Synthesis Of Dielectric Polymers With Bipyridyl Ligand And Metal Complex Pendants By Ring-Opening Metathesis Polymerization

The development of advanced dielectric energy storage technology is a major issue of global concern,and the innovation of materials will play a vital role in the next generation of electrical and electronic applications.Dielectric polymers have an important direction for the development of modern dielectric materials due to their good processing flexibility,low loss,high dielectric strength,and faster charging-discharging efficiency.However,a lower dielectric constant(<4)of polymers results in a lower energy density,which can increase the volume of the capacitor.Therefore,it is necessary to design new high-performance polymers.In this thesis,polymers containing bipyridine and its metal complex side groups were designed to improve the dielectric properties of the polymers.The main contents were as follows.In second chapter,we designed and synthesized N-butyric acid(4-methoxy-4'-methyl-2,2'-bipyridyl undecyl)ester norbornene dicarboxyimide(BNDI),N-butyric acid[bis(2,2'-bipyridine)-(4-methoxy-4'-methyl-2,2'-bipyr-idine)undecyl]ruthenium(II)norbornene dicarboxyimide(TBNDI-Ru),and N-butyric acid[bis(2-phenylpyridine)-(4-methoxy-4'-methyl-2,2'-bipyridine)undecyl]iridium(III)norbornene dicarboxyimide(TBNDI-Ir).Moreover,in order to improve the solubility and film-forming properties of the polymers,the monomer N-butyric acid(triethylene glycol monomethyl ether)ester norbornene dicarboximide(TENDI)was also synthesized.The corresponding polymers were prepared by ring-opening metathesis polymerization(ROMP).The effects of the content and types of metal ions on dielectric and energy storage properties were explored.Dielectric and energy storage tests shown that the dielectric energy storage properties of polymers were significantly improved due to a variety of interactions(dipole polarization,interface polarization,and the long-range polaron hopping process).The block copolymer(PTNP₂₀₀-co-PTENDI₁₀₀)-b-PTBNDI-Ir₁₅ had high?_r(27.5-27.2),the U_r/U_s could reach4.17/4.86 J cm^-3 at 280 MV m^-1 with a high?of 85.8%.In the third chapter,bis(11-butyl ester)2,2'-bipyridine-5,5'-dicarboxylate norbornene dicarboximide(BBNDI)was synthesized,and the corresponding polymers were prepared by ROMP.The ruthenium(II)-bipyridine complex was introduced into the polymer side chain by"post-modification method"to investigate the influence of the length of the insulating block PTNP on the dielectric performance.Dielectric and energy storage tests showed that the metal ions could be better separated and wrapped by extending the length of the insulating PTNP,which could improve the dielectric energy storage of polymers bearing the ruthenium(II)-bipyridyl side group.The block copolymer PBBNDI20-(PTNP200)2-Ru had relatively high?_r(17.5-16.1),the U_r/U_s could reach 3.96/4.53 J cm^-3at 280 MV m^-1 with a high ? of 87.5%.