Performance of ionic liquid as catalyst in the copolymerization of phenyl glycidyl ether with carbon dioxide

Summary Selective ammoxidation of ethylene over Co-ZSM-5 prepared by aqueous and solid-state ion exchange has been studied. The catalyst prepared using solid-state exchange showed higher activity and selectivity to acetonitrile. Catalysts tested in the ammoxidation of ethylene were previously characterized by chemical analysis, XRD, N₂-BET measurements and FTIR. TPD of ammonia and FTIR of pyridine used as probe molecule showed that solid-state ion exchange of H-ZSM-5 with cobalt generates new Lewis acid sites which seem to play a role in the ammoxidation reaction.     

Dispersion of functional tetraphenylporphyrin-ligated metal into ultra-thin flexible acrylate films. 2. Oxygen-uptake properties

Cobalt(II) meso-tetraphenylporphyrin (CoTPP)/acrylate hybrid thin films were prepared by CoTPP sublimation and reactive monomer evaporation onto the glass substrate in vacuum conditions. Deposited CoTPP/acrylate thin films were in situ photopolymerized. The oxygen-uptake behaviors of CoTPP/acrylate films were investigated by means of sorption measurements, monitored by gravimetric means, and analyzed using dual mode sorption model. The loading percent of CoTPP in the film was adjusted up to 60% by controlling the CoTPP sublimation rate. The thickness of the CoTPP/acrylate hybrid film was about 200 nm and oxygen-uptake data obtained from the sorption measurements indicated that CoTPP molecules in the CoTPP/acrylate hybrid films were able to bind oxygen molecules reversibly.     

A transonic quasi-3D analysis for gas turbine engines including split-flow capability for turbofans

A numerical approximation is taken to the solution of the complex flows existing in gas turbine engines with transonic blading. The quasi-3D approach decouples the problem into through-flow and blade-to-blade solutions. An industrially practical finite element through-flow solution is developed and for blade-to-blade solutions a transonic finite areas method is utilized. The finite element code developed is capable of operating in an analysis or a design mode. In both modes a dynamic relaxation factor is employed and considerable reduction in solution time can be achieved. Comparisons to streamline curvature methods are carried out for simple analytical and complex industrial problems.     

A catalytic approach of blending CO2-activating MOF struts for cycloaddition reaction in a helically interlaced Cu(II) amino acid imidazolate framework: DFT-corroborated investigation

In CO₂ transformation catalysis, the synthesis of cyclic carbonates using two classes of MOF catalysts viz., zeolitic imidazolate frameworks (ZIF) and MOFs with carboxylate-capped SBUs have gained large attention. Herein we propose the strategy of employing a unified multifunctional framework formed in the metal-centered assembly of imidazole and amino-carboxylates for CO₂ transformation, such as propylene carbonate (PC) by the cycloaddition of CO₂ with propylene oxide. The framework {[Cu(L-asp)(1,4-bix)_0.5]·3H₂O}_n (CuAspBix) comprises of the amino acid building units, L-aspartic acid (L-Asp) and the flexible ligand, 1,4-bis(imidazole-1-yl methyl)benzene [1,4-Bix]. The 1,4-Bix ligand with imidazole terminals renders elongated M-M distances and flexibility in comparison with pristine ZIF materials. The cumbersome synthesis procedure poor phase purity of the bulk catalyst in solvothermal conditions were improved by a microwave-assisted synthesis, preserving the structural and physicochemical properties. Minimal energy input or room temperatures for the catalysis occurred via the synergistic participation of CuAspBix and quaternary ammonium bromide salt, demonstrated by density-functional theory computational studies to propose mechanistic pathway of the reaction. Reaction conditions were optimized by altering the parameters. The heterogeneous catalyst was reused four times without a significant change in activity.

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Scalable ambient synthesis of water‐soluble poly(β‐hydroxythio‐ether)s

Proton transfer polymerization through thiol‐epoxy “click” reaction between commercially available and hydrophilic di‐thiol and di‐epoxide monomers is carried out under ambient conditions to furnish water‐soluble polymers. The hydrophilicity of monomers permitted use of aqueous tetrahydrofuran as the reaction medium. A high polarity of this solvent system in turn allowed for using a mild catalyst such as triethylamine for a successful polymerization process. The overall simplicity of the system translated into a simple mixing of monomers and isolation of the reactive polymers in an effortless manner and on any scale required. The structure of the resulting polymers and the extent of di‐sulfide defects are studied with the help of 13C‐ and ¹H‐NMR spectroscopy. Finally, reactivity of the synthesized polymers is examined through post‐polymerization modification reaction at the backbone sulfur atoms through oxidation reaction. The practicality, modularity, further functionalizability, and water solubility aspects of the described family of new poly(β‐hydroxythio‐ether)s is anticipated to accelerate investigations into their potential utility in bio‐relevant applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3381–3386     

