Synthesis Of Functionalized Ethylene-Propylene Rubber Using Half-Sandwich Scandium Complexes

Functionalized ethylene-propylene rubber can improve the adhesion,printing and dyeing properties of tradtional ethylene-propylene rubber,and compatibility with other materials while maintaining the excellent anti-aging properties,low-temperature properties,and mechanical properties of ethylene-propylene rubber,thereby widening the application field of ethylene-propylene rubber as a high-performance material.In this thesis,the direct copolymerization of ethylene,propylene and functional?-olefins by half-sandwich scandium complexes have also been achieved to afford bromine-containing and nitrogen-containing ethylene-propylene rubbers.A series of ethylene-propylene rubbers containing multiple double bonds were also obtained by the terpolymerization of ethylene,propylene and myrcene by using half-sandwich scandium complexes.By efficiently transforming the C=C double bonds into other polar groups,a series of new ethylene-propylene rubber with strong polar groups was obtained.1.By use of scandium complex C₅Me₄SiMe₃Sc?CH₂SiMe₃?₂?THF??2?,the copolymerization of propylene and 10-bromo-1-decene?BrDC?has also been achieved for the first time to afford the random Br DC-propylene copolymers containing 4²2 mol%isolated BrDC units.The terpolymerization of ethylene,propylene and BrDC has also been achieved with high activity by use of 2,affording the corresponding random ethylene-propylene-BrDC terpolymers containing 2¹1 mol%BrDC units.The scandium complexe 2 can also realize high-activity random tetrapolymerization of ethylene,propylene,BrDC with three different kinds of dienes?ethylene norbornene,isoprene and myrcene?,which afforded the novel brominated ethylene-propylene rubbers with controllable double bonds.2.The copolymerization of ethylene with 5-?N,N-diethylamino?-l-pentene?DEAP?could be efficiently realized by using scandium complexe?C₅Me₄SiMe₃?Sc?CH₂C₆H₄NMe₂-o?₂?1?,but it cannot realize the copolymerization of propylene and DEAP.By use of scandium complexe1,the terpolymerization of ethylene,propylene with DEAP has also be achieved for the first time to afford nitrogen-functionalized ethylene-propylene rubbers with controllable composition?DEAP units content 8³1 mol%?,adjustable molecular weight and excellent thermodynamic properties.3.By use of scandium complexes 1 and 2,the copolymerization of myrcene with propylene and the terpolymerization of myrcene with propylene and ethylene have also been achieved for the first time.In the copolymerization of myrcene with propylene,the scandium complex 1afforded the multiblock myrcene?ethylene copolymers with different myrcene contents;the scandium complex 2 afforded the random myrcene?ethylene copolymers with isolated BrDC units.More remarkably,the terpolymerization of myrcene with ethylene and propylene has also been realized by use of scandium complex 2,yielding a new family of myrcene-based ethylene?propylene?diene rubbers?EPDM?with high activity(up to 10⁵ g of polymer?mol of Sc?^-1 h^-1).The compositions of terpolymers were controllable with myrcene units content 5²4 mol%and propylene content 8³7 mol%.The terpolymers possessed high molecular weighets?M_n=1.0⁴.6×10⁴?,low glass-transition temperature?T_g=-63^-52 ^oC?.By efficiently transforming the C=C double bonds of the resulting myrcene-based EPDM into other polar groups,the versatile functionalized polyolefins were obtained in an efficient and environmentally friendly manner.The results suggested that all of C=C double bonds in the myrcene-based EPDM were completely converted into sulfonic groups by thioacetylate and oxidation.All of C=C double bonds in myrcene-based EPDM except vinylidene of 3,4-myrcene units were completely transformed into hydroxyl groups and chloride groups by epoxidation and the ring-opening reaction.