The chemical functionalization of polyolefins to access responsive materials is a long-standing challenge in materials science. Current protocols do not typically tolerate polar functional groups, and postpolymerization modification often leads to material defects. Here the catalytic synthesis of amine-functionalized polyolefins has been achieved using a two-step catalytic combination of hydroaminoalkylation and ring-opening metathesis polymerization (ROMP). Furthermore, reduction was used to obtain an aminated polyethylene analogue. This preparation transforms simple starting materials into polar-functionalized polymers with complete atom economy. Utilizing dynamic associative interactions, including hydrogen bonding, these materials demonstrate tunable rheological properties, autonomous self-healing, and unexpected adhesion to polytetrafluoroethylene (PTFE).
Amine-functionalized polymeric materials have a wide variety of applications; however, the preparation of these materials is often plagued by laborious, multistep synthetic routes. Herein, a modified and improved synthetic protocol utilizes the hydroaminoalkylation reaction to catalytically assemble amine-functionalized monomers on a gram scale with 100% atom economy. Combined with ring-opening metathesis polymerization (ROMP), amine-functionalized polymers with varying electronic properties have been synthesized. Extensive rheological characterizations show that modification of the electronic properties of the amine substituent influences the bulk material properties through modification of hydrogen bonding and π-stacking interactions to afford dynamic cross-linking within the polymeric material. Tertiary amine-containing polymers display distinct rheological properties that differ from those of polymers with pendant hydrogen-bond-donating secondary amines. The profound viscoelastic effects that result from the incorporation of tunable dynamic interactions are presented.
Currently, finding a suitable anode material for sodium-ion batteries (NIBs) is the major challenge as graphite is not an ideal anode candidate. Recently, organic anode materials hold promise as potential alternatives. In this study, naphthalene based dicarboxylate (Na 2 -NDC) has been explored as anode material for NIBs. The electrochemical sodiation/desodiation process of Na 2 -NDC is a biphasic reaction and it shows a good capacity retention even after 100 cycles. Ex-situ XRD studies reveal structurally robust nature of Na 2 -NDC during sodiation/desodiation process. Moreover, the Na 2 -NDC anode was paired with Na 3 V 2 O 2 (PO 4 ) 2 F/rGO cathode and demonstrated a full cell for the first time.
The synthesis, characterization and electrochemical sodiation/desodiation performance of two novel disodium diimide carboxylates, disodium salt of N,N'-bis (glycinyl) pyromellitic diimide (Na 2 -BPDI) and disodium salt of N,N'-bis (glycinyl) naphthalene diimide (Na 2 -BNDI) were reported for the first time. The Na 2 -BNDI electrode material delivers a reversible capacity of 122 mAh g −1 in the first cycle and retains a reasonable capacity of 92 mAh g −1 after 50 cycles at a current density of 50 mA g −1 , whereas a rapid capacity fading is observed in the case of Na 2 -BPDI electrode material in subsequent cycles. Ex-situ NMR and FT-IR studies confirmed that the decomposition of Na 2 -BPDI electrode material upon continuous electrochemical sodiation/desodiation process. These results demonstrate that the importance of extended conjugation, as in Na 2 -BNDI, for efficient electrochemical sodium storage in the redox active aromatic compound.
Ring-opening metathesis polymerization (ROMP) of two different types of amine-functionalized monomers, aminonorbornenes (ANs) and aminocyclooctenes (ACs), has been studied using [(H2IMes)(PCy3)(Cl)2Ru = CHPh] Grubbs second generation catalyst, G2, and [(H2IMes)(pyr)2(Cl)2Ru = CHPh] Grubbs third generation catalyst, G3. Despite the known detrimental effects of unprotected amine functionalities on Ru-based ROMP catalysts, aminopolyolefins can be readily prepared using G2 and G3. The influence of the amine substituent of the monomer on the polymerization process, as probed by monitoring reaction kinetics, confirmed that the basicity/nucleophilicity of the amine group has a detrimental influence on the ROMP process. Reaction kinetics of homopolymerization of both these classes of monomers revealed faster polymerization of ACs than the more strained AN counterpart, which has been attributed to the favored chelated catalyst resting states in the case of ANs. Hammett studies show increased polymerization rates in the presence of electron-withdrawing aryl amine-containing monomers. These observed kinetic effects were used to advantage in the copolymerization of AN and AC monomers to access a gradient polymer. Polymerization kinetics of combined monomers displayed different reactivity profiles than observed during homopolymerization. Polyolefins with unprotected secondary alkyl amines could be synthesized by leveraging the unfavorable chelate formation in the case of AC monomers. The strategic selection of cyclic alkene and relative positioning of amine substituent allows for the diverse incorporation of secondary amines into polymers by ROMP.
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