| Polyelectrolytes are polymers with ionizable groups in the backbone or side-chain.In recent years,they have aroused considerable attention in the field of new ionic conducting materials,who combine the conductivity of electrolyte materials and physical properties of polymers.In this paper,several polymers with triazole groups were synthesized,after that,poly（triazolium）s were obtained by N-alkylation and anion exchange reactions.Hence,it is focus on the ionic conductivity of these poly（triazolium）s,and investigate the relationship between structure and ionic conductivity of these polymers,as depicted in the follows:Hyperbranched polymer[hb-PTA-PEG]+[TFSI]-containing hybrid quaternary ammonium ion and triazolium ion was synthesized.The structure of the monomers and polymers were determined by FT-IR,NMR,HR-EISMS and EA.These hyperbranched polymers presented broad electrochemical stability window of above 6.0 V versus Ag+/Ag and4.3 V versus Li+/Li,and displayed low glass transition temperature（Tg）in the range of-13?-37 oC,owing to the hyperbranched structure combined with the hybrid ionic groups and long flexible PEG end-group.[hb-PTA-PEG]+[TFSI]-showed superior ionic conductivity,which was were all above 10-5 S?cm-1 at 30 oC.The ionic conductivity of hybrid ions polyelectrolyte was higher than that only contained triazolium ion.In order to further investigate the metathesis cyclopolymerization（MCP）of ion-containing1,6-heptadiyne,1,6-heptadiynes containing quaternary ammonium ion or triazolium ion were synthesized,which were used to prepare block copolymers by MCP.The structure of the monomers and polymers were determined by FT-IR,NMR,and HR-EISMS technologies.DLS testing showed that the copolymers self-assembly in tetrahydrofuran solution.TEM testing showed that the copolymer self-assembly into‘core-shell’nanostructure.Block copolymer poly[MDTA]+[TFSI]-25-b-poly[TMPA]+[TFSI]-50 doped with 0.15 molar ratio of LiTFSI performed the highest ionic conductivity about 1.0×10-4 S?cm-1,which was much higher than the corresponding homopolymers at room temperature.Ionic copolymers poly（TDPAA-[MDTA]+[TFSI]-）were successfully prepared by MCP of diyne monomer[MDTA]+[TFSI]-and trifunctional diyne monomer TDPAA.By varying the ratio of TDPAA to[MDTA]+[TFSI]-,the physical state of polymers were regulated from the viscous semi-solid to the sticky soft solid with star structure,flexible solid with branched or slight crosslinked structure,and insoluble hard solid with deep crosslinked structure.The star copolymer poly(TDPAA1-[MDTA]+[TFSI]-75)exhibited high ionic conductivity of 2.9?10-5S?cm-1,and poly(TDPAA6-[MDTA]+[TFSI]-75)performed simultaneous ionic and electric conductivities of 6.3?10-6 and 3.2?10-6 S?cm-11 after I2 doped.Eucommia ulmoide gum（EUG）is a biomass-based polymer,and has a number of double bonds on the backbone,which can be post-functionalized.1,2,4-triazoline-3,5-dione derivative was synthesized and used to modify EUG by Alder-ene reaction,yielding a viscous modified EUG polyelectrolyte bearing 1,2,3-triazolium and polyethylene glycol pendants,which exhibited a relatively high ionic conductivity of 1.3×10-5 S?cm-1 at 30 oC.The viscous EUG polyelectrolyte was further crosslinked by bis（1,2,4-triazoline-3,5-dione）-hexane（bHTAD）,and transformed to a solid state with a tensile strength of 2.0 MPa and an elongation at break of 150%.The crosslinked flexible EUG polyelectrolyte can take up ionic liquids with good compatibility to form the ion gel,and demonstrated an enhanced ionic conductivity of 1.4×10-4 S?cm-1 at 30 oC when containing 50 wt%of ionic liquid,while maintaining good mechanical properties,which will have a potential application in the field of dielectric elastomer and flexible electronic devices.Finally,it was discussed the possibility of the preparation polyurazole by the Alder-ene based addition reaction of bHTAD or bPTAD reacted with the compounds who containing bifunctional unsaturated bonds,such as bifunctional imidazoles（DIH,DIDO,[HBIH]+[Br]-,and[HBIH]+[PF6]-）,dicyclopentadiene,and 1,5-cyclooctadiene.The structure of monomers and polymers was characterized by NMR and FT-IR spectroscopy.The molecular weight of the polymer was characterized by GPC testing.The resultant additive product of bHTAD and 1,5-cyclooctadiene could be dissolved in polar solvents,and showed a molecular weight of 6.2 kDa with a PDI of 1.1. |
