Abstract
Hybrid copolymerization of structurally different, reactivity and mechanism distinct monomers (e.g., cyclic and vinyl type monomers) is of great interest and challenge for both academic research and practical application. Herein, ethylene oxide-co-tert-butyl methacrylate-co-poly(ethylene glycol) benzyl methacrylate (EO-co-BMA-co-bPEO), a statistical copolymer was synthesized via hybrid copolymerization of EO and BMA using an uncharged, non-nucleophilic organobase t-BuP4 as the catalyst. Detailed characterizations indicate that hybrid copolymerization of ethylene oxide and vinyl monomer forms a statistical copolymer concurrently with the transesterification of tert-butyl group and oligomer PEO anions. The application of the copolymer as all solid lithium-ion battery polymer electrolyte was investigated by detecting the ionic conductivity (σ) with electrical impedance spectrum measurement.
Highlights
Livingpolymerization is a powerful tool to construct well-defined homopolymers or copolymers with a narrow dispersity, high molecular weight, controlled composition and architecture
Hybrid copolymerization makes cyclic and vinyl monomers copolymerize into a statistical copolymer possibly, where each monomer can form propagating species and combine with either similar or dissimilar monomers
The 1H NMR analysis of the resulting product showed that the proton signals for PEO and PBMA were all presented in the product while a new peak appeared at 4.10 ppm (Figure 1A), indicating that ethylene oxide (EO) and butyl methacrylate (BMA) segments were both in the obtained product but with something new
Summary
Living (co)polymerization is a powerful tool to construct well-defined homopolymers or copolymers with a narrow dispersity, high molecular weight, controlled composition and architecture (e.g., block, brush and star polymers). Copolymers are commonly prepared by sequentially adding different monomers or using a mixture of co-monomers [1,2,3,4,5,6]. Combining polymerization techniques with different mechanisms is an alternative route to fabricate copolymers from conventional methods, but it is still a great challenge in terms of polymer synthesis. Concurrent vinyl-addition and ring-opening hybrid copolymerization is of particular importance because large quantities of (meth)acrylates and oxiranes have been widely used to prepare various functional copolymers [7,8,9,10]. Only a few studies have reported such copolymerization reactions concerning vinyl and cyclic monomers, including cyclic imino ethers, dioxaphospholanes, aziridines and (meth)acrylates [11,12,13,14], methacrylate (MMA)/tert-butyl methacrylate (BMA) and ε-caprolactone (CL) [15,16], and vinyl ethers and oxiranes [17,18,19], and the reaction mechanism is zwitterionic, anionic or cationic
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