One-dimensional patchy nanostructures are interesting materials due to their excellent interfacial activity and their potential use as carrier for functional nanoparticles. Up to now only wormlike crystalline-core micelles (wCCMs) with a nonfunctional patchy PS/PMMA corona were accessible using crystallization-driven self-assembly (CDSA) of polystyrene-block-polyethylene-block-poly­(methyl methacrylate) (SEM) triblock terpolymers. Here, we present a facile approach toward functional, patchy wCCMs, bearing tertiary amino groups in one of the surface patches. The corona forming PMMA block of a SEM triblock terpolymer was functionalized by amidation with different N,N-dialkyl­ethylene­diamines in a polymer analogous fashion. The CDSA of the functionalized triblock terpolymers in THF was found to strongly depend on the polarity/solubility of the amidated PMMA block. The lower the polarity of the amidated PMMA block (increased solubility), the higher is the accessible degree of functionalization upon which defined, well-dispersed wCCMs are formed. Interestingly, also the structure of the patchy corona can be tuned by the composition/chemistry of the functional patch, giving rise to spherical patches for R = methyl, ethyl and rectangular patches for R = isopropyl. Patchy wCCMs were successfully used as template for the selective incorporation of Au nanoparticles within the amidated corona patches, showing their potential as versatile platform for the construction of functional, mesostructured hybrid materials.

For next generation lithium batteries, solid polymer electrolytes (SPEs) are essential to meet the challenges of higher safety standards, higher specific energy, and easy processing. Linear polyethylene glycol (PEG) based SPEs are by far the most investigated systems for these requirements. However, the weak mechanical properties, high crystallinity, and consequently moderate ionic conductivity prevent these systems from being used in electrochemical storage devices. We address the question of the influence of the polymer architecture on the above properties by synthesizing bottlebrush copolymers carrying PEG side chains and comparing their electrochemical properties and ionic conductivity with those of the respective linear PEG polymers. For obtaining bottlebrush polymers, first methacrylate (PEGMEMA) and norbornene (Nb-PEGME) macromonomers carrying PEG side chains were synthesized and polymerized using either free radical polymerization or ring-opening metathesis polymerization (ROMP), respectively. We varied the lengths of PEG side chains (1 kg mol–1 and 2 kg mol–1), and the selection of two different backbones results in polymethacrylate Poly­(MA)m-graft-PEGME1k,2k and polynorbornene Poly­(Nb)m-graft-PEGME2k brushes. All synthesized brush polymers are thermally stable up to 350 °C and show a decreased crystallinity compared to their linear counterparts. Finally, the influence of polymer architecture on ionic conductivity, Li-ion transport number, and electrochemical stability of a series of SPEs obtained thereof by mixing with different amounts of LiTFSI is investigated. The implications of changing a linear polymer system to a brush architecture for potential applications in batteries were examined with respect to thermal properties of the SPEs carrying different O/Li ratios, and we found out that the ionic conductivity scales with the T g of the system as a generic rule. Electrochemical impedance spectroscopy data facilitated the correlation of the occurring processes in the cell with the distribution of relaxation times (DRT). Ionic conductivities in the range of 10–3–10–4 S cm–1 for the solvent-free SPEs were obtained for a temperature range of 80–25 °C. Furthermore, Li ion transport numbers and electrochemical stability of the brush polymer SPEs are comparable to linear PEG SPEs.

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A series of novel polymethacrylates and polyacrylates carrying diester sidechain moieties with varying alkyl spacer lengths are designed, synthesized, and evaluated as solid polymer electrolytes (SPEs) in lithium metal batteries...