基于微胶囊化聚磷酸铵和微胶囊化膨胀石墨的阻燃硬质聚氨酯泡沫复合材料的制备及性能

杨亚东; 姜浩浩; 张冰; 刘新亮; 王浩; 刘秀玉; 唐刚

doi:10.13801/j.cnki.fhclxb.20200727.003

基于微胶囊化聚磷酸铵和微胶囊化膨胀石墨的阻燃硬质聚氨酯泡沫复合材料的制备及性能

doi: 10.13801/j.cnki.fhclxb.20200727.003

杨亚东^1,,
姜浩浩^1,,
张冰¹,
刘新亮^1,,
王浩^2,,
刘秀玉^{1, 3},
唐刚^{1, 3, ,}

1.
安徽工业大学　建筑工程学院，马鞍山 243032
2.
中冶华天工程技术有限公司节能环保研究院，马鞍山 243005
3.
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:
唐刚，博士，副教授，硕士生导师，研究方向为阻燃聚合物复合材料、有机建筑保温材料　E-mail：gangtang@mail.ustc.edu.cn

中图分类号: TQ328.3
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出版历程
- 收稿日期: 2020-06-15
- 录用日期: 2020-07-14
- 网络出版日期: 2020-07-27
- 刊出日期: 2021-05-01

Preparation and properties of flame retardant rigid polyurethane foam composites based on microencapsulated ammonium polyphosphate and microencapsulated expanded graphite

YANG Yadong^1
,,
JIANG Haohao^1
,,
ZHANG Bing¹,
LIU Xinliang^1
,,
WANG Hao^2
,,
LIU Xiuyu^{1, 3},
TANG Gang^{1, 3
, ,}

1.
School of Architecture and Civil Engineering, Anhui University of Technology, Ma’anshan 243032, China
2.
Energy Conservation & Environmental Protection Research Institute, Huatian Engineering & Technology Corporation MCC, Ma’anshan 243005, China
3.
Nanjing GongdaKaiyuan Environmental Protection Technology (Chuzhou) Co., Ltd., Chuzhou, 239000, China

