材料的制备及其热解动力学特性

doi: 10.13801/j.cnki.fhclxb.20201110.002

张冰^1,,
杨素洁^1,,
杨亚东¹,
刘新亮¹,
刘梦茹^1,,
唐刚^{1, 2},
刘秀玉^{1, 2, ,}

1.
安徽工业大学　建筑工程学院，马鞍山 243032
2.
南京工大开元环保科技(滁州)有限公司，滁州 239000

基金项目: 国家自然科学基金(51403004)；中国博士后科学基金面上项目(2017M610399)

详细信息

通讯作者:
刘秀玉，博士，副教授，硕士生导师，研究方向为有机建筑保温材料、阻燃聚合物复合材料　 E-mail：cristalliu@163.com

中图分类号: TB332；TQ328.3
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出版历程
- 收稿日期: 2020-09-03
- 录用日期: 2020-10-27
- 网络出版日期: 2020-11-10
- 刊出日期: 2021-08-15

Preparation and pyrolysis kinetics of melamine phytates/rigid polyurethane foam composites

ZHANG Bing^1
,,
YANG Sujie^1
,,
YANG Yadong¹,
LIU Xinliang¹,
LIU Mengru^1
,,
TANG Gang^{1, 2},
LIU Xiuyu^{1, 2
, ,}

1.
School of Architecture and Civil Engineering, Anhui University of Technology, Ma’anshan 243032, China
2.
Nanjing Gongda Kaiyuan Environmental Protection Technology (Chuzhou) CO. LTD., Chuzhou 239000, China

摘要

摘要: 以实验室自制的三聚氰胺植酸(MEL-PA)为阻燃剂，采用一步法全水发泡工艺制备一系列三聚氰胺植酸/硬质聚氨酯泡沫(MEL-PA/RPUF)复合材料。采用热重分析(TG)与热分析动力学研究复合材料热稳定性，揭示其降解机制。研究表明，随着MEL-PA负载量的增加，MEL-PA/RPUF在700 ℃的残炭率逐渐提升。结合TGA数据，通过Coats-Redfern和Horowitz-Metzger积分法计算复合材料主要降解阶段的反应等级n、活化能E及指前因子A。结果表明，空气氛围中MEL-PA促进了复合材料的初始降解，而在高温阶段使复合材料具有更高的热稳定性，并且两种计算方法具有相同规律。N₂氛围中，MEL-PA30/RPUF(MEL-PA质量分数为10.3wt%)与RPUF相比，n增大，E升高。表明MEL-PA30/RPUF的反应更为复杂，热稳定性更高。通过Criado法进行数学模型与实验分析，验证了Coats-Redfern法的可行性。MEL-PA/RPUF复合材料的热氧化降解动力学研究结果为分析不同阻燃体系的RPUF的阻燃性能提供参考依据。
- 硬质聚氨酯泡沫 /
- 三聚氰胺植酸 /
- 复合材料 /
- 热稳定性 /
- 热解动力学
Abstract: A series of melamine phytates/rigid polyurethane foam (MEL-PA/RPUF) composites were prepared by one-step water-blown method with MEL-PA as flame retardant. Thermogravimetric analysis (TG) and thermal analysis kinetics were used to study the thermal stability of the composites and reveal its degradation mechanism. The results show that the char residues of MEL-PA/RPUF gradually increases at 700℃ with the increase of MEL-PA loading. Based on TGA data, the reaction grade n, activation energy E and pre exponential factor A of the main degradation stage for the composites were calculated by the Coats-Redfern and Horowitz-Metzger integration methods. The results show that MEL-PA promotes the initial degradation of the composites in air atmosphere, while the MEL-PA/RPUF composites have higher thermal stability in the high temperature stage, and the two calculation methods have the same law. In N₂ atmosphere, MEL-PA30/RPUF (mass fraction of MEL-PA is 10.3wt%) has higher n and E compared with RPUF. The results indicate that the reaction of MEL-PA30/RPUF is more complex and the thermal stability is higher. The mathematical model and experimental analysis by Criado method verify the feasibility of the Coats-Redfern method. The results of thermal degradation kinetics of MEL-PA/RPUF composites provide reference for the analysis of flame retardation performance of RPUF with different flame retardation systems.
- rigid polyurethane foam /
- melamine phytates /
- composites /
- thermal stability /
- pyrolysis kinetics

HTML全文

图 1 RPUF及MEL-PA/RPUF复合材料在空气 ((a)、(b)) 和N₂((c)、(d)) 条件下的TG及DTG曲线

Figure 1. TG and DTG curves of RPUF and MEL-PA/RPUF composites under air ((a), (b)) and N₂ ((c), (d)) conditions

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图 2 空气氛围下RPUF和MEL-PA/RPUF复合材料在α为0.05~0.45范围内的Coats-Redfern分析结果

