Ionic Liquid Catalyzed Synthesis And Application Of Flame Retardant Tris(?-chloropropyl) Phosphate And Tetrakis(?-chloropropyl)-1-methylethylene Bisphosphate

Phosphate ester flame retardants have a number of advantages,such as low volatility,resistance to hydrolysis,high thermal decomposition stability,low toxicity,low smoke and little additive amount.Therefore they are widely used in various polymer materials,especially in polyurethane.The traditional method of synthesizing phosphate ester flame retardants has a big flaw:the inorganic acid-base catalyst used in the synthesis process is easy to hydrolyze,highly corrosive and difficult to recycle.To overcome the weakness mentioned above and to follow the trend of green chemistry,ionic liquid is adopted as the catalyst;and the ionic liquid is supported by silica gel to reduce the consumption as well as improve the circulation utilization.In this thesis,three kinds of acid ionic liquid:[Bmim]Cl-XAlCl3,[1-BuPy]Cl-XAlCl3,[Et3NH]Cl-XAlCl3 and four kinds of base ionic liquid:[Bmim]OAc,[Bmim]2CO3,[1-BuPy]OAc,[1-BuPy]2CO3(part of them were characterized by IR,1H NMR)have been synthesized.After the application of the above acid ionic liquid to the synthesis of flame retardant tris(?-chloropropyl)phosphate ester(TCPP),the thesis has found that[Et3NH]Cl-XAlCl3 has the best catalytic effect.Catalyst[Et3NH]Cl-XAICl3/SiO2was prepared by supporting ionic liquid[Et3NH]Cl-XAlCl3 with silica gel with the application of sol-gel method.The ionic liquid was characterized by IR,SEM,and the results showed that the ionic liquid loaded on the surface of SiO2.The optimum conditions were confirmed by single factor method:the material ratio of n(POCl3):n(ethylene oxide)= 1:3.1,the reaction temperature of 65 ?-75 ?,the percentage of catalyst:0.045%(before of support);0.27%(after the loading,load factor of 15.8%,relative to the SiO2),the reaction time of 3 h,the yield of 98.8%.After the loading,the amount of ionic liquid is reduced,and the times of circulation reached six.After the application of the above base ionic liquid to the synthesis of flame retardant tetrakis(?-chloropropyl)-1-methyl-diphosphate(TCMD),the thesis has found that the[Bmim]2CO3 has the best catalytic effect.Catalyst[Bmim]2CO3/SiO2 was prepared by loading ionic liquids[Bmim]2CO3 with silica gel with the application of silica gel after grafting method.The ionic liquid was characterized by IR,SEM,and the results showed that the ionic liquid loaded on the surface of SiO2.The optimum conditions were confirmed by single factor method:the reaction temperature of 190 ?,the percentage of catalyst:2.0%(before loading);7.48%(after loading,load factor of 20.4%,relative to the SiO2),the reaction time of 3 h,the yield of 79.8%.After loading,the amount of ionic liquid is reduced,and the times of circulation reached at least six.IR,1H NMR,LC-MS and ICP were used to characterize the flame retardants chemical structures,which was proved to be the structure of the target molecules.What's more,its physical properties were tested by TGA,acid value titration,viscometer,and the result could meet the standard.In order to effectively prevent the acid value of TCPP from increasing while it is stored,the thesis has explored the influences that different acid value stabilizers exert on the acid value of TCPP.Moreover,this thesis examines the change of the flame retardant of the soft polyurethane foam plastics when tetrakis(?-chloropropyl)-1-methyl-diphosphate was added to it,and studies the influence of the addition amount on its flame retardant properties and mechanical properties.