摘要

摘要: 采用原位聚合法，以聚氨酯为壳材，制备微胶囊化聚磷酸铵(PUAPP)和微胶囊化膨胀石墨(PUEG)。采用XPS、FTIR、TG和SEM分别对PUAPP和PUEG进行表征，结果表明，聚氨酯有效包覆在聚磷酸铵和膨胀石墨表面，成功制备了PUAPP和PUEG。在此基础上，采用一步法全水发泡工艺将PUAPP和PUEG引入到聚氨酯硬泡(RPUF)中，制备出一系列阻燃RPUF复合材料。采用极限氧指数(LOI)、垂直燃烧(UL-94)、TG、万能试验机、导热及密度测试研究了PUAPP/RPUF、PUEG/RPUF及PUAPP-PUEG/RPUF复合材料的阻燃性能、力学性能、保温性能及热稳定性。研究表明，微胶囊化阻燃剂的加入可以提高RPUF复合材料的高温稳定性，PUEG/RPUF、PUAPP/RPUF和PUAPP-PUEG/RPUF复合材料在700℃的残炭率从1.2wt%分别提高至6.9wt%、11.2wt%和10.7wt%。阻燃测试表明，PUAPP和PUEG可以有效提高RPUF复合材料的阻燃性能，当加入10.4wt% PUAPP时，PUAPP/RPUF复合材料的LOI提高到22.3vol%，UL-94等级为V-0级；当加入10.4wt% PUEG时，PUEG/RPUF复合材料的LOI达到25.3vol%，UL-94等级为V-0级；PUAPP-PUEG/RPUF复合材料的LOI达到24.3vol%，UL-94等级为V-0级。SEM和拉曼测试表明，PUAPP和PUEG可以提高RPUF复合材料的炭渣石墨化程度，使炭渣的致密性更强。
- 硬质聚氨酯泡沫 /
- 原位聚合法 /
- 微胶囊 /
- 聚磷酸铵 /
- 膨胀石墨 /
- 阻燃
Abstract: Microencapsulated ammonium polyphosphate (PUAPP) and microencapsulated expanded graphite (PUEG) were prepared by in situ polymerization with polyurethane as shell material. XPS, FTIR, TG and SEM were used to characterize PUAPP and PUEG. The results show that polyurethane is effectively coated on the surface of ammonium polyphosphate and expanded graphite, and PUAPP and PUEG are successfully fabricated. On this basis, a series of flame-retardant rigid polyurethane foam (RPUF) composites were prepared with PUAPP and PUEG loading by one-step water-blown method. The flame retardancy, mechanical properties, thermal insulation and thermal stability of PUAPP/RPUF, PUAPP/RPUF and PUAPP-PUEG/RPUF composites were investigated by limiting oxygen index (LOI), underwriters laboratories vertical burning test (UL-94), TG, universal testing machine, heat conduction and density test. The results show that the thermal stability at high temperature of RPUF composites can be improved by the addition of PUAPP and PUEG. The charresidues of PUAPP/RPUF, PUAPP/RPUF and PUAPP-PUEG/RPUF at 700℃ are increased from 1.2wt% to 6.9wt%, 11.2wt% and 10.7wt%, respectively. Flame retardant tests show that the microencapsulated flame retardant can effectively improve flame retardancy of RPUF composites. When 10.4wt% PUAPP is added, the LOI of the PUAPP/RPUF composite is increased to 22.3vol% with V-0 rating in UL-94 test; when 10.4 wt% PUEG is added, the LOI of the PUAPP/RPUF composite is increased to 25.3vol% with UL-94 V-0 rating; PUAPP-PUEG/RPUF composite presents LOI of 24.3vol% with UL-94 V-0 rating. SEM and Raman tests indicate that PUAPP and PUEG can increase graphitization degree of char residues for RPUF composites with enhanced compactness of the char residues.
- rigidpolyurethane foam /
- in-situ polymerization method /
- microcapsulation /
- ammonium polyphosphate /
- expanded graphite /
- flame retardant

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图 1 聚磷酸铵(APP)和PUAPP的FTIR图谱

Figure 1. FTIR spectra of ammonium polyphosphate (APP) and PUAPP

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图 2 膨胀石墨(EG)和PUEG的FTIR图谱

Figure 2. FTIR spectra of expanded graphite (EG) and PUEG

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图 3 APP和PUAPP的XPS图谱

Figure 3. XPS spectra of APP and PUAPP

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图 4 EG和PUEG的XPS图谱

Figure 4. XPS spectra of EG and PUEG

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图 5 APP (a)和PUAPP (b)的SEM图像

Figure 5. SEM images of APP (a) and PUAPP (b)

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图 6 EG (a)和PUEG (b)的SEM图像

Figure 6. SEM images of EG (a) and PUEG (b)

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图 7 空气条件下APP、PUAPP、EG与PUEG的TG和DTG曲线

Figure 7. TGA and DTG curves of APP, PUAPP, EG and PUEG under air conditions

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图 8 空气条件下RPUF、PUAPP/RPUF、PUEG/RPUF和PUAPP-PUEG/RPUF复合材料的TG和DTG曲线

Figure 8. TGA and DTG curves of RPUF, PUAPP/RPUF, PUEG/RPUF and PUAPP-PUEG/RPUF composites under air conditions

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图 9 RPUF (a)、PUAPP/RPUF (b)、PUEG/RPUF (c)和PUAPP-PUEG/RPUF (d)复合材料的SEM图像

Figure 9. SEM images of RPUF (a), PUAPP/RPUF (b), PUEG/RPUF (c) and PUAPP-PUEG/RPUF (d) composites

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图 10 RPUF、PUAPP/RPUF、PUEG/RPUF和PUAPP-PUEG/RPUF复合材料的极限氧指数(LOI)和垂直燃烧(UL-94)测试结果

Figure 10. Results of limiting oxygen index (LOI) and underwriters laboratories vertical burning (UL-94) test for RPUF, PUAPP/RPUF, PUEG/RPUF, PUAPP-PUEG/RPUF composites