Figure 2. Results of Coats-Redfern method for RPUF and RPUF/MEL-PA composites with α of 0.05~0.45 under air condition

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图 3 空气氛围下RPUF和MEL-PA/RPUF复合材料在α为0.65~0.90范围内的Coats-Redfern分析结果

Figure 3. Results of Coats-Redfern method for RPUF and RPUF/MEL-PA composites with α of 0.65~0.90 under air condition

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图 4 空气氛围下RPUF和MEL-PA/RPUF复合材料在α为0.05~0.45范围内Horowitz-Metzger分析结果

Figure 4. Results of Horowitz-Metzger method for RPUF and MEL-PA/RPUF composites with α of 0.05~0.45 under air condition

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图 5 空气氛围下RPUF和MEL-PA/RPUF复合材料在α为0.65~0.90范围内Horowitz-Metzger分析结果

Figure 5. Results of Horowitz-Metzger method for RPUF and MEL-PA/RPUF composites with α of 0.65~0.90 under air condition

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图 6 N₂氛围下RPUF和MEL-PA30/RPUF在α为0.1~0.7范围内Coats-Redfern法((a)、(b))和Horowitz-Metzger法((c)、(d))分析结果

Figure 6. Results of Coats-Redfern ((a), (b)) and Horowitz-Metzger ((c), (d)) methods for RPUF and MEL-PA30/RPUF with α of 0.1~0.7 under N₂ condition

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图 7 Criado法获得的固相反应机制的理论曲线与RPUF和MEL-PA30/RPUF的实验曲线

Figure 7. Theoretical curves of solid-phase reaction mechanism and experimental curves of RPUF and MEL-PA30/RPUF obtained by Criado method

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表 1 硬质聚氨酯泡沫(RPUF)及三聚氰胺植酸/硬质聚氨酯泡沫(MEL-PA/RPUF)复合材料组成

Table 1. Composition of rigid polyurethane foam (RPUF) and melamine phytates/rigid polyurethane foam (MEL-PA/RPUF) composites

Sample	LY-4110/g	PM-200/g	A33/g	AK-8805/g	LC/g	TEOA/g	Water/g	MEL-PA/g	MEL-PA/wt%
RPUF	100	150	1	2	0.5	3	2	0	0
MEL-PA10/RPUF	100	150	1	2	0.5	3	2	10	3.7
MEL-PA20/RPUF	100	150	1	2	0.5	3	2	20	7.1
MEL-PA30/RPUF	100	150	1	2	0.5	3	2	30	10.3
Notes: LY-4110—Polyether polyol; PM-200—Polyaryl polymethylene isocyanate; A33—Triethylene diamine; AK-8805—Silicone surfactant; LC—Dibutyltin dilaurate; TEOA—Triethanolamine.

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表 2 RPUF和MEL-PA/RPUF在空气条件下的TGA结果

Table 2. TGA results of RPUF and MEL-PA/RPUF under air condition

Sample	T_−5%/℃	T_−50%/℃	T_max/℃		V_max/(%·℃⁻¹)		Char residueat 700℃/wt%
Sample	T_−5%/℃	T_−50%/℃	Step 1	Step 2	Step 1	Step 2	Char residueat 700℃/wt%
RPUF	271	376	312	569	0.569	0.425	1.2
MEL-PA10/RPUF	266	370	310	567	0.595	0.411	4.2
MEL-PA20/RPUF	250	373	326	570	0.582	0.391	4.4
MEL-PA30/RPUF	233	375	325	566	0.602	0.392	4.8
Notes: T_−5%—Onset degradation temperature; T_−50%—Midpoint temperature of the degradation; T_max—Maximum decomposition temperature; V_max—Maximum decomposition rate.

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表 3 RPUF和MEL-PA/RPUF30在N₂条件下的TGA结果

Table 3. TGA results of RPUF and MEL-PA/RPUF30 under N₂ condition

Sample	T_−5%/℃	T_−50%/℃	T_max/℃		Char residueat 700℃/wt%
Sample	T_−5%/℃	T_−50%/℃	Step 1	Step 2	Char residueat 700℃/wt%
RPUF	254	338	335	463	12.4
MEL-PA30/ RPUF	242	347	340	487	20.6

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表 4 Criado法的积分机理函数$ g\left(\alpha \right) $和微分机制函数$ f\left(\alpha \right) $表达式

Table 4. Expressions of integral mechanism function $ g\left(\alpha \right) $ and differential mechanism function $ f\left(\alpha \right) $ of Criado method

