空心玻璃微珠/硬质聚氨酯泡沫复合材料的制备及性能

刘秀玉; 张冰; 韩祥祥; 刘亚辉; 赵石旭; 唐刚

doi:10.13801/j.cnki.fhclxb.20200115.002

空心玻璃微珠/硬质聚氨酯泡沫复合材料的制备及性能

doi: 10.13801/j.cnki.fhclxb.20200115.002

刘秀玉^{1, 2,},
张冰^1,,
韩祥祥^1,,
刘亚辉^3,,
赵石旭^3,,
唐刚^1, ,

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
3.
中钢集团马鞍山矿院新材料科技有限公司，马鞍山 243004

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)；四川省非金属复合与功能材料重点实验室-省部共建国家重点实验室培育基地开放基金(17kffk14)

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: TQ 328.3
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出版历程
- 收稿日期: 2019-10-16
- 录用日期: 2020-01-13
- 网络出版日期: 2020-01-15
- 刊出日期: 2020-09-15

Preparation and properties of hollow glass microspheres/rigid polyurethane foam composites

LIU Xiuyu^{1, 2
,},
ZHANG Bing^1
,,
HAN Xiangxiang^1
,,
LIU Yahui^3
,,
ZHAO Shixu^3
,,
TANG Gang^{1
, ,}

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
3.
Sinosteel Maanshan New Material Technology Co. Ltd., Ma’anshan 243004, China

摘要

摘要: 以空心玻璃微珠(HGM)为添加剂，采用一步法全水发泡制备了一系列HGM/硬质聚氨酯泡沫(RPUF)复合材料。通过SEM、TG、极限氧指数(LOI)和水平燃烧，研究了HGM/RPUF复合材料的泡孔结构、炭层形貌、热稳定性及阻燃性能。采用万能材料试验机测试了HGM/RPUF复合材料的压缩强度和压缩弹性模量。采用热重-傅里叶红外光谱(TG-FTIR)研究了HGM/RPUF复合材料燃烧过程中的气相产物。研究表明，HGM有成核剂作用，可以缩小HGM/RPUF复合材料泡孔孔径。HGM在燃烧过程中迁移到炭层表面，促进形成致密厚实的炭层。当加入5.4wt% HGM时，HGM/RPUF复合材料的压缩强度及压缩弹性模量分别提高至0.14 MPa和4.53 MPa，相对RPUF，分别提高了37.30%和67.16%。同时发现，HGM能明显抑制HGM/RPUF复合材料在燃烧过程中CO的释放，有效提高了其火灾安全性。
- 硬质聚氨酯泡沫 /
- 空心玻璃微珠 /
- 复合材料 /
- 力学性能 /
- 热稳定性
Abstract: The hollow glass microspheres(HGM) were used as additives to prepare a series of HGM/rigid polyurethane foam(RPUF) composites by one-step water-blown method. SEM, TG, limiting oxygen index(LOI) and horizontal combustion were applied to investigate the cell structure, char layer morphology, thermal stability and flame retardancy of the HGM/RPUF composites. The universal material testing machine was applied to study the compressive strength and compressive elastic modulus of the HGM/RPUF composites. Thermogravimetric analysis-Fourier transform infrared spectrophotometer(TG-FTIR) was applied to investigate the gaseous phase products of the HGM/RPUF composites. The results show that the HGM work as nucleating agent, which can reduce the pore diameter of the HGM/RPUF composites. In combustion, the HGM particles migrate to the surface of the char layer, promoting the formation of the compact char layer. When 5.4wt% of HGM were added, the compressive strength and compressive elastic modulus of the HGM/RPUF composites are increased to 0.14 MPa and 4.53 MPa, respectively, which are increased by 37.30% and 67.16% compared with those of the RPUF. At the same time, it is found that the HGM can significantly inhibit the release of toxic CO in combustion process, enhancing the fire safety of the HGM/RPUF composites.
- rigid polyurethane foam /
- hollow glass microspheres /
- composite /
- mechanical property /
- thermal stability

