硅藻土基表面有机化氢氧化镁的制备及性能

doi:10.16085/j.issn.1000-6613.2021-0411

摘要/Abstract

摘要：

针对现有氢氧化镁阻燃剂在制备过程中存在氢氧化镁浆料过滤性能差的问题，采用正向沉淀法，以六水氯化镁和氢氧化钠为原料，在制备氢氧化镁的过程中加入硅藻土和油酸，制备出了硅藻土基表面有机化氢氧化镁。通过过滤性能测试考察了硅藻土添加量对氢氧化镁浆料过滤性能的影响，同时采用全自动比表面及孔径分析仪（BET）、场发射扫描电子显微镜（FESEM）、傅里叶红外光谱仪（FTIR）、同步热分析仪（STA）等对产物进行了分析。过滤性能和BET分析表明，添加硅藻土后，氢氧化镁浆料的过滤速率明显提高，当硅藻土与氢氧化镁质量比为0.10∶1时，所制备的硅藻土基表面有机化氢氧化镁的孔容最大，且氢氧化镁浆料的过滤性能提高了61.9%；FESEM分析表明，硅藻土的表面负载了分散性较好的片状氢氧化镁；FTIR分析表明，油酸成功地结合在氢氧化镁和硅藻土表面，提高了硅藻土基氢氧化镁的疏水性；热重（TG）分析表明，硅藻土对氢氧化镁具有协同阻燃效应，少量硅藻土的加入可以提高氢氧化镁的热稳定性，提高残重率，降低热释放速率，延长热分解时间。

关键词: 硅藻土, 氢氧化镁, 表面, 制备, 阻燃剂, 过滤

Abstract:

In order to solve the problems of filtration difficulty of the magnesium hydroxide slurry in the preparation of magnesium hydroxide flame retardant,diatomite supported hydrophobic magnesium hydroxide was prepared by positive precipitation method with MgCl₂·6H₂O and NaOH as raw material and adding diatomite and oleic acid as a surface modifier in the preparation process. The influence of diatomite amount on the filtration property of magnesium hydroxide slurry was discussed by means of filtration property test. Simultaneously, the products were characterized by Automatic specific surface and aperture analyzer (BET), Field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR) and Thermogravimetry-differential scanningcalorimetry (STA). The results of filtration property test and BET showed that the filtration rate of magnesium hydroxide slurry was increased evidently after adding diatomite. When the mass ratio of diatomite to magnesium hydroxide was 0.10∶1, the pore volume of diatomite supported hydrophobic magnesium hydroxide was the biggest, and the filtration rate of magnesium hydroxide slurry was increased 61.9%. The result of FESEM indicated that the surface of diatomite was loaded with flake magnesium hydroxide with good dispersion. The result of FTIR showed that OA bonded to the surface of magnesium hydroxide and diatomite with excellent hydrophobic properties. The result of TG found that diatomite had a synergistic flame retardant effect on magnesium hydroxide. Adding a small amount of diatomite can improve the thermal stability of magnesium hydroxide, increase the residual weight ratio, reduce the heat release rate and increase the thermal decomposition time.

Key words: diatomite, magnesium hydroxide, surface, preparation, flame retardant, filtration

中图分类号:

TQ132.2

申红艳, 刘有智, 朱海林, 赵凌波. 硅藻土基表面有机化氢氧化镁的制备及性能[J]. 化工进展, 2022, 41(2): 848-853.

SHEN Hongyan, LIU Youzhi, ZHU Hailin, ZHAO Lingbo. Preparation and property of diatomite supported hydrophobic magnesium hydroxide[J]. Chemical Industry and Engineering Progress, 2022, 41(2): 848-853.

图/表 10

图1 硅藻土基表面有机化氢氧化镁的制备工艺流程

图2 制备硅藻土基表面有机化氢氧化镁的实验装置图1—电动搅拌器；2—恒压滴液漏斗；3—温度计；4—三口烧瓶；5—恒温水浴锅

图3 硅藻土添加量对氢氧化镁浆料过滤速率的影响

图4 获得相同滤液体积下硅藻土添加量对氢氧化镁浆料过滤速率的影响

图5 硅藻土添加量对硅藻土基表面有机化氢氧化镁比表面积与孔容的影响

图6 氢氧化镁和硅藻土基表面有机化氢氧化镁的吸附-脱附等温线

图7 不同样品的SEM图

图8 红外光谱（FTIR）图

图9 样品的热失重曲线

表1 样品的热分析数据

样品	热分解温度区间	800℃残余质量/%
Dia	48.7～800℃	98.21
MH	43.7～376.2℃	67.01
OA	161～463℃	0
MH/Dia	33.4～383.4℃	67.83
OA/MH/Dia	35.1～487℃	67.87