Improving Efficiency of Organic Photovoltaic Cells Using PEDOT:PSS and MWCNT Nanocomposites as a Hole Conducting Layer

In this study, polymeric nanocomposites of poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) and functionalized multi-walled carbon nanotubes (MWCNTs) were spin coated on a pre-patterned ITO glass and used as a hole conducting layer in organic photovoltaic cells. The multi-layered ITO/MWCNT-PEDOT:PSS/CuPc/C60/Al devices were fabricated to investigate the current density-voltage characteristics and power conversion efficiency. The power conversion efficiency obtained from the device with a concentration of 1.0 wt% MWCNT in the PEDOT:PSS layer was increased twice as those adopted from device without MWCNT doping in the PEDOT:PSS layer and current density-voltage characteristics was also improved well with incorporation of MWCNTs.     

Influence of residual impurities on ring‐opening metathesis polymerization after copper(I)‐catalyzed alkyne‐azide cycloaddition click reaction

Bottlebrush polymers (BBPs) are three‐dimensional polymers with great academic and industrial potential owing to their highly tunable and intricate architecture. The most popular method to synthesize BBPs is ring‐opening metathesis polymerization (ROMP) with Grubbs' catalyst, allowing living grafting‐through polymerization of macromonomers of up to ultrahigh molecular weights with narrow molecular weight distribution. In this case, it has been well recognized that the purity of macromonomers (MMs) is critical for a successful ROMP reaction. For MMs synthesized from reversible‐deactivation radical polymerization, Grubbs and Xia demonstrated that the better control of ROMP reaction can be achieved when they are prepared via “growth‐then‐coupling” method that is coupling a norbornenyl group to end‐functionalized prepolymers. However, these MMs can also contain various residual impurities from previous synthetic steps, which can potentially poison the catalyst and hamper the ROMP reaction. Herein, we intentionally doped possible impurities into purified MMs to identify the most poisoning species. As a result, it was found that alkyne‐functionalized norbornene most significantly retarded the ROMP reaction due to a formation of Ru‐vinyl‐carbene intermediates having low catalytic reactivity, whereas the other reagents such as solvent, Cu‐catalyst, ligands, and azido‐terminated prepolymers were relatively inert. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 726–737     

Dispersion of functional tetraphenylporphyrin-ligated metal into ultra-thin flexible acrylate films. 1. Preparation of thin films

As functional metal complexes, copper phthalocyanine (CuPc) and Cobalt (II) meso-tetraphenylporphyrin (CoTPP) were chosen to prepare metal complex/polymer hybrid thin films which were prepared by metal complex sublimation and reactive monomer evaporation onto the glass substrate in the bell jar reactor in vacuum conditions. The polarized transmission micrograph images show that the film deposited at 80 °C contains uniformly dispersed tiny grains and the film deposited at 30 °C is amorphous and homogeneous. As the deposition rate increases, the crystalline clusters were found and were dispersed uniformly. Those crystalline clusters are not to be developed by recrystallization process. Deposited metal complex/acrylate hybrid thin films were in situ photopolymerized. The kinetics of photopolymerization was investigated by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). The thickness of the films was about 200 nm. The reactive monomer acts as a solvent to avoid the recrystallization of metal complexes and to have two-compositional continuous phase. The percent of metal complex can be adjusted up to 60% by controlling the metal complex sublimation rate. A good achievement in the uniformity and continuity of the film matrix has been made and the recrystallization of metal complex in the hybrid films has not been observed.     

Reactive Core-Shell Bottlebrush Copolymer as Highly Effective Additive for Epoxy Toughening

Herein,we designed a core-shell structured bottlebrush copolymer (BBP),which is composed of rubbery poly(butyl acrylate) (PBA)core and an epoxy miscible/reactive poly(glycidyl methacrylate) (PGMA) shell,as an epoxy toughening agent.The PGMA shell allows BBP to be uniformly dispersed within the epoxy matrix and to react with the epoxy groups,while the rubbery PBA block simultaneously induced nanocavitation effect,leading to improvement of mechanical properties of the epoxy resin.The mechanical properties were measured by the adhesion performance test,and the tensile and fracture test using universal testing machine.When BBP additives were added to the epoxy resin,a significant improvement in the adhesion strength (2-fold increase) and fracture toughness (2-fold increase in Klc and 5-fold increase in Glc)compared to the neat epoxy was observed.In contrast,linear additives exhibited a decrease in adhesion strength and no improvement of fracture toughness over the neat epoxy.Such a difference in mechanical performance was investigated by comparing the morphologies and fracture surfaces of the epoxy resins containing linear and BBP additives,confirming that the nanocavitation effect and void formation play a key role in strengthening the BBP-modified epoxy resins.