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图 1 HGM的SEM图像及XPS图谱

Figure 1. SEM image and XPS spectrum of HGM

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图 2 RPUF和HGM/RPUF复合材料的SEM图像

Figure 2. SEM images of RPUF and HGM/RPUF composites((a) RPUF; (b) HGM_3.7/RPUF; (c) HGM_7.1/RPUF; (d) HGM_10.3/RPUF)

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图 3 HGM添加量对HGM/RPUF复合材料极限氧指数(LOI)的影响

Figure 3. Effect of HGM loading on limiting oxygen index(LOI) of HGM/RPUF composites

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图 4 RPUF和HGM/RPUF复合材料压缩强度和压缩弹性模量

Figure 4. Compressive strength and compressive elastic modulus of RPUF and HGM/RPUF composites

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图 5 RPUF和HGM/RPUF复合材料在空气条件下的TG及DTG曲线

Figure 5. TG and DTG curves of RPUF and HGM/RPUF composites under air condition

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图 6 RPUF和HGM/RPUF复合材料炭渣的SEM图像

Figure 6. SEM images of char residues for RPUF and HGM/RPUF composites((a) RPUF; (b) HGM_3.7/RPUF; (c) HGM_7.1/RPUF; (d) HGM_10.3/RPUF)

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图 7 RPUF和HGM_10.3/RPUF复合材料气相产物的3D TG-FTIR图谱

Figure 7. 3D TG-FTIR spectra of volatilized products of RPUF and HGM_10.3/RPUF composite

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图 8 RPUF和HGM_10.3/RPUF复合材料最大热失重速率裂解产物的FTIR图谱

Figure 8. FTIR spectra of pyrolysis products at maximum decomposition rate for RPUF and HGM_10.3/RPUF composite

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图 9 RPUF和HGM_10.3/RPUF复合材料的裂解产物强度随时间的变化曲线

Figure 9. Absorbance changes of pyrolysis products for RPUF and HGM_10.3/RPUF composite with time

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图 10 HGM对HGM/RPUF复合材料的阻燃机制

Figure 10. Flame retardant mechanism of HGM to HGM/RPUF composites

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表 1 硬质聚氨酯泡沫(RPUF)和空心玻璃微珠(HGM)/RPUF复合材料组成

Table 1. Composition of rigid polyurethane foam(RPUF) and hollow glass microspheres(HGM)/RPUF composites

Sample	LY-4110/g	PM-200/g	LC/g	AK-8805/g	A33/g	Water/g	TEOA/g	HGM/g	HGM/wt%
RPUF	100	150	0.5	2	1	4	3	0	0
HGM_1.9/RPUF	100	150	0.5	2	1	4	3	5	1.9
HGM_3.7/RPUF	100	150	0.5	2	1	4	3	10	3.7
HGM_5.4/RPUF	100	150	0.5	2	1	4	3	15	5.4
HGM_7.1/RPUF	100	150	0.5	2	1	4	3	20	7.1
HGM_8.8/RPUF	100	150	0.5	2	1	4	3	25	8.8
HGM_10.3/RPUF	100	150	0.5	2	1	4	3	30	10.3
Notes: LY-4110—Polyether polyol; PM-200—Polyaryl polymethylene isocyanate; LC—Dibutyltin dilaurate; AK-8805—Silicone surfactant; A33—Triethylene diamine; TEOA—Triethanolamine; HGM_1.9/RPUF—Hollow glass microspheres/rigid polyurethane foam composites (subscript number represents the mass fraction of hollow glass microspheres).

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表 2 HGM的EDS结果

Table 2. EDS results of HGM

Element	C	O	Na	Si	Ca
Mass fraction/wt%	27.50	46.57	2.63	18.78	4.52
Atom fraction/at%	37.56	47.75	1.88	10.97	1.85

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表 3 RPUF和HGM/RPUF复合材料的密度及导热系数

Table 3. Density and thermal conductivity of RPUF and HGM/RPUF composites

Sample	ρ/(kg·m^–3)	λ/(W (m·K) ^–1)
RPUF	38.55	0.0363
HGM_1.9/RPUF	39.18	0.0365
HGM_3.7/RPUF	38.89	0.0373
HGM_5.4/RPUF	39.78	0.0379
HGM_7.1/RPUF	39.49	0.0363
HGM_8.8/RPUF	41.64	0.0363
HGM_10.3/RPUF	40.95	0.0371
Notes: ρ—Density; λ—Thermal conductivity.

