RESUMEN

The development of low-temperature self-healing polymers is crucial because high-temperature or softening conditions for rapid self-healing inevitably reduce their mechanical strength. Herein, we first report cellulose nanocrystal (CNC)/polymer nanocomposites with a rapid low-temperature self-healing performance. The nanocomposite was prepared by simple blending of grafted CNC and matrix prepolymer made from the monomers having metal-ligand coordination and lower critical solution temperature functionalities along with the presence of hexamethylene diisocyanate and dibutyltin dilaurate. Owing to the dynamic nature of both hydrogen bonds and metal-ligand coordinated covalent bonds, the resultant nanocomposites showed excellent self-healing efficiency (99 %, within 1 h) at a low temperature (5 °C) with robust mechanical properties including a high stretchability (230 %), high toughness (2538 MJ/m3), enhanced tensile strength (25.49 ± 0.02 MPa), and improved thermomechanical properties. Self-healing performance of the coordinated covalent bonds requiring active hydrogen was considerably improved by the introduction of CNCs with abundant hydrogen bonds.

Asunto(s)

Nanocompuestos , Nanopartículas , Celulosa/química , Ligandos , Nanocompuestos/química , Nanopartículas/química , Polímeros , Temperatura

RESUMEN

In this study, poly(2,2,2-trifluoroethyl methacrylate)-block-poly(4-vinylpyridine) (PTFEMA-b-PVP) was synthesized by stepwise reversible addition-fragmentation chain transfer (RAFT) polymerization for the preparation of graphene by the exfoliation of graphite nanoplatelets (GPs) in supercritical CO2 (SCCO2). Two different block copolymers (low and high molecular weights) were prepared with the same block ratio and used at different concentrations in the SCCO2 process. The amount of PTFEMA-b-PVP adsorbed on the GPs and the electrical conductivity of the SCCO2-treated GP samples were evaluated using thermogravimetric analysis (TGA) and four-point probe method, respectively. All GP samples treated with SCCO2 were then dispersed in methanol and the dispersion stability was investigated using online turbidity measurements. The concentration and morphology of few-layer graphene stabilized with PTFEMA-b-PVP in the supernatant solution were investigated by gravimetry, scanning electron microscopy, and Raman spectroscopy. Destabilization study of the graphene dispersions revealed that the longer block copolymer exhibited better affinity for graphene, resulting in a higher yield of stable graphene with minimal defects.

RESUMEN

This article describes a comprehensive study for the preparation of graphene dispersions by liquid-phase exfoliation using amphiphilic diblock copolymers; poly(ethylene oxide)-block-poly(styrene) (PEO-b-PS), poly(ethylene oxide)-block-poly(4-vinylpyridine) (PEO-b-PVP), and poly(ethylene oxide)-block-poly(pyrenemethyl methacrylate) (PEO-b-PPy) with similar block lengths. Block copolymers were prepared from PEO using the Steglich coupling reaction followed by reversible addition-fragmentation chain transfer (RAFT) polymerization. Graphite platelets (G) and reduced graphene oxide (rGO) were used as graphene sources. The dispersion stability of graphene in ethanol was comparatively investigated by on-line turbidity, and the graphene concentration in the dispersions was determined gravimetrically. Our results revealed that the graphene dispersions with PEO-b-PVP were much more stable and included graphene with fewer defects than that with PEO-b-PS or PEO-b-PPy, as confirmed by turbidity and Raman analyses. Gravimetry confirmed that graphene concentrations up to 1.7 and 1.8mg/mL could be obtained from G and rGO dispersions, respectively, using PEO-b-PVP after one week. Distinctions in adhesion forces of PS, VP, PPy block units with graphene surface and the variation in solubility of the block copolymers in ethanol medium significantly affected the stability of the graphene dispersion.

