γ-Al2O3催化合成聚甲基膦酸乙二醇酯的适宜活化温度的确定

doi:10.11944/j.issn.1000-0518.2020.03.190233

摘要/Abstract

摘要：

聚甲基膦酸乙二醇酯(PEMP)作为一种良好的阻燃剂,具有无毒、低烟、含磷量高、阻燃效果好的优点。 γ-Al₂O₃是催化乙二醇(EG)和甲基磷酸二甲酯(DMMP)缩合生成PEMP的良好催化剂。但是由于γ-Al₂O₃容易吸附CO₂和水分,降低其催化活性,所以使用前需要活化。活化温度影响着γ-Al₂O₃的催化活性。本文分别在300、400、500、600、700和800 ℃不同温度下对γ-Al₂O₃进行活化,用X射线粉末衍射(XRD)分析了γ-Al₂O₃晶型变化、用低温氮吸附比表面积测试法(BET法)测量了γ-Al₂O₃比表面积、孔径和孔容积,用傅里叶变换红外光谱(FTIR)分析了红外吸收变化,用吡啶吸附-FTIR测定了γ-Al₂O₃的Brønsted酸位点与Lewis酸位点相对含量。比较了不同温度下活化的γ-Al₂O₃催化合成PEMP产品的纯度和粘度,找到了γ-Al₂O₃催化合成PEMP的适宜活化温度为400~600 ℃。此时,γ-Al₂O₃属于典型的γ-Al₂O₃晶型,比表面积较大,孔径较小,所得PEMP产品纯度最高。

关键词: 聚甲基膦酸乙二醇酯, γ-Al₂O₃, 活化温度, 催化活性

Abstract:

Poly(oxy-1,2-ethanediyl)methylphosphonate(PEMP) as a good flame retardant has lots of benefits such as non-toxic, low smoke, high phosphorus content and better flame retardant effects. γ-Al₂O₃ is a good catalyst for the condensation of ethylene glycol (EG) and dimethyl phosphate (DMMP) to produce PEMP. However, since γ-Al₂O₃ is easy to absorb CO₂ and water to reduce its catalytic activity, activation is needed before use. The activation temperature affects the catalytic activity of γ-Al₂O₃. In this paper, γ-Al₂O₃ was activated at different temperatures from 300 ,400, 500, 600, 700 and 800 ℃. γ-Al₂O₃ crystal form was analyzed by X-ray difraction (XRD) and its specific surface area, pore diameter and pore volume were measured by Brunauer-Emmett-Teller (BET) method. The change of infrared absorption was analyzed by Fourier transfer infrared (FTIR). The relative contents of Brønsted acid and Lewis acid sites in γ-Al₂O₃ were determined by pyridine adsorption-FTIR. The purity and viscosity of PEMP catalyzed by γ-Al₂O₃ were compared, and the optimal activation temperature of γ-Al₂O₃ was found to be 400, 500 and 600 ℃. At this time, γ-Al₂O₃ is a typical γ-Al₂O₃ with large specific surface area and small pore diameter, and the obtained PEMP product has the highest purity.

Key words: poly(oxy-1,2-ethanediyl)methylphosphonate, γ-Al₂O₃, activation temperature, catalyzed activity

孙才英, 任彪彪, 董天贺, 代秋波, 肖博. γ-Al₂O₃催化合成聚甲基膦酸乙二醇酯的适宜活化温度的确定[J]. 应用化学, 2020, 37(3): 307-313.

SUN Caiying, REN Biaobiao, DONG Tianhe, DAI Qiubo, XIAO Bo. Optimal Activation Temperature of γ-Al₂O₃ for Catalytic Synthesis of Poly(oxy-1,2-ethanediyl)methylphosphonate[J]. Chinese Journal of Applied Chemistry, 2020, 37(3): 307-313.

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γ-Al₂O₃催化合成聚甲基膦酸乙二醇酯的适宜活化温度的确定

Optimal Activation Temperature of γ-Al₂O₃ for Catalytic Synthesis of Poly(oxy-1,2-ethanediyl)methylphosphonate

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