水性聚氨酯阻燃纳米复合材料的Click反应制备及性能

doi:10.7503/cjcu20160177

摘要/Abstract

摘要：

以4,4'-二羟甲基-1,4-庚二炔功能单体作为扩链剂制备了端炔基功能化聚氨酯, 与叠氮基改性纳米蒙脱土(MMT-N₃)、纳米氢氧化铝(ATH-N₃)和纳米氢氧化镁(MH-N₃)通过Click反应制备了水性聚氨酯(WPU)阻燃纳米复合材料. 采用红外光谱(FTIR)、核磁氢谱(¹H NMR)和扫描电子显微镜(SEM)对WPU阻燃纳米复合材料的结构进行了表征, 对比研究了纳米阻燃剂配比和制备方法对WPU阻燃纳米复合材料的氧指数、动态燃烧行为和热稳定性的影响. 阻燃性能研究结果表明, 当MMT-N₃, MH-N₃和ATH-N₃的质量分数分别为7%, 2%和1%时, 采用Click反应制备的复合材料的氧指数比纯WPU高7%, 点燃时间从10 s延长到29 s, 峰值热释放速率和烟释放速率分别降低了41%和42%. 热失重分析结果表明, 当MMT-N₃质量分数为10%时, 与WPU相比, 采用Click反应制备的MMT/WPU复合材料在热失重50%时的温度提高了21 ℃. 复合材料断面和燃烧后残渣的SEM分析证明在聚合物基体中Click反应是分散纳米材料的一种有效方法.

关键词: 阻燃水性聚氨酯, 纳米蒙脱土, 纳米氢氧化物, Click反应, 动态燃烧行为

Abstract:

Polyurethane bearing the alkyne functions as pendant groups was synthesized via functional monomer 2,2-di(prop-2-ynyl) propane-1,3-dio as chain extender. Flame retardant waterborne polyurethane(WPU) nanocomposites were prepared by the Click reaction between alkyne-functionalized PU and azido-modified nano-montmorillonite(MMT), nano-aluminum hydroxide(ATH) and magnesium hydroxide(MH). The structures of the flame retardant WPU nanocomposites were characterized by Fourier transform Infrared spectrometer(FTIR), proton nuclear magnetic resonance spectroscopy(¹H NMR) and scanning electron microscopy(SEM). The influence of the ratio of nano flame retardants and preparation methods on limit oxygen index, dynamic combustion performance and thermal degradation behavior of the WPU nanocomposites were studied by the comparative study. The findings on flame resistance study indicated that when the mass fractions of MMT-N₃, MH-N₃ and ATH-N₃ were 7%, 2% and 1%, respectively, the oxygen index of the composites prepared by Click reaction was 7% higher than that of pure WPU, time to ignition was lengthened from 10 s to 29 s, and the peak heat release rate and smoke release rate were reduced by 41% and 42%, respectively. TGA results showed that when the mass fraction of MMT-N₃of 10%, the temperature at 50% mass loss of MMT/WPU composites prepared by Click reaction increased 21 ℃ compared with the WPU. SEM analysis of the composite section and combustion residue showed that Click reaction is an effective method to disperse nanomaterials in polymer matrices.

Key words: Flame retardant waterborne polyurethane, Nano-montmorillonite, Nano-hydroxide, Click reaction, Dynamic combustion behavior

中图分类号:

O631

TrendMD:

李兴建, 鞠云鹏, 常德功, 张宜恒. 水性聚氨酯阻燃纳米复合材料的Click反应制备及性能. 高等学校化学学报, 2016, 37(8): 1580.

LI Xingjian,JU Yunpeng,CHANG Degong,ZHANG Yiheng. Preparation and Properties of Flame Retardant Waterborne Polyurethane Nanocomposites via Click Reaction^†. Chem. J. Chinese Universities, 2016, 37(8): 1580.

图/表 16

Scheme 1 Synthesis of 3-azidopropyltriethoxysilane

Scheme 2 Synthesis of DPPD

Scheme 3 Strategy for the azidation of MMT, ATH and MH

Scheme 4 Click reaction between alkyne-functionalized PU and azido-nano fillers

Table 1 Recipes of WPU flame retardant nanocomposites

Sample	Component(mass fraction, %)			Composite mechanism
Sample	MMT-N₃		MH-N₃	ATH-N₃
WPU
MMT/WPU	10	0	0	Click reaction
PBWPU	7	2	1	Physical blending
CRWPU	7	2	1	Click reaction

Fig.1 FTIR spectra of DPPD(a) and alkyne-functionalized PU(b)

Fig.2 FTIR spectra of MH(A), ATH(B) and MMT(C) befor(a) and after(b) modification of N3

Fig.3 FTIR spectra of alkyne-WPU(a) and functionalized WPU after Click reaction(b)

Fig.4 1H NMR spectra(500 MHz, DMSO-d6) of alkyne-functionalized WPU before(a) and after(b) Click reaction

Fig.5 SEM images of WPU(A), MMT/WPU(B), PBWPU(C) and CRWPU(D)

Table 2 LOI, tign, pkHRR and pkSPR of WPU nanocomposites

Sample	LOI(%)	t_ign/s	pkHRR/(kW·m^-2)	pkSPR/(m²·s^-1)
WPU	17.0	10	397.1	0.033
MMT/WPU	19.8	9	293.3	0.024
PBWPU	22.2	17	274.6	0.023
CRWPU	24.0	29	235.6	0.019

Fig.6 HRR curves for WPU(a), MMT/WPU(b),PBWPU(c) and CRWPU(d)

Fig.7 Smoke production rate curves of WPU(a), MMT/WPU(b), PBWPU(c) and CRWPU(d)

Fig.8 SEM residue images of WPU(A), MMT/WPU(B), PBWPU(C) and CRWPU(D) after the cone calorimeter tests

Fig.9 TGA(A) and DTG(B) curves of WPU nanocomposites a. WPU; b. MMT/WPU; c. PBWPU; d. CRWPU.

Table 3 Temperature of thermal lost weight of the film and the final char yield of WPU nanocomposites

Sample	T_5%/℃	T_50%/℃	T_max/℃	Char yield(500 ℃)(%)
WPU	158	317	325	-2.9
MMT/WPU	183	338	339	11.5
PBWPU	247	320	321	12.6
CRWPU	253	325	323	13.3

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