RESUMEN

Despite the superior properties of graphene, the strong π⁻π interactions among pristine graphenes yielding massive aggregation impede industrial applications. For non-covalent functionalization of highly-ordered pyrolytic graphite (HOPG), poly(2,2,2-trifluoroethyl methacrylate)-block-poly(4-vinyl pyridine) (PTFEMA-b-PVP) block copolymers were prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization and used as polymeric dispersants in liquid phase exfoliation assisted by ultrasonication. The HOPG graphene concentrations were found to be 0.260⁻0.385 mg/mL in methanolic graphene dispersions stabilized with 10 wt % (relative to HOPG) PTFEMA-b-PVP block copolymers after one week. Raman and atomic force microscopy (AFM) analyses revealed that HOPG could not be completely exfoliated during the sonication. However, on-line turbidity results confirmed that the dispersion stability of HOPG in the presence of the block copolymer lasted for one week and that longer PTFEMA and PVP blocks led to better graphene dispersibility. Force⁻distance (F⁻d) analyses of AFM showed that PVP block is a good graphene-philic block while PTFEMA is methanol-philic.

RESUMEN

The ability to disperse pristine (unfunctionalized) graphene is important for various applications, coating, nanocomposites, and energy related systems. Herein we report that amphiphilic copolymers of poly(4-vinyl pyridine)-block-poly(ethylene oxide) (PVP-b-PEO) are able to disperse graphene with high concentrations about 2.6mg/mL via sonication and centrifugation. Ethanolic and aqueous highly-ordered pyrolytic graphite (HOPG) dispersions with block copolymers were prepared and they were compared with the dispersions stabilized by P-123 Pluronic® (P123) and poly(styrene)-block-poly(ethylene oxide) (PS-b-PEO) synthesized. Transmission electron microscopy, scanning electron microscopy, atomic force microscopy, X-ray diffraction, Raman and UV-visible spectroscopic studies confirmed that PVP-b-PEO block copolymers are better stabilizers for HOPG graphene than P123 and PS-b-PEO. X-ray photoelectron spectroscopy and force-distance (F-d) curve analyses revealed that the nitrogen of vinyl pyridine plays a vital role in better attractive interaction with surface of graphene sheet. Thermogravimetric analysis showed that larger amount of PVP-b-PEO was adsorbed onto graphene with longer poly(4-vinyl pyridine) (PVP) block length and in aqueous medium, respectively, and which was consistent with electrical conductivity decreases. This study presents the dispersion efficiency of graphene using PVP-b-PEO varies substantially depending on the lengths of their hydrophobic (PVP) domains.

RESUMEN

The photoresponsive phase separation of a poly(N-isopropylacrylamide-co-spironaphthoxazine methacryloyl-co-allyl-2-(2,6-bis((E)-4-(diphenylamino)styryl)-4H-pyran-4-ylidene)-2-cyanoacetate) random copolymer, i.e., poly(NIPAAm-co-SPO-co-fluorophore), in water-in-oil (W/O) droplets is described. The photoresponsive aqueous droplets were generated in the coflow regime of a simple tubular microfluidic device. The phase separation of the copolymer in the W/O droplets was induced by UV light at 365 nm and was affected significantly by the presence of 2,2-diethoxyacetophenone (DEAP) and sorbitan monooleate (Span 80). When the droplets were subjected to UV irradiation for more than 2 min, the phase-separated copolymer was transferred completely from the aqueous droplet to the continuous phase of hexadecane. The phase separation arises from the photoisomerization shifting the spiro to the merocyanine form of the SPO pendant group in the copolymer, which in turn reduces the hydrophilicity of the copolymer via attractive hydrogen-bonding interactions between the merocyanine group and hydrophobic additives, i.e., Span 80, DEAP, and some stable fragments derived from the photocleavage of DEAP under UV irradiation. These interactions cause the copolymer to associate with the additives and then accelerate the phase separation of the copolymer and subsequent phase transfer of copolymer aggregates. The separate effects of DEAP and Span 80 were also investigated by UV spectrophotometric analysis of the rate coefficient of the reverse transformation (merocyanine to spiro) of the photochromic monomer. We propose a mechanism of phase separation of the copolymer in the W/O droplet based on the NMR and GC-MASS analyses of DEAP.