Although the rational designed mechanochromic polymer (MCP) materials have evoked major interest and experienced significant progress recently, it is still a great challenge to develop a facile and effective strategy for preparation of reversible broad-spectrum MCPs with a combination of wide-range color switch ability and high sensitivity, which thus make it possible to mimic gorgeous color change as in nature. Herein, we designed and synthesized a novel rhodamine-based mechanochromic elastomer. Our results demonstrated that the elastomer exhibited very promising and unique properties. Three primary fluorescence colors were presented during continuous uniaxial extension and relaxing process, and reversible broad-spectrum fluorescence color change could be achieved consequently. The fluorescence quantum yield of the opened zwitterion of this new mechanophore was as high as 0.67. In addition, the elastomer showed very high sensitivity to stress with a detectable activation strain of ∼0.24, which was much smaller than those reported in the previous literature reports. Meantime, the easy-to-obtain material, facile preparation, and good mechanical property also made it suitable for potential practical applications.
polymer has attracted considerable attention due to its excellent properties. Although a number of 2D polymers have been reported, preparation of free-standing single-layer 2D polymers in solution is still a big challenge. Here we report a facile and highly efficient strategy for synthesis of free-standing single-layer covalent pseudo-2D polymers via free radical polymerization in water on a large scale. The strategy designated as "two-dimensional selfassembly polymerization (2DSP)" includes formation of supramolecular 2D nanosheets by self-assembly of bolaamphiphilic monomer that bearing two maleic acid moieties and transformation of supramolecular 2D nanosheets to covalent pseudo-2D polymers by copolymerization with vinyl monomers. We find that the counterion of the bola-amphiphile has a significant influence on formation of single-layer supramolecular 2D nanosheets, and the formation of 2D polymer sheets is highly related to the vinyl monomers. The unique 2D polymer sheets were used to prepare hydrogels with excellent mechanical properties.
2D polymer sheets containing azobenzene are successfully prepared by a facile strategy of "2D self-assembly polymerization (2DSP)" via free radical polymerization in solution. A bola amphiphile containing azobenzene as a novel monomer is designed and synthesized. The results indicate that single-layer covalent pseudo-2D polymers on a micrometer scale are obtained after polymerization with vinyl monomers. Moreover, the 2D polymer sheets are highly sensitive to UV light due to incorporation of azobenzene groups into the polymer. Upon alternative irradiation with UV and visible light, the morphological transformation between sheets and rolled-up nanotubes can be achieved based on the reversible trans-to-cis photoisomerization of azobenzene units in the 2D polymer sheets.
Carbon nanotubes can be used as promising reinforcement materials to improve the mechanical properties of hydrogels, but their poor dispersibility in aqueous solution severely limits their application in preparation of composite hydrogels. Therefore, to develop method for modification of carbon nanotubes is still highly desired. In this paper, a facile approach for preparation of the hydrophilic carbon nanotube was reported. The encapsulated multiwalled carbon nanotubes (E-CNT-PAA) with cross-linked shell structure were obatined through the self-assembly of the amphipathic azide diblock copolymers poly(acrylic acid)-b-poly(4-vinylbenzyl azide-co-styrene) (PAA-b-(PVBA-co-PS)), and the cross-linking of inside azide groups under UV irradiation. The encapsulated MWCNT was characterized by FT-IR, Raman and TEM. It was demonstrated that the dispersibility of the hydrophilic encapsulated MWCNTs was related to the length of the poly(acrylic acid) brushes. Subsequently, thermal-responsive composite hydrogels (PNIPAM/E-CNT-PAA) were prepared by in situ polymerization of N-isopropylacrylamide (NIPAM) in the solution of dispersed E-CNT-PAA. The results showed that the composite hydrogels possessed high mechanical properties compared to the pure PNIPAM hydrogel. The tensile strength and elongation of the composite hydrogels were highly dependent on the content of the modified MWCNTs. The composite hydrogels with 0.46 wt % MWCNTs exhibited tensile strength of 97.7 kPa and elongation of 465%, which were at least 3.5× higher than those of the PNIPAM hydrogel. Moreover, the composite hydrogels displayed significant and reversible stimuli-responsiveness.
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