Zwitterionic ring-opening polymerization of macrocyclic ethyleneoxy-substituted carbonate:Access to cyclic PEG-like polycarbonate

The innovation in polymer design to rival conventional polyethylene glycol(PEG)is an important approach to achieving a more sustainable society.Here,cyclic PEG-like polycarbonates having high molecular weight(4.4–49.5 kg/mol)were enabled through zwitterionic ring-opening polymerization(ZROP)of macrocyclic carbonates(MCs)mediated by N-heterocyclic carbene(NHC).The thermodynamic behavior of polymerization depends on the ring size of monomers.During this process,the ZROP of 11-membered MC was driven by the change of enthalpy(ΔH_(p))which differed from the ZROP of 14-membered MC driven by the entropic change(ΔS_(p)).Cyclic polycarbonates depicted improved thermostability(T_(d5%)≥204℃)and higher glass transition temperatures(T_(g)>–40℃)in comparison to their linear analogues(T_(d5%)≤185℃,T_(g)~–50℃).In addition,the mechanism of ZROP of MC was addressed through computational study.A distinct mechanism of polymerization distinguishable from the well-known NHC-mediated ZROP of cyclic esters was revealed,where the zwitterion from nucleophilic addition to MC,i.e.tetrahedral intermediate,cannot be ring-opened probably due to the delocalization of negative charge on the carbonate group,but serves as an active center for the polymerization.In comparison to PEG,the attained polymer demonstrated comparable hydrophilic and biocompatible properties,as revealed by the results of contact angle and in vitro cytotoxicity studies,suggesting that cyclic polycarbonate hold the promise as the alternative of PEG.

Constructing mild expanded graphite microspheres by pressurized oxidation combined microwave treatment for enhanced lithium storage

The modified graphite anode materials have some prominent advantages over other anode materials in the industrial applications.A novel simple and gentle method is proposed to synthesize the mild expanded graphite microspheres(MEGMs) from flake graphite spheres through a combined modified pressurized oxidation combined with the microwave treatment.The microstructural results demonstrate that moderately expanded MEGMs with an expansion volume between 4 and 10 ml·g^(-1)exhibit a highly microporous structure with an enlarged interlayer spacing,a decreased microcrystalline size,as well as an increased number of functional groups on the surface,resulting in the increased storage sites and spaces for lithium ions and the enhanced diffusion rate of lithium ions.When used as the anode material for lithium-ion batteries,the MEGM-T75t30 obtained by oxidation treatment at 75℃ for 30 min followed by microwave irradiation for expansion displays a high reversible capacity of 446.7 mAh·g^(-1) at 100 mA·g^(-1) after 100 cycles and excellent rate performance(330 and 116 mAh·g^(-1) at 800 and 3200 mA·g^(-1),respectively).Therefore,the MEGMs prepared by this convenient and mild method show excellent electrochemical properties and good application potential.