RESUMO
The introduction of ceramic fillers into a polymer matrix is an effective way to obtain dielectric nanocomposites with high energy storage density. However, the inorganic fillers are difficult to disperse evenly into the polymer matrix because of the poor compatibility, which stems from the large surface energy difference and the mismatch in dielectric constant between the fillers and polymer matrix. Polymer nanocomposites with high dielectric constant while maintaining high breakdown strength have great potential to achieve high energy storage density. In this work, poly(dodecafluoroheptyl methacrylate) terminated with a thiol end group (PDFMA-SH) was synthesized via a two-step process including Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization and subsequent aminolysis reaction. The polymer was then grafted into the surface of BaTiO3 (BT) nanoparticles by a "thiol-ene" click reaction to reduce the surface energy of BT nanoparticles. A novel nanocomposite consisted of the core-shell structured PDFMA@BT hybrid nanoparticles and poly(vinylidene fluoride-chlorotrifluoroethylene) (P(VDF-CTFE)) matrix was prepared. The influence of the fluoropolymer shell on the dispersion of fillers, the compatibility between the fillers and polymer matrix, dielectric properties and breakdown strength were investigated systematically. The results indicate that the strong interfacial adhesion between the hybrid nanoparticles and P(VDF-CTFE) matrix makes the fillers uniformly dispersed in the polymer matrix. Meanwhile, the excellent compatibility between the two components is favorable for enhancing the breakdown strength and suppressing dielectric loss, providing a condition to prepare dielectric materials with high energy storage density.
RESUMO
Preparation of stable water-in-oil (W/O) high internal phase emulsion (HIPE) containing methyl methacrylate (MMA) monomer as oil phase is a difficult task due to the significant solubility of MMA in water. Here, for the first time a fluorinated di-block copolymer (FDBC) poly (2-dimethylamino)ethylmethacrylate-b-poly (trifluoroethyl methacrylate) (PDMAEMA-b-PTFEMA) is proposed to stabilize HIPEs of MMA without the use of any co-stabilizer or thickening agent. Fluorinated segments in FDBC anchored well at oil/water interface of HIPE, offering high hydrophobicity to the partially hydrophilic MMA monomer and in turn stabilization to MMA-HIPE. By using fluorinated di-block copolymer as stabilizer, highly stable HIPEs can be obtained. In addition, highly interconnected porous monoliths were obtained after free radical polymerization, which are highly desirable materials in various practical applications including tissue engineering scaffolds, separation science, bio-engineering and so on. The as-prepared MMA-HIPEs possess high thermal stability without phase separation. The textural characteristics of as-prepared composites, such as pore size and distribution, can be easily controlled by simply varying the amount of FDBC and/or dispersed phase fraction. Moreover, the influence of di-block concentration on water uptake (WU) capability of the prepared porous monoliths is explored.
RESUMO
A facile preparation for a series of porous poly(2,2,2-trifluoroethylmethacrylate-divinylbenzene) P(TFEMA-DVB) foams is discussed in this paper. The foams have adjustable morphology utilizing a suitable commercial surfactant, Hypermer B246, as stabilizer, and were compared with traditional organic surfactants or macromolecular block-polymers. Combining the porous properties and advantages of fluorine atoms, this type of fluoropolymer exhibited superb chemical stability and hydrophobicity performances with high porosity. These porous fluoro-monoliths preserved their regular porous structure without any degradation after immersion into strong acidic or basic solution for three days, hence demonstrating an excellent potential to deal with environmental pollution caused by oil spillages in severe environments. The tunable morphology (open and closed pores) and pore sizes were achieved by investigating various parameters like surfactant concentration, amount of external crosslinker, and aqueous phase volume. Droplet sizes of HIPEs were characterized using an optical microscope under different experimental conditions. The influence of pore structure and surface properties of polyHIPE on water contact angle and oil adsorption capacity was also explored. The results indicated that the porous material has an excellent oleophilicity and hydrophobicity, with water contact angles (WCA) up to 146.4°. Additionally, the results presented a noticeable adsorption with a very fast rate towards organic oils from either a water surface or bottom with adsorption saturation achieved in about 120 s. The prepared polyHIPEs showed a good recycling ability; even after 10 adsorption-centrifugation experiments, the adsorption capacity was still more than 85%.
RESUMO
In this work, a thermo-responsive and cross-linked fluoropolymer poly(2,2,2-Trifluoroethyl) methacrylate (PTFEMA) was successfully prepared by reversible addition-fragmentation chain transfer (RAFT) mediated aqueous polymerization with a thermo-responsive diblock poly(dimethylacrylamide-b-N-isopropylacrylamide) (PDMA-b-PNIPAM) that performed a dual function as both a nanoreactor and macro-RAFT agent. The cross-linked polymer particles proved to be in a spherical-like structure of about 50 nm in diameter and with a relatively narrow particle size distribution. ¹H-NMR and 19F-NMR spectra showed that thermo-responsive diblock P(DMA-b-NIPAM) and cross-linked PTFEMA particles were successfully synthesized. Influence of the amount of ammonium persulfate (APS), the molar ratio of monomers to RAFT agent, influence of the amount of cross-linker on aqueous polymerization and thermo-responsive characterization of the particles are investigated. Monomer conversion increased from 44% to 94% with increasing the molar ratio of APS and P(DMA-b-NIPAM) from 1:9 to1:3. As the reaction proceeded, the particle size increased from 29 to 49 nm due to the consumption of TFEMA monomer. The size of cross-linked nanoparticles sharply decreased from 50.3 to 40.5 nm over the temperature range 14-44 °C, suggesting good temperature sensitivity for these nanoparticles.
