Synthesis Of The Corrdinated Function Ionic Liquids And Its Application In ATRP Reaction

Ionic liquid,as a new high efficient green solvent,has been widely concerned in the scienence and industry.The ATRP reaction in ionic liquids combines the advantages of green reaction and live polymerization.However,the catalyst used is obtained by coordinating the organic ligands with transition metal compounds.The organic ligands not only cause easily environment pollution,but also presents the poor compatibility with ionic liquid.In addition,it is not easy to separate from the obtained polymer.In this paper,a series of novel ligands containing N functional ionic liquids were synthesized according to catalytic system of ATRP in ionic liquids.The catalytic system was obtained by coordinating the transition metal compounds to catalyze the ATRP in ionic liquids,which can overcome the deficiency of organic ligands.By the designability of ionic liquids,three ligand ionic liquids were synthesized by introducing amino group?ethylenediamine,N,N' – Dimethyl – 1,2-ethanediamine,diethylenetriamine?with coordination properties onto the imidazolium cation through N-alkylation,respectively.The structure of ionic liquids was characterized by FT-IR,1H NMR and MS,and the physical properties of coordinated ionic liquid was studied.The coordinated ionic liquid with the anion Cl-have good solubility in polar solvent and the viscosity of coordinated ionic liquids becomes high with the increasing of cationic alkyl group.The effects of reaction condition on the yield of ionic liquids was studied.It showed that the reaction time was shorter and the yield was higher in the microwave reactor than that in the oil bath.The yield of coordinated ionic liquids is up to 90% when the reaction temperature was 75 ?,reaction power 320 W and microwave reaction time 3h.The coordination properties of the ionic liquid obtained with catalyst CuBr were investigated by cyclic voltammetry.The result indicated that the E1/2 of copper complex formed by [N₃MIM]Cl and CuBr has lower redox potential?E1/2 =-0.511 V?.The coordination mechanism of the ionic liquids with catalyst was analyzed.The dissolution mechanism of ionic liquid coordination complexes in ionic liquid solvents was studied as well organic coordination complexes.It showed that the tridentate coordinated ionic liquid[N₃MIM]Cl could provide three nitrogen atoms with the catalyst of copper ion to coordinate to form a stable three-dimensional space structure.The catalytic activity ofcatalyst was improved in the system with increasing of the solubility of catalyst.The catalyst formed by the functionalized ionic liquids [N₃MIM]Cl coordinating with CuBr was used to catalyze ATRP reaction of methyl methacrylate?MMA?in ionic liquid solvents [AMIM]Cl.The conversion of monomer?MMA?was up to 78.5% with a narrow distribution of molecular weight?Mw/Mn = 1.21?when the mole ratio of MMAl/2-EBiB/CuBr/[N₃MIM]Cl was 100:3:1:4,reaction temperature 60 ? and reaction time 250 min.By investigating the kinetics of this reaction,it was found that the polymerization reaction was first-order kinetics and presented the apparent controllability.