Green Synthesis And Application Of Flame Retardants Of Tris(1,3-dichloro-2-propyl) Phosphate And Tris(β-chloropropyl) Phosphate

As a common phosphorus-based flame retardant,Phosphate has been widely used in various polymer materials,particular in polyurethane.As a catalyst,Lewis acid is usually used in conventional phosphate flame retardants synthesis,and also extremely unstable in air and water,easily hydrolyzed,serious equipment corrosion,large usage of dose and can not be recycled.Synthetic crude phosphates must be washed by acid solution,caustic solution as well as a lot of water,and also some other steps.Only in this way can it achieve the use standard of the product tedious post-treatment process resulted in not only large amount of sewage discharge,but also increasing the cost of investment,besides aggravated environmental pollution,and then restricted the development of enterprises.In this thesis,in order to solve the conventional Lewis acid catalysts’ problems of unstable,easily hydrolyzed,difficult to recycle.we choose the supported ionic liquid instead of the traditional catalysts.Three kinds of acid ionic liquid:[1-BuPy]Cl-XMgCl2,[Et3NH]Cl-XMgCl2,[Bmim]Cl-XMgCl2 have been synthesized,and three kinds of acid ionic liquid were supported by silica gel as a carrier to synthetic supported ionic liquid.[1-BuPy]Cl-XMgC12 were characterized by IR and SEM.It was showed that[1-BuPy]Cl-XMgCl2 ionic liquid supported on the surface of SiO2.After the application of the above three kinds of loaded acid ionic liquid to the synthesis of flame retardant tris(1,3-dichloro-2-propyl)phosphate(TDCPP),the thesis has found that loaded acid ionic liquid[1-BuPy]Cl-XMgCl2 has the best catalytic effect.The optimum conditions were confirmed by orthogonal and single factor method:the material ratio of n(POCl3):n(epichlorohydrin)=1:3.10,the reaction temperature for 70℃～80℃,the percentage of catalyst:0.105%,the reaction time for 5-6h,the yield for 98.1%.Supported ionic liquids were recyclable,and the times of cycle increased to six.IR,1H NMR,and ICP were used to characterize the flame retardant’s chemical structure,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.We have completed a pilot scale experiment of tris(1,3-dichloro-2-propyl)ester,which was added by an acid stabilizer synthesized,and we also explored the effect on different amount of the acid stabilizer.Based on the optimization of its original production process route,we completed the design the new production processes of tris(1,3-dichloro-2-propyl)ester,including recyclable loaded ionic liquid catalyst,and treatment of the acid value.Without acid washing,caustic washing,as well as cleaning,the crude product can achieve the quality standards,so that the post-processing can be simplified.Using acid stabilizer,we make sure that the life of the flame retardant is extended to six months,and the acid value of it without change.Making the green synthetic of tris(1,3-dichloro-2-propyl)phosphate,tris(β-chloroethyl)phosphate ester and the other phosphate series come to reality.