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表 4 RPUF和HGM/RPUF复合材料的LOI及水平燃烧速度

Table 4. LOI and horizontal burning rate of RPUF and HGM/RPUF composites

Sample	LOI/%	V/(mm·min⁻¹)
RPUF	19.6	313.5
HGM_1.9/RPUF	20.2	290.3
HGM_3.7/RPUF	20.3	261.2
HGM_5.4/RPUF	20.4	243.0
HGM_7.1/RPUF	20.6	228.7
HGM_8.8/RPUF	20.8	200.0
HGM_10.3/RPUF	20.9	184.6
Note: V—Horizontal burning rate.

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表 5 RPUF和HGM/RPUF复合材料在空气条件下的TG及DTG数据

Table 5. TG and DTG data of RPUF and HGM/RPUF composites under air condition

Sample	T_–5%/℃	T_–50%/℃	T_max1/℃	T_max2/℃	Residue at 700℃/wt%
RPUF	254	360	337	568	2.0
HGM_3.7/RPUF	280	380	338	564	7.1
HGM_7.1/RPUF	274	418	337	566	7.8
HGM_10.3/RPUF	262	365	339	568	10.9
Notes: T_–5%—Onset degradation temperature; T_–50%—Midpoint temperature of degradation; T_1max, T_2max—Maximum decomposition temperature in the first and second stage, respectively.

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参考文献(33)

