Grafting of Maleic Anhydride onto Poly(vinylidene fluoride) Using Reactive Extrusion.

Poly(vinylidene fluoride) was grafted with maleic anhydride through reactive extrusion by using diisopropyl benzene peroxide as an initiator and 9-vinyl anthracene as a stabilizer. Effects of various parameters on grafting degree were investigated including the amounts of monomer, initiator and stabilizer. The maximum extent of grafting achieved was 0.74%. The graft polymers were characterized using FTIR, water contact angle, thermal, mechanical and XRD studies. Improved hydrophilic and mechanical properties were observed for graft polymers.

A solution-processable and ultra-permeable conjugated microporous thermoset for selective hydrogen separation.

The synthesis of a polymer that combines the processability of plastics with the extreme rigidity of cross-linked organic networks is highly attractive for molecular sieving applications. However, cross-linked networks are typically insoluble or infusible, preventing them from being processed as plastics. Here, we report a solution-processable conjugated microporous thermoset with permanent pores of ~0.4 nm, prepared by a simple heating process. When employed as a two-dimensional molecular sieving membrane for hydrogen separation, the membrane exhibits ultrahigh permeability with good selectivity for H2 over CO2, O2, N2, CH4, C3H6 and C3H8. The combined processability, structural rigidity and easy feasibility make this polymeric membrane promising for large-scale hydrogen separations of commercial and environmental relevance.

MoS2 Membranes for Organic Solvent Nanofiltration: Stability and Structural Control.

This paper reveals the chemical, structural, and separation stability of stacked molybdenum disulfide (MoS2) membranes and establishes a low-cost and facile approach to developing stable, selective membranes for efficient molecular separation in an organic solvent. MoS2 nanoflakes that were dominant  by monolayer MoS2 sheets as prepared via direct chemical exfoliation (chem-MoS2) were found to be chemically and structurally instable, with a sharp decrease in the level of solute rejection within a few days. Few-layer MoS2 nanoflakes were then fabricated using a hydrothermal method (hydro-MoS2). A "supportive" drying process involving glycerol pretreatment and drying in an oven was established to allow realignment of nanoflakes and adjustment of interflake spacing. We have shown that the hydro-MoS2 membranes provide a mean interflake free spacing of ∼1 nm, which is ideal for the separation of a model solute (Rose Bengal, size of ∼1.45 nm) from the solvent isopropanol (size of 0.58 nm) with good long-term stability over a 7 day test.

Advanced Porous Materials in Mixed Matrix Membranes.

Membrane technology has gained great interest in industrial separation processing over the past few decades owing to its high energy efficiency, small capital investment, environmentally benign characteristics, and the continuous operation process. Among various types of membranes, mixed matrix membranes (MMMs) combining the merits of the polymer matrix and inorganic/organic fillers have been extensively investigated. With the rapid development of chemistry and materials science, recent studies have shifted toward the design and application of advanced porous materials as promising fillers to boost the separation performance of MMMs. Here, first a comprehensive overview is provided on the choices of advanced porous materials recently adopted in MMMs, including metal-organic frameworks, porous organic frameworks, and porous molecular compounds. Novel trends in MMMs induced by these advanced porous fillers are discussed in detail, followed by a summary of applying these MMMs for gas and liquid separations. Finally, a concise conclusion and current challenges toward the industrial implementation of MMMs are outlined, hoping to provide guidance for the design of high-performance membranes to meet the urgent needs of clean energy and environmental sustainability.

Biobased polyelectrolyte multilayer-coated hollow mesoporous silica as a green flame retardant for epoxy resin.

