Study On Synthesis Of Amine Coordination Functional Ionic Liquids And Its Structure In ATRP Reaction

Atom transfer radical polymerization(ATRP)reaction is developed rapidly in recent years,a kind of important active polymerization technology.It can synthesize novel structure and composition of new functional polymer materials because of the advantages of the controllable reactivity of ATRP technology.Two types of seven kinds of amine coordination functional ionic liquids were synthesized as the complexants of ATRP reaction system replacing of the traditional organic complex in [AMIM]Cl.The effects of the different structure of coordination functional ionic liquids to the coordination with Cu+ as well as to the ATRP reaction were studied,respectively.7 ionic liquids such as [N2C2MIM]Cl,[N2C3MIM]Cl,[N2MeC3MIM]Cl,[N2Me2C3MIM]Cl,[N3MIM]Cl,[N3Me5MIM]Cl,[N4MIM]Cl were prepared on the base of N-methylimidazole and 1,2-dichloroethane intermediates [CeMIM]Cl and reacting with different fatty amines.The chemical structure of amine coordination functional ionic liquids was confirmed by the results of FT-IR,1HNMR.The optimal synthesis technology(ratio of [CeMIM]Cl and amine was 1:1,reaction time was 20 h,reaction temperature was 80?)was determined through the orthogonal experiment.The oxidation reduction potential(E1,2)of amine coordinated functional ionic liquids and organic ligands were measured by cyclic voltammetry(CV).It turned out that coordination functional ionic liquids have good coordination property compared with traditional organic ligand,and with the number of N in amine coordination functional ionic liquids increasing,the coordination property was enhanced;as the growth of the C chain,coordination ability was enhanced;along with the substituent in amine coordination functional ionic liquids increaseing,the coordination property was weakened.The coordination functional ionic liquids coordinated with CuBr were used to catalyze the ATRP reaction of MMA in [AMIM]Cl.The variation of ln(M0/Mt)was evidently linear with time throughout the whole reaction process,thus indicating a first-order reaction.The Mw/Mn was 1.50-1.90,it indicated by GPC that the coordination ionic liquid presented the perfect controllability to the ATRP reactions and as the growth of the C chain,the controllability was enhanced;along with the substituent in amine coordination functional ionic liquids increaseing,the controllability was weakened.The residues Cu2+ in the PMMA was measured by AAS and the result showed that the Cu catalyst was easily separated from the polymer.The separation ability of Cu from product became better with the increase of its coordination performance.The coordination functional ionic liquids can overcome the shortages of the traditional organic ligands such as poisonous,poor compatibility and poor separation ability of catalyst from product.It displays a perfect application potential on the ATRP field.