[1]	PARUZEL A, MICHALOWSKI S, HODAN J, et al. Rigid polyurethane foam fabrication using medium chain glycerides of coconut oil and plastics from end-of-life vehicles[J]. ACS Sustainable Chemistry & Engineering,2017,5(7):6237-6246.
[2]	FURTWENGLER P, AVEROUS L. Renewable polyols for advanced polyurethane foams from diverse biomass resources[J]. Polymer Chemistry,2018,9(32):4258-4287. doi: 10.1039/C8PY00827B
[3]	YANG R, HU W T, XU L, et al. Synthesis, mechanical properties and fire behaviors of rigid polyurethane foam with a reactive flame retardant containing phosphazene and phosphate[J]. Polymer Degradation and Stability,2015,122:102-109. doi: 10.1016/j.polymdegradstab.2015.10.007
[4]	XU W Z, WANG G S, XU J Y, et al. Modification of diatomite with melamine coated zeolitic imidazolate framework-8 as an effective flame retardant to enhance flame retardancy and smoke suppression of rigid polyurethane foam[J]. Journal of Hazardous Materials,2019,379:120819.
[5]	BIAN X C, TANG J H, LI Z M. Flame retardancy of whisker silicon oxide/rigid polyurethane foam composites with expandable graphite[J]. Journal of Applied Polymer Science,2008,110(6):3871-3879. doi: 10.1002/app.28921
[6]	PIELICHOWSKI K, SLOTWINSKA D. Morphological features and flammability of MDI/HMDI-based segmented polyurethanes containing 3-chloro-1,2-propanediol in the main chain[J]. Polymer Degradation and Stability,2003,80(2):327-331. doi: 10.1016/S0141-3910(03)00016-8
[7]	CAO Z J, DONG X, FU T, et al. Coated vs. naked red phosphorus: A comparative study on their fire retardancy and smoke suppression for rigid polyurethane foams[J]. Polymer Degradation and Stability,2017,136:103-111. doi: 10.1016/j.polymdegradstab.2016.12.004
[8]	LUO F B, WU K, LU M G, et al. Thermal degradation and flame retardancy of microencapsulated ammonium polyphosphate in rigid polyurethane foam[J]. Journal of Thermal Analysis and Calorimetry,2015,120(2):1327-1335. doi: 10.1007/s10973-015-4425-3
[9]	XU D M, LIU X, FENG J, et al. Preparation of boron-coated expandable graphite and its application in flame retardant rigid polyurethane foam[J]. Chemical Research in Chinese Universities,2015,31(2):315-320. doi: 10.1007/s40242-015-4101-y
[10]	ZHENG X R, WANG G J, XU W. Roles of organically-modified montmorillonite and phosphorous flame retardant during the combustion of rigid polyurethane foam[J]. Polymer Degradation and Stability,2014,101:32-39. doi: 10.1016/j.polymdegradstab.2014.01.015
[11]	LUO F B, WU K, LI Y W, et al. Reactive flame retardant with core-shell structure and its flame retardancy in rigid polyurethane foam[J]. Journal of Applied Polymer Science,2015,132(46):42800.
[12]	ACUNA P, LI Z, SANTIAGO-CALVO M, et al. Influence of the characteristics of expandable graphite on the morphology, thermal properties, fire behaviour and compression performance of a rigid polyurethane foam[J]. Polymers,2019,11(1):168. doi: 10.3390/polym11010168
[13]	KIM H, PARK J, MINN K S, et al. Flame retardant composite foam modified by silylated nanocellulose and tris(2-chloropropyl) phosphate[J]. Fibers and Polymers,2019,20(11):2280-2288. doi: 10.1007/s12221-019-9491-x
[14]	GENG H T, LIU J C, GUO A R, et al. Fabrication of heat-resistant syntactic foams through binding hollow glass microspheres with phosphate adhesive[J]. Materials & Design,2016,95:32-38.
[15]	REN S, LIU J C, GUO A R, et al. Mechanical properties and thermal conductivity of a temperature resistance hollow glass microspheres/borosilicate glass buoyance material[J]. Materials Science and Engineering A,2016,674:604-614. doi: 10.1016/j.msea.2016.08.014
[16]	VAHTRUS M, ORAS S, ANTSOV M, et al. Mechanical and thermal properties of epoxy composite thermal insulators filled with silica aerogel and hollow glass microspheres[J]. Proceedings of the Estonian Academy of Sciences,2017,66(4):339-346. doi: 10.3176/proc.2017.4.03
[17]	YANG H Y, JIANG Y P, LIU H Y, et al. Mechanical, thermal and fire performance of an inorganic-organic insulation material composed of hollow glass microspheres and phenolic resin[J]. Journal of Colloid and Interface Science,2018,530:163-170. doi: 10.1016/j.jcis.2018.06.075