参考文献 13

1	LAOUTID F, BONNAUD L, ALEXANDRE M, et al. New prospects in flame retardant polymer materials: from fundamentals to nanocomposites[J]. Materials Science and Engineering R: Reports, 2009, 63 (3): 100-125.
2	王健康, 张志宏, 王婧, 等. 反应物浓度对氢氧化镁沉降性能和粒度的影响[J]. 硅酸盐通报, 2017, 36(6): 1976-1980.
	WANG J K, ZHANG Z H, WANG J, et al. Influence of reactant concentration on setting property and particle size of magnesium hydroxide[J]. Bulletin of the Chinese Ceramic Society, 2017, 36(6): 1976-1980.
3	张建忠. 氢氧化镁料浆性能实验[J]. 盐业与化工, 2015, 44(5): 11-13.
	ZHANG J Z. Performance test of magnesium hydroxide slurry[J]. Journal of Salt and Chemical Industry, 2015, 44(5): 11-13.
4	牛永效. 利用水镁石水热法制备定形氢氧化镁晶体的研究[D]. 沈阳: 东北大学, 2010.
	NIU Y X. Research on hydrothermal preparation of form stable magnesium hydroxide crystal by brucite[D]. Shenyang: Northeastern University, 2010.
5	申红艳, 刘有智, 白俊红. 改善氢氧化镁过滤性能的实验研究[J]. 无机盐工业, 2014, 46(8): 33-36.
	SHEN H Y，LIU Y Z，BAI J H. Study on improvement of magnesium hydroxide filtration performance[J]. Inorganic Chemicals Industry, 2014, 46(8): 33-36.
6	曹俊雅, 宋昱霖, 孙振华, 等. 阳离子型聚丙烯酰胺对含超细氢氧化镁浆料过滤性能的影响[J]. 化工进展, 2020, 39(7): 2775-2781.
	CAO J Y， SONG Y L， SUN Z H, et al. Effect of cationic polyacrylamide on the filtration performance of ultrafine magnesium hydroxide[J]. Chemical Industry and Engineering Progress, 2020, 39(7): 2775-2781.
7	余建川, 向兰, 金涌. 常温合成方式对Mg(OH)₂粒径及过滤性能的影响[J]. 昆明理工大学学报 (理工版), 2005, 30(4): 96-98, 124.
	YU J C, XIANG L, JIN Y. Effect of slurry seed on size and filtration of Mg(OH)₂ particles[J]. Journal of Kunming University of Science and Technology (Science and Technology), 2005, 30(4): 96-98, 124.
8	CHEN G, YU Y, CHEN Z Q, et al. Fabrication of diatomite-based microencapsulated flame retardant and its improved fire safety of unsaturated polyester resin[J]. Polymers for Advanced Technologies, 2020, 31(5): 967-979.
9	CAVODEAU F, OTAZAGHINE B, SONNIER R, et al. Fire retardancy of ethylene-vinyl acetate composites—Evaluation of synergistic effects between ATH and diatomite fillers[J]. Polymer Degradation and Stability, 2016, 129: 246-259.
10	贺春江, 党佳, 张国文, 等. 硅藻土对氢氧化镁/红磷协同阻燃三元乙丙橡胶性能的影响[J]. 合成橡胶工业, 2012, 35(6): 463-465.
	HE C J, DANG J, ZHANG G W, et al. Effect of diatomite on properties of ethylene-propylene-dienemonomer with synergistic flame retardant of magnesium hydroxide and red phosphorus[J].China Synthetic Rubber Industry, 2012, 35(6): 463-465.
11	徐文总, 汪贵松, 许琼, 等.三聚氰胺包覆ZIF-67改性硅藻土阻燃抑烟剂及其制备方法: CN110591387A[P]. 2019-12-20.
	XU W Z, WANG G S, XU Q, et al. Melamine coated ZIF-67 modified diatomite flame retardant and smoke suppressant and preparation method there of: CN110591387A[P]. 2019-12-20.
12	任华峰，苗英霞，邱金泉, 等. 硅藻土助滤剂在海水净化中的应用[J]. 化工进展, 2014, 33(1): 238-241, 246.
	REN H F，MIAO Y X，QIU J Q, et al. Application of the diatomite aids in seawater filtration[J]. Chemical Industry and Engineering Progress, 2014, 33(1): 238-241, 246.
13	吴照洋, 张永兴, 张利珍, 等. 硅藻土资源特点及在战略新兴产业中的应用[J]. 矿产保护与利用, 2019, 39(6): 134-141.
	WU Z Y, ZHANG Y X, ZHANG L Z, et al. Characteristic of diatomite and its application in strategic emerging industries[J]. Conservation and Utilization of Mineral Resources, 2019, 39(6): 134-141.

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