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图 11 RPUF (a)、PUAPP/RPUF (b)、PUEG/RPUF (c)和PUAPP-PUEG/RPUF (d)复合材料炭渣的SEM图像

Figure 11. SEM images of char residues of RPUF (a), PUAPP/RPUF (b), PUEG/RPUF (c) and PUAPP-PUEG/RPUF (d) composites

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图 12 RPUF、PUAPP/RPUF、PUEG/RPUF和PUAPP-PUEG/RPUF复合材料炭渣的Raman图谱

Figure 12. Raman spectra of char residues of RPUF, PUAPP/RPUF, PUEG/RPUF and PUAPP-PUEG/RPUF composites

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表 1 硬质聚氨酯泡沫(RPUF)、微胶囊化聚磷酸铵(PUAPP)/RPUF、微胶囊化膨胀石墨(PUEG)/RPUF和PUAPP-PUEG/RPUF复合材料配比

Table 1. Formulation of rigid polyurethane foam (RPUF), microencapsulated ammonium polyphosphate (PUAPP)/RPUF, microencapsulated expanded graphite (PUEG)/RPUF and PUAPP-PUEG/RPUF composites

Sample	LY-4110/g	PM-200/g	LC/g	AK-8805/g	A33/g	TEOA/g	Water/g	PUEG/g	PUEG/wt%	PUAPP/g	PUAPP/wt%
RPUF	100	150	0.5	2	1	3	2	0	0	0	0
PUEG/RPUF	100	150	0.5	2	1	3	2	30	10.4	0	0
PUAPP/RPUF	100	150	0.5	2	1	3	2	0	0	30	10.4
PUAPP-PUEG/ RPUF	100	150	0.5	2	1	3	2	10	3.5	20	6.9
Notes: LY-4110—Polyether polyol; PM-200—Polyarylpolymethyleneisocyanate; LC—Dibutyltindilaurate; AK-8805—Silicone surfactant; A33—Triethylenediamine; TEOA—Triethanolamine.

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表 2 空气条件下APP、PUAPP、EG和PUEG的TGA数据

Table 2. TGA data of APP, PUAPP, EG and PUEG under air conditions

Sample	T_−5%/℃	T_max1/℃	T_max2/℃	Residues at 700℃/wt%
APP	331	357	606	10.4
EG	204	215	—	24.8
RPUF	271	313	569	1.2
PUAPP	285	299	568	10.0
PUEG	203	216	—	21.8
Notes: T_−5%—Onset degradation temperature; T_max1, T_max2—Maximum decomposition temperature in the first and second stage, respectively.

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表 3 空气条件下RPUF、PUAPP/RPUF、PUEG/RPUF和PUAPP-PUEG/RPUF的TGA数据

Table 3. TGA data of RPUF, PUAPP/RPUF, PUEG/RPUF and PUAPP-PUEG/RPUF under air conditions

Sample	T_−5%/℃	T_max1/℃	T_max2/℃	Residues at 700℃/wt%
RPUF	271	312	569	1.2
PUEG/RPUF	249	319	572	6.9
PUAPP/RPUF	264	315	565	11.2
PUAPP-PUEG/RPUF	262	308	566	10.7

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表 4 RPUF、PUAPP/RPUF、PUEG/RPUF和PUAPP-PUEG/RPUF复合材料的密度、导热系数和压缩强度

Table 4. Density, thermal conductivity and compressive strength of RPUF, PUAPP/RPUF, PUEG/RPUF, PUAPP-PUEG/RPUF composites

Sample	RPUF	PUEG/RPUF	PUAPP/RPUF	PUAPP-PUEG/RPUF
ρ/(kg·m⁻³)	64.16±0.91	57.92±0.23	59.92±5.77	55.84±1.36
λ/(W(m·K)⁻¹)	0.0390±0.00038	0.0394±0.000436	0.0389±0.000493	0.0395±0.00029
Pressure/MPa	0.325±0.0075	0.276±0.0151	0.286±0.0205	0.271±0.0411
Notes: ρ—Density; λ—Thermal conductivity; Pressure—Compressive strength.

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