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* Correspondence: cgwu@mail [...].
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A poly(methyl methacrylate)-supported Pd0 nanocatalyst was successfully prepared from solution reaction of Pd(CH3COO)2 with a copolymer acid, poly(methyl methacrylate-ran-methacrylic acid) (MMA-MAA). The reaction was carried out in a benzene/methanol mixed solvent in the dark at room temperature (â¼25 °C) in the absence of a typical chemical reductant. There was coordination between the Pd0 nanoclusters and MMA-MAA, resulting in Pd0 nanoclusters being stably and uniformly dispersed in the MMA-MAA matrix, with an average particle size of â¼2.5 ± 0.5 nm. Mechanistically, it can tentatively be proposed that PMMA-ionomerization of the Pd2+ ions produces intramolecular -2COO--Pd2+ aggregate cross-links in the solution. On swelling of the chain-segments that are covalently bound via multiple C-C bonds, the resultant elastic forces cause instantaneous dissociation at the O-Pd coordination bonds to give transient bare (i.e., uncoordinated), highly-oxidative Pd2+ ions and H+-associative carboxylate groups, both of which rapidly scavenge electrons and protons, respectively, of the active α-H atoms abstracted from the methanol molecules of the solvent to make Pd0 nanoclusters supported by the re-formed MMA-MAA. The MMA-MAA acid copolymer, without itself undergoing any permanent chemical change, serves as a mechanical activator or catalyst for the mechanochemical reduction of Pd(CH3COO)2 under mild conditions. Compared with traditional Pd/C catalysts, this Pd0 nanocatalyst exhibited more excellent catalytic efficiency and reusability in the Heck reaction between iodobenzene and styrene, and it could be easily separated. The supported Pd0 nanocatalyst prepared using this novel and simple preparation method may display high-efficiency catalytic properties for other cross coupling reactions.
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A poly(styrene-ran-cinnamic acid) (SCA) containing 6.8 mol% of CA, with a MÌ w (â¼217 000) comparable to commercial polystyrene (PS), was successfully synthesised via emulsion free-radical copolymerisation as evidenced by 1744 and 1703 cm-1 infrared peak occurrences, respectively characteristic of free and dimeric carboxyl C[double bond, length as m-dash]O stretches. Upon the interchain hydrogen bond cross-linking by CA, the impact toughness of the SCA was considerably improved by 47.2% against PS, the glass transition, heat deflection and Vicat softening temperatures were significantly enhanced until 117.0, 108.0 and 118.3 °C, respectively, compared with PS (95.2, 87.6 and 96.0 °C), while the extensional viscosities were near one order-of-magnitude higher than PS by which the temperature window required for appropriate melt-strengths would be greatly broadened. Meanwhile, the SCA displayed other properties basically analogous to PS. This work presents a modified PS, SCA, with enhanced toughness, heat resistance and melt strength that potentially extend its styrofoam and commodity applications.
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When a small-molecule ionic crystal is group-substituted with polymer chain-segments to form an ionomer, do its constrained ionic aggregates maintain ordered internal structures? This work presents, for a Na-salt sulfonated-polystyrene ionomer, reconciled TEM electron-diffraction schlieren textures and WAXS Bragg-type reflections from the ionic-aggregate nanodomains, which solidly prove the aggregates' internal (mono)crystalline order. The observed DSC endotherm of the ionomer, identified by WAXS as an order-disorder transition interior to its aggregates, gradually becomes enhanced over a 3-month, room-temperature physical aging process, indicating that the aggregates' ordering is a slow relaxation process in which the degree of order increases with time. This work corroborates an uncommon form of order, i.e., polymer-bound small-molecule ionic (quasi)crystal, which is supplementary to the order phenomena in small molecules, polymers, and liquid crystals.