Reaction mechanism	Code	$ f\left(\alpha \right) $	$ g\left(\alpha \right) $
Random nucleation and nuclei growth
Two-dimensional	A2	2(1−$ \alpha $)[−ln(1−$ \alpha $)]^1/2	[−ln(1−$ \alpha $)]^1/2
Three-dimensional	A3	3(1−$ \alpha $)[−ln(1−$ \alpha $)]^2/3	[−ln(1−$ \alpha $)]^1/3
Four-dimensional	A4	4(1−$ \alpha $)[−ln(1−$ \alpha $)]^3/4	[−ln(1−$ \alpha $)]^1/4
Limiting surface reaction between both phases
One-dimensional	R1	1	$ \alpha $
Contracting sphere	R2	2(1−$ \alpha $)^1/2	1−(1−a)^1/2
Contracting cylinder	R3	3(1−$ \alpha $)^2/3	1−(1−a)^1/3
Diffusion
One-way transport	D1	1/(2$ \alpha $)	$ \alpha $²
Two-way transport	D2	[−ln(1−a)]⁻¹	(1−$ \alpha $) ln(1−$ \alpha $)+$ \alpha $
Three-way transport	D3	3/2[1−(1−$ \alpha $)^1/3]⁻¹(1−$ \alpha $)^2/3	[1−(1−$ \alpha $)^1/3]²
Ginstling-Brounshtein equation	D4	3/2[(1−$ \alpha $)^−1/3−1]⁻¹	(1−2/3$ \alpha $)− (1−$ \alpha $)^2/3
Order of reaction
First order	F1	1−$ \alpha $	−ln(1−$ \alpha $)
Second order	F2	(1−$ \alpha $)²	(1−$ \alpha $)⁻¹−1
Third order	F3	(1−$ \alpha $)³	[(1−$ \alpha $)⁻²−1]/2
Exponential nucleation
Power law, n = 1/2	P2	2$ \alpha $^1/2	$ \alpha $^1/2
Power law, n = 1/2	P3	3$ \alpha $^2/3	$ \alpha $^1/3
Power law, n = 1/4	P4	4$ \alpha $^3/4	$ \alpha $^1/4

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表 5 空气氛围下加热速率为20℃/min的Coats-Redfern法获得的RPUF及MEL-PA/RPUF复合材料动力学参数

Table 5. Kinetic parameters of RPUF and MEL-PA/RPUF composites obtained by Coats-Redfern method with heating rates of 20℃/min in air atmosphere

α	Sample	n	E/(kJ·mol⁻¹)	lnA	R²
0.05-0.45	RPUF	5.5	126.15	25.03	0.99963
	MEL-PA10/RPUF	4	107.65	21.02	0.99915
	MEL-PA20/RPUF	2.5	70.07	13.66	0.99867
	MEL-PA30/RPUF	0.2	45.45	6.94	0.99526
0.65-0.90	RPUF	0.4	25.33	1.13	0.98784
	MEL-PA10/RPUF	0.2	17.30	−0.47	0.97172
	MEL-PA20/RPUF	0.6	30.36	2.13	0.99286
	MEL-PA30/RPUF	0.8	38.00	3.61	0.99332
Notes: α—Conversion rate; n—Reaction grade; E—Activation energy; A—Pre exponential factor.

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表 6 空气氛围下加热速率为20℃/min的Horowitz-Metzger法获得的RPUF及MEL-PA/RPUF复合材料动力学参数

Table 6. Kinetic parameters of RPUF and MEL-PA/RPUF composites obtained by Horowitz-Metzger method with heating rates of 20℃/min in air atmosphere

α	Sample	n	E/(kJ·mol⁻¹)	lnA	R²
0.05-0.45	RPUF	7	157.06	31.82	0.99967
	MEL-PA10/RPUF	5.5	139.87	28.16	0.99942
	MEL-PA20/RPUF	3.5	103.21	20.09	0.99931
	MEL-PA30/RPUF	1.5	72.35	13.10	0.99782
0.65-0.90	RPUF	0.4	39.22	3.55	0.99552
	MEL-PA10/RPUF	0.1	28.85	1.63	0.99345
	MEL-PA20/RPUF	0.8	51.83	5.86	0.99703
	MEL-PA30/RPUF	1	60.01	7.36	0.99695

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表 7 N₂氛围下加热速率为20℃/min的Coats-Redfern和Horowitz-Metzger法获得的RPUF及MEL-PA30/RPUF复合材料动力学参数

Table 7. Kinetic parameters of RPUF and MEL-PA30/RPUF composites obtained by Coats-Redfern and Horowitz-Metzger methods with heating rate of 20℃/min in N₂ atmosphere

Method	Sample	n	E/(kJ·mol⁻¹)	lnA	R²
Coats-Redfern	RPUF	0.8	61.14	10.75	0.99820
Coats-Redfern	MEL-PA30/RPUF	1.8	80.93	15.46	0.99752
Horowitz-Metzger	RPUF	1.4	89.13	16.86	0.99891
Horowitz-Metzger	MEL-PA30/RPUF	2.3	109.66	21.67	0.99766

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