Here, we describe a multifunctional biobased polyelectrolyte multilayer-coated hollow mesoporous silica (HM-SiO2@CS@PCL) as a green flame retardant through layer-by-layer assembly using hollow mesoporous silica (HM-SiO2), chitosan (CS) and phosphorylated cellulose (PCL). The electrostatic interactions deposited the CS/PCL coating on the surface of HM-SiO2. Subsequently, this multifunctional flame retardant was used to enhance thermal properties and flame retardancy of epoxy resin. The addition of HM-SiO2@CS@PCL to the epoxy resin thermally destabilized the epoxy resin composite, but generated a higher char yield. Furthermore, HM-SiO2 played a critical role and generated synergies with CS and PCL to improve fire safety of the epoxy resin due to the multiple flame retardancy elements (P, N and Si). This multi-element, synergistic, flame-retardant system resulted in a remarkable reduction (51%) of peak heat release rate and a considerable removal of flammable decomposed products. Additionally, the incorporation of HM-SiO2@CS@PCL can sustainably recycle the epoxy resin into high value-added hollow carbon spheres during combustion. Therefore, the HM-SiO2@CS@PCL system provides a practical possibility for preparing recyclable polymer materials with multi-functions and high performances.

Hyper-branched polymer grafting graphene oxide as an effective flame retardant and smoke suppressant for polystyrene.

A well-defined functionalized graphene oxide (FGO) grafted by hyper-branched flame retardant based on N-aminoethyl piperazine and phosphonate derivative was synthesized to reduce flammability and toxicity of polystyrene (PS). The chemical structure, morphological and thermal properties were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and thermogravimetric analysis, respectively. Micro combustion calorimeter and steady state tube furnace were employed to evaluate the heat and non-heat fire hazards of PS nanocomposites. The incorporation of FGO into PS matrix effectively improved the flame retardancy and restrained the toxicity of the volatiles escaped, which is attributed to that the homogeneous dispersion of FGO in the PS matrix enhanced barrier effect that reduced peak heat release rate, total heat release and toxic gas release during combustion. Furthermore, PS-FGO nanocompsites obviously decreased the amount of flammable and toxic volatiles evolved, such as the aromatic compounds, carbonyl compounds, carbon monoxide, indicating suppressed fire hazards of the PS composites.

Self-assembly fabrication of hollow mesoporous silica@Co-Al layered double hydroxide@graphene and application in toxic effluents elimination.

Here, we propose a self-assembly process to prepare hierarchical HM-SiO2@Co-Al LDH@graphene, with the purpose of combining their outstanding performance. Hollow mesoporous silica was first synthesized as the core, using a novel sonochemical method, followed by a controlled shell coating process and chemical reduction. As a result of the electrostatic potential difference among HM-SiO2, Co-Al LDH, and graphene oxide, the HM-SiO2 spheres were coated by Co-Al LDH and graphene. Subsequently, the HM-SiO2@Co-Al LDH@graphene spheres were introduced into an epoxy resin (EP) matrix for investigation of their toxic effluents capture and elimination effectiveness during combustion. The amount of toxic CO and volatile organic compounds from the epoxy resin decomposition significantly suppressed after incorporating the HM-SiO2@Co-Al LDH@graphene hybrids, implying a reduced toxicity.

Synthesis of mesoporous silica@Co-Al layered double hydroxide spheres: layer-by-layer method and their effects on the flame retardancy of epoxy resins.

Hierarchical mesoporous silica@Co-Al layered double hydroxide (m-SiO2@Co-Al LDH) spheres were prepared through a layer-by-layer assembly process, in order to integrate their excellent physical and chemical functionalities. TEM results depicted that, due to the electrostatic potential difference between m-SiO2 and Co-Al LDH, the synthetic m-SiO2@Co-Al LDH hybrids exhibited that m-SiO2 spheres were packaged by the Co-Al LDH nanosheets. Subsequently, the m-SiO2@Co-Al LDH spheres were incorporated into epoxy resin (EP) to prepare specimens for investigation of their flame-retardant performance. Cone results indicated that m-SiO2@Co-Al LDH incorporated obviously improved fire retardant of EP. A plausible mechanism of fire retardant was hypothesized based on the analyses of thermal conductivity, char residues, and pyrolysis fragments. Labyrinth effect of m-SiO2 and formation of graphitized carbon char catalyzed by Co-Al LDH play pivotal roles in the flame retardance enhancement.