三聚氰胺聚磷酸盐和次磷酸铝协效阻燃高密度纤维板复合材料

唐启恒; 任一萍; 郭文静

doi:10.13801/j.cnki.fhclxb.20200727.004

三聚氰胺聚磷酸盐和次磷酸铝协效阻燃高密度纤维板复合材料

doi: 10.13801/j.cnki.fhclxb.20200727.004

中国林业科学研究院　木材工业研究所，北京 100091

基金项目: 中央级公益性科研院所基本科研业务费专项资金（CAFYBB2018GD002-02）

详细信息

通讯作者:
郭文静，研究生，研究员，博士生导师，研究方向为新型绿色复合材料　 E-mail：guowj@caf.ac.cn

中图分类号: TB332; TQ323.4
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出版历程
- 收稿日期: 2020-03-26
- 录用日期: 2020-07-24
- 网络出版日期: 2020-07-28
- 刊出日期: 2021-01-15

Melamine polyphosphate and aluminium phosphinate synergistic flame retardant high density fiberboard composite

Research Institute of Wood Industry, Chinese Academy of Forestry, Beijing 100091, China

摘要

摘要: 将三聚氰胺聚磷酸盐(MPP)和次磷酸铝(AP)阻燃剂添加到木纤维/酚醛树脂(WF/PR)复合材料中，通过人造板热压工艺技术制备阻燃高密度纤维板(MPP-AP-WF/PR)复合材料，探索了MPP和AP组成复配阻燃剂时，MPP-AP-WF/PR复合材料达到最佳阻燃性能时MPP与AP的最佳质量比。采用弯曲强度、吸水厚度膨胀率、吸水率、热失重和极限氧指数(LOI)研究阻燃剂对MPP-AP-WF/PR复合材料的力学性能、耐水性能、耐热性能和阻燃性能的影响，探讨其阻燃机制。结果表明，添加阻燃剂之后，MPP-AP-WF/PR复合材料的力学性能和耐水性能明显降低；而热失重测试结果表明，阻燃剂对MPP-AP-WF/PR复合材料的初始耐热性能没有明显影响，但两者在高温下的协同效应有助于提高残炭量；LOI测试结果表明，单独使用时，MPP比AP具有更好的阻燃效果，当MPP和AP复配使用、MPP与AP的质量比为1∶2时，MPP-AP-WF/PR复合材料具有最好的阻燃效果，这是由于MPP和AP存在协同效用。且SEM和EDS表征发现，MPP-AP-WF/PR复合材料燃烧之后形成致密的含磷酸类物质的炭层，有效阻止了O₂和热量进入到炭层的内部，从而提高了MPP-AP-WF/PR复合材料的阻燃性能。
- 三聚氰胺聚磷酸盐 /
- 次磷酸铝 /
- 木纤维 /
- 复合材料 /
- 力学性能 /
- 阻燃性能
Abstract: Flame retardant high density fiberboard (MPP-AP-WF/PR) composites were prepared with hot-pressing technology for wood-based products by adding melamine polyphosphate (MPP) and aluminium phosphate (AP) flame retardant to wood fiber/phenolic resin (WF/PR) composite. To investigate the optimum flame retardancy of the MPP-AP-WF/PR composites, the mass ratio of MPP to AP was explored. The effects of the mass ratio of MPP to AP on the mechanical properties, water resistance, thermal stability and flame retardancy of MPP-AP-WF/PR composites were studied based on the bending strength, thickness swelling rate, water absorption, thermogravimetic analysis and limiting oxygen index (LOI), and the flame retardant mechanism was also studied. The results show that the mechanical properties and water resistance of MPP-AP-WF/PR composites decrease significantly with the addition of flame retardant. However, the thermogravimetric results show that the flame retardant has no obvious effect on the initial heat resistance of MPP-AP-WF/PR composites, but the synergistic effect of both flame retardant at high temperature contributes to the carbon residue. LOI test results show that MPP has better flame retardant effect than AP when the flame retardant is used alone. Further, when MPP and AP are used together, the MPP-AP-WF/PR composite has the best flame retardant effect when the mass ratio of MPP to AP is 1∶2. It is due to both flame retardants exhibit the synergistic effect, which can promote the formation of dense char residue containing phosphoric acid compounds after the combustion of MPP-AP-WF/PR composite. The char can effectively prevent oxygen and heat from permeating into the internal carbon layer, thus improving the flame retardancy of the MPP-AP-WF/PR composite.
- melamine pyrophosphate /
- aluminum hypophosphite /
- wood fiber /
- composites /
- mechanical properties /
- flame retardancy

