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

作　　者：孙才英[1] 任彪彪 董天贺 代秋波 肖博 SUN Caiying;REN Biaobiao;DONG Tianhe;DAI Qiubo;XIAO Bo(Heilongjiang Key Laboratory of Molecular Design and Preparation of Flame Retarded Materials,College of Chemistry,Chemical Engineering and Resource Utilization,Northeast Forestry University,Harbin 150040,China;School of Landscape Architecture,Northeast Forestry University,Harbin 150040,China;Chifeng Product Quality and Mearurement Inspect Institute,Chifeng,Inner Mongolia 024000,China)

机构地区：[1]东北林业大学化学化工与资源利用学院,黑龙江省高校阻燃新材料重点实验室,哈尔滨150040 [2]东北林业大学园林学院,哈尔滨150040 [3]赤峰市产品质量计量检测所,内蒙古赤峰024000

出　　处：《应用化学》2020年第3期307-313,共7页Chinese Journal of Applied Chemistry

基　　金：中央高校基本科研业务费专项资金项目(2572018BK04)资助。

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Br nsted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。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,sinceγ-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 Br nsted acid and Lewis acid sites inγ-Al2O3 were determined by pyridine adsorption-FTIR.The purity and viscosity of PEMP catalyzed byγ-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.

关 键 词：聚甲基膦酸乙二醇酯 Γ-AL2O3 活化温度 催化活性 

分 类 号：O621[理学—有机化学] O647[理学—化学]