Stereogenic 2-(N-carbamoyl)pyrrolidinylcuprates prepared from scalemic (i.e., enantioenriched) N-Boc-2-lithiopyrrolidine and THF soluble CuCN.2LiCl react with vinyl iodides, vinyl triflates, beta-iodo-alpha,beta-enoates, propargyl mesylates, and allyl bromide to afford the substitution products with excellent enantioselectivity. Excellent enantiomeric ratios are obtained in the conjugate addition reactions with methyl vinyl ketone while low enantiomeric ratios can be achieved with acrylate esters using HMPA/TMSCl activation. Enantiomeric ratios vary with substrate substitution patterns and the observed enantioselectivities appear to be more a function of cuprate-electrophile reactivities than of the reaction type (e.g., substitution, conjugate addition). Low enantiomeric ratios are obtained with the alpha-(N-carbamoyl)benzylcuprates. The lithium-copper transmetalation and cuprate vinylation reactions proceed with retention of configuration.
Ethylene vinyl acetate rubber (vinyl acetate (VA) content = 50 wt %) (EVM) and ethylene vinyl acetate copolymer (VA content < 50 wt %) (EVA) are polymers with a very similar chemical structure. In this study, a novel thermoplastic vulcanizate (TPV) based on EVM/EVA28 (VA content = 28 wt %) blend has been successfully fabricated by dynamic vulcanization due to the selective cross-linking of EVM. The morphologies and properties of the TPVs have been investigated. It was found that the cross-linked EVM phase and the thermoplastic EVA28 phase form a perfect cocontinuous structure with the rubber phase size of about 100 nm. The fabricated TPV exhibits not only excellent stretchability (>900% elongation at break), nice elasticity (only about 19% remnant strain at 100% stretching), and good flexibility but also superior oil resistance.
Magnesium hydroxide (MH) and an intumescent flame retardant (IFR) have been incorporated into a thermoplastic vulcanizate (TPV) for the purpose to fabricate halogen-free flame retardant elastomeric materials. Significant synergistic effects of MH and IFR have been observed for the TPV in terms of both flame retardant properties and mechanical performance. The mechanism of the synergistic effects has been investigated. The results indicate that a small amount of IFR accelerates the degradation of the matrix and induces a shrinkage matrix, leading to a compact and unbroken MgO protective layer. Such compact MgO layer on the surface of the material prevents the bulk material from further degradation, and a high flame retardant performance was achieved. Obviously, this novel flame retardant system paves new possibility for the high performance nonhalogen flame retardant polymeric materials and should also be applied to other polymers.
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