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图 1 WF/PR、MPP-WF/PR、AP-WF/PR、MPP-AP-WF/PR复合材料的弯曲强度和弹性模量

Figure 1. Bending strength and elastic modulus of WF/PR, MPP-WF/PR, AP-WF/PR and MPP-AP-WF/PR composites

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图 2 WF/PR、MPP-WF/PR、AP-WF/PR、MPP-AP-WF/PR复合材料的SEM图像

Figure 2. SEM images of WF/PR, MPP-WF/PR, AP-WF/PR, MPP-AP-WF/PR composites

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图 3 WF/PR、MPP-WF/PR、AP-WF/PR、MPP-AP-WF/PR复合材料24 h的吸水率和吸水厚度膨胀率

Figure 3. Water absorption and thickness swelling rate of WF/PR, MPP-WF/PR, AP-WF/PR, MPP-AP-WF/PR composites in 24 h

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图 4 WF/PR、MPP-WF/PR、AP-WF/PR、MPP-AP-WF/PR复合材料在N₂中的TG曲线

Figure 4. TG curves of WF/PR, MPP-WF/PR, AP-WF/PR andMPP-AP-WF/PR composites in N₂

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图 5 WF/PR、MPP-WF/PR、AP-WF/PR、MPP-AP-WF/PR复合材料的极限氧指数(LOI)和燃烧测试后的照片

Figure 5. Limiting oxygen index (LOI) and photographs after combustion test of WF/PR, MPP-WF/PR, AP-WF/PR and MPP-AP-WF/PR composites

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图 6 MPP-WF/PR和AP-WF/PR复合材料燃烧测试后残炭表面((a)、(b))和内部((c)、(d))的SEM图像及AP-WF/PR复合材料残炭的元素分布((e)~(h))

Figure 6. SEM images of external ((a), (b)) and internal ((c), (d)) char of MPP-WF/PR and AP-WF/PR composites after combustion test and elemental distribution ((e)–(h)) of char of AP-WF/PR composite

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图 7 MPP-AP-WF/PR复合材料燃烧测试后残炭表面((a)~(c))和内部((d)~(f))的SEM图像

Figure 7. SEM images of external ((a)–(c)) and internal ((d)–(f)) char of MPP-AP-WF/PR composites after combustion test

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表 1 阻燃高密度纤维板(MPP-AP-WF/PR)复合材料的配方

Table 1. Formulation of flame retardant high density fiberboard (MPP-AP-WF/PR) composites

No.	Sample	Mass ratio of MPP to AP	Mass fraction of MPP and/or AP/wt%
1^#	WF/PR	0∶0	0
2^#	MPP-WF/PR	1∶0	10
3^#	AP-WF/PR	0∶1	10
4^#	MPP-AP-WF/PR	2∶1	10
5^#	MPP-AP-WF/PR	1∶1	10
6^#	MPP-AP-WF/PR	1∶2	10
Notes: MPP—Melamine polyphosphate; AP—Aluminium phosphate; WF—Wood fiber; PR—Phenolic resin.

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表 2 WF/PR、MPP-WF/PR、AP-WF/PR、MPP-AP-WF/PR复合材料的TG数据

Table 2. TG data of WF/PR, MPP-WF/PR, AP-WF/PR and MPP-AP-WF/PR composites

No.	1^#	2^#	3^#	4^#	5^#	6^#
T_5%/℃	254.9	254.9	254.9	255.1	257.4	257.3
T_max/℃	349.6	346.4	339.6	338.6	333.7	335.7
Char at 600℃/%	23.9	27.8	30.8	31.7	34.4	33.0
Notes: T_5%—Decomposition temperature when mass of sample loss 5%,; T_max—Maximum thermal decomposition temperature of sample.

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表 3 MPP-WF/PR和AP-WF/PR复合材料的炭层元素分布

Table 3. Elemental distribution of char for MPP-WF/PR and AP-WF/PR composites

Element	2^#		3^#
Element	External/ wt%	Internal/ wt%	External/ wt%	Internal/ wt%
C	85.73	76.15	64.42	55.61
O	9.51	19.90	25.60	22.23
Al	0	0	1.92	5.43
P	4.26	3.95	8.06	16.73

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