[18]	JIAO C M, WANG H Z, CHEN X L. Preparation of modified fly ash hollow glass microspheres using ionic liquids and its flame retardancy in thermoplastic polyurethane[J]. Journal of Thermal Analysis and Calorimetry,2018,133(3):1471-1480. doi: 10.1007/s10973-018-7190-2
[19]	XIANG Y S, WANG L J, YANG Z, et al. Effect of aluminum phosphinate on the flame-retardant properties of epoxy syntactic foams[J]. Journal of Thermal Analysis and Calorimetry,2019,137(5):1645-1656. doi: 10.1007/s10973-019-08051-9
[20]	王彩华, 李慧剑, 余为, 等. 空心玻璃微珠增强环氧树脂复合材料的动态力学性能[J]. 复合材料学报, 2018, 35(5):1105-1113. WANG C H, LI H J, YU W, et al. Dynamic mechanical properties analysis of hollow glass microsphere reinforced epoxy resin composite[J]. Acta Materiae Compositae Sinica,2018,35(5):1105-1113(in Chinese).
[21]	余为, 薛海龙, 钱蒙, 等. 浸泡腐蚀对玻璃纤维-空心玻璃微珠/环氧树脂复合泡沫材料弯曲性能的影响[J]. 复合材料学报, 2015, 32(6):1688-1695. YU W, XUE H L, QIAN M, et al. Influence of soak corrosion on flexural properties of glass fiber-hollow glass microsphere/epoxy syntactic foam material[J]. Acta Materiae Compositae Sinica,2015,32(6):1688-1695(in Chinese).
[22]	ASTM International. Standard test method for measuring the minimum oxygen concentration to support candle-like combustion of plastics (oxygen index): ASTM D2863—19[S]. West Conshohocken: ASTM International, 2019.
[23]	中国国家标准化管理委员会. 塑料燃烧性能的测定水平法和垂直法: GB/T 2408—2008[S]. 北京: 中国标准出版社, 2009. Standardization Administration of the People’s Republic of China. Plastics: Determination of burning characteristics: Horizontal and vertical test: GB/T 2408—2008[S]. Beijing: China Standards Press, 2009(in Chinese).
[24]	中国国家标准化管理委员会. 泡沫塑料及橡胶表观密度的测定: GB/T 6343—2009[S]. 北京: 中国标准出版社, 2009. Standardization Administration of the People’s Republic of China. Cellular plastics and rubbers: Determination of apparent density: GB/T 6343—2009[S]. Beijing: China Standards Press, 2009(in Chinese).
[25]	中国国家标准化管理委员会. 非金属固体材料导热系数的测定热线法: GB/T 10297—2015[S]. 北京: 中国标准出版社, 2016. Standardization Administration of the People’s Republic of China. Test method for thermal conductivity of nonmetal solid materials: Hot-wire method: GB/T 10297—2015[S]. Beijing: China Standards Press, 2016(in Chinese).
[26]	中国国家标准化管理委员会. 硬质泡沫塑料压缩性能的测定: GB/T 8813—2008[S]. 北京: 中国标准出版社, 2008. Standardization Administration of the People’s Republic of China. Rigid cellular plastics: Determination of compression properties: GB/T 8813—2008[S]. Beijing: China Standards Press, 2008(in Chinese).
[27]	王洪志. 离子液体改性空心材料阻燃TPU的研究[D]. 青岛: 青岛科技大学, 2018. WANG H Z. Study on flame retardant thermoplastic polyurethane based on modified hollow materials with ionic liquid[D]. Qingdao: Qingdao University of Science & Technology, 2018(in Chinese).
[28]	刘娟, 李青芳, 韩悦, 等. 磷/硅比值对硬质聚氨酯泡沫性能的影响[J]. 塑料, 2017, 46(2):54-57. LIU J, LI Q F, HAN Y, et al. Effect of the P/Si ratio on properties of rigid polyurethane foam[J]. Plastics,2017,46(2):54-57(in Chinese).
[29]	BIAN X C, TANG J H, LI Z M. Flame retardancy of hollow glass microsphere/rigid polyurethane foams in the presence of expandable graphite[J]. Journal of Applied Polymer Science,2008,109(3):1935-1943. doi: 10.1002/app.27786
[30]	CHATTOPADHYAY D K, WEBSTER D C. Thermal stability and flame retardancy of polyurethanes[J]. Progress in Polymer Science,2009,34(10):1068-1133. doi: 10.1016/j.progpolymsci.2009.06.002
[31]	YUAN Y, MA C, SHI Y Q, et al. Highly-efficient reinforcement and flame retardancy of rigid polyurethane foam with phosphorus-containing additive and nitrogen-containing compound[J]. Materials Chemistry and Physics,2018,211:42-53. doi: 10.1016/j.matchemphys.2018.02.007
[32]	MODESTI M, LORENZETTI A, BESCO S, et al. Synergism between flame retardant and modified layered silicate on thermal stability and fire behaviour of polyurethane nanocomposite foams[J]. Polymer Degradation and Stability,2008,93(12):2166-2171. doi: 10.1016/j.polymdegradstab.2008.08.005
[33]	YUAN Y, YU B, SHI Y Q, et al. Highly efficient catalysts for reducing toxic gases generation change with temperature of rigid polyurethane foam nanocomposites: A comparative investigation[J]. Composites Part A: Applied Science and Manufacturing,2018,112:142-154. doi: 10.1016/j.compositesa.2018.05.028