Synthesis And Application Of Amino-Functionalize D Polystyrenes Catalyzed By Half-Sandwich Scandium Complexes

High stereospecific polystyrene has stimulated widely attention in recent years because of its high melting point,high glass transition temperature,high elastic modulus,strong chemical resistance and other outstanding advantages.However,due to the lack of polar groups in the high stereoselective polystyrene,the poor compatibility with other materials limitting its application.In this thesis,three amine-functionalized styrene derivatives?DMAS?were synthesized and the two complexes?C₅H₅?Sc?CH₂C₆H₄NMe₂-o?₂?1-Sc?and the complex?C₅Me₄SiMe₃?Sc?CH₂C₆H₄NMe₂-o?₂?2-Sc?were used as a catalyst,and the[Ph₃C][B?C₆F₅?₄]was used as a cocatalyst for the polymerization of the three amine-functionalized styrene derivatives and their copolymerization with conjugated diolefins.A serious of functionalized polystyrene materials was obtained.The High stereospecific amine-functionalized polystyrenes were used as a carrier to support Pd nanoparticles to synthesize novel Pd@PDMAS catalysts.?1?When 1-Sc catalyst is used to catalyze three kinds of monomers,the polymerization of o-DMAS and m-DMAS needs to be high temperature at 60 ^oC,and the catalyst reaction activity is very low.When p-DMAS polymerization is catalyzed by 1-Sc,the reactivity is high,and obtained polymer which be a random structure;when the three monomers are catalyzed by the 2-Sc catalyst,the o-DMAS still needs a high temperature of 60 ^oC,but p-DMAS and m-DMAS are catalyzed by high activity which is much higher than the polymerization of o-DMAS.The polymers are high stereoselective polystyrene.?2?The 2-Sc catalyst was chosen to catalyze the copolymerization of three amine-functionalized styrenes with the conjugated diolefins.o-DMAS and BD can be copolymer and the polymer which o-DMAS contents in 14-53 mol%.The glass transition temperature of the copolymer increased with the increase of o-DMAS content.o-DMAS and IP can be copolymerized by 2-Sc.The copolymer which o-DMAS content in 10-48 mol%could be adjustable,and the molecular weight of the copolymer is controllable;m-DMAS and BD can be polymerized,the copolymer with m-DMAS content of 7-57 mol%,The glass transition temperature of the copolymer increases with increasing m-DMAS content.When m-DMAS and p-DMAS with IP do not copolymerize under the same conditions.?3?The three nitrogen-containing functionalized polymers can be supported 3 wt%of Pd metal atom and it can be used as a catalyst to catalyze the Suzuki coupling reaction.The loaded nano Pd particle size is between 3-10 nm,and the particle size dispersiveness is Pd@p-PDMAS<Pd@m-PDMAS<Pd@o-PDMAS.For the catalytic Suzuki-Miyaura coupling reaction conditions,when the reaction solvent is a water/ethanol mixed solvent and K ₂CO₃ be used in an amount of 2 equivalents of 4-bromotoluene,the conversion of 4-bromotoluene can be reached 95%,which could be used calalyze other groups reactants.The brominated reactants with other group also have a very good catalytic effect.