Effect of multi-ethers and conventional alkoxysilanes as external donors on the 4th generation Ziegler-Natta catalysts for propylene polymerization

The multi-ether compounds with different numbers of methoxy groups containing 1,3-dimethoxy-2,2-bis(methoxymethyl)propane and 1-methoxy-2,2-bis(methoxymethyl)butane were synthesized using the Williamson reaction from pentaerythritol and 1,1,1-tris(hydroxymethyl)propane, respectively, in the presence of sodium hydride and methyl iodide in tetrahydrofuran and they were characterized by ¹H NMR, ¹³C NMR, and FTIR spectroscopy. These compounds were employed as external donors in the polymerization of propylene using the industrial Ziegler-Natta catalyst. A commercial spherical MgCl₂-supported Ziegler-Natta catalyst containing diisobutyl phthalate as the internal donor was used for the polymerization of propylene. The role of ether compounds and industrial alkoxysilanes on the properties of polypropylene were studied using the xylene solubility method, melt flow index, gel permeation chromatography, scanning electron microscopy, and differential scanning calorimetry. The addition of the electron donors has led to improvements in the activity and selectivity of the Ziegler-Natta catalyst system.     

Effect of fiber geometry on macroscale friction of ordered low-density polyethylene nanofiber arrays

Ordered low-density polyethylene (LDPE) nanofiber arrays are fabricated from silicon nanowire (SiNW) templates synthesized by a simple wet-chemical process based on metal-assisted electroless etching combined with colloidal lithography. The geometrical effect of nanofibrillar structures on their macroscale friction is investigated over a wide range of diameters and lengths under the same fiber density. The optimum geometry for contacting a smooth glass surface is presented with discussions on the compromise between fiber tip-contact area and fiber compliance. A friction design map is developed, which shows that the theoretical optimum design condition agrees well with the LDPE nanofiber geometries exhibiting high measured friction.     

Selective and Sensitive Fluorometric Determination of Piroxicam Based on Nitrogen-doped Graphene Quantum Dots and Gold Nanoparticles Coated with Phenylalanine

Journal of Fluorescence - In this study, a sensitive fluorimetric method is proposed for the determination of piroxicam using nitrogen graphene quantum dots (N-GQDs) and gold nanoparticles coated...     

Conductometric study of complexation reaction between 15-crown-5 and Cr3+, Mn2+ and Zn2+ metal cations in pure and binary mixed organic solvents

The stability constants (K_f) for the complexation reactions of Cr³⁺, Mn²⁺ and Zn²⁺ metal cations with macrocyclic ligand, 15-crown-5 (15C5), in acetonitrile (AN), ethanol (EtOH) and also in their binary solutions (AN–EtOH) were determined at different temperatures, using conductometric method. 15C5 forms 1:1 complexes with Cr³⁺, Mn²⁺ and Zn²⁺ cations in solutions. A non-linear behaviour was observed for changes of logK_f of the metal ion complexes versus the composition of the mixed solvent. The order of stability of the metal–ion complexes in pure AN and in a binary solution of AN–EtOH (mol% AN?=?52) at 25?°C was found to be: (15C5Zn)²⁺?>?(15C5·Mn)²⁺?>?(15C5·Cr)³⁺, but in the case of pure EtOH at the same temperature, it changes to: (15C5·Zn)²⁺?>?(15C5·Cr)³⁺?>?(15C5·Mn)²⁺. The results also show that the stability sequence of the complexes in the other binary solutions of AN–EtOH (mol% AN?=?26 and mol% AN?=?76) varies in order: (15C5·Cr)³⁺?~?(15C5·Zn)²⁺?>?(15C5·Mn)²⁺. The values of the standard thermodynamic quantities (ΔH_C°, ΔS_C°) for formation of (15C15-Cr³⁺), (15C5-Mn²⁺) and (15C5-Zn²⁺) complexes were obtained from the temperature dependence of the stability constants and the results show that the thermodynamics of complexation reactions is affected by nature and composition of the solvent systems and in most solution systems, the complexes are enthalpy stabilized but entropy destabilized.     

2-Chloro-1-methylpyridinium iodide,an efficient reagent for the conversion of alcohols into alkyl thiocyanates both under solvent and solvent-free conditions

A new application of the Mukaiyama reagent for the simple phosphine-free conversion of alcohols into the corresponding alkyl thiocyanates is described. This transformation can be achieved either in acetonitrile or under solvent-free conditions and the products obtained in good to excellent yields. The solvent-free procedure described here is the first report on the solvent-free thiocyanation of alcohols.     

Isocyanide-based four-component synthesis of 1,3-indandionylamidinium betaines

An efficient approach for the synthesis of novel 1,3-indandionylamidinium betaines via four-component reaction of 1,3-indandione, aldehydes, amines, and isocyanides, without assistance of any catalyst and under mild reaction conditions has been reported. The structures of these compounds were confirmed by IR, mass spectroscopic, ¹H NMR, ¹³C NMR, and single-crystal X-ray diffraction studies.     

A catalytic asymmetric approach to C1-chiral 3-methylene-indan-1-ols

A sequential (R)-BINAP·Ag^IF (2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) (6–10 mol %), and (Ph₃P)₂Pd^IICl₂ (bis(triphenylphosphine)palladium(II) dichloride) (2 mol %) catalyzed asymmetric Sakurai–Hosomi–Yamamoto allylation/Mizoroki–Heck reaction that affords C₁-chiral 3-methylene-indan-1-ols with enantiomeric excess (ee) up to 80% is reported. Notably, this protocol allows for the use of various o-substituted benzaldehydes and allyltrimethoxysilane. It was also discovered that the presence of electron-rich groups had no effect on the enantioselectivity of the reaction, whereas electron-withdrawing groups lead to erosion in product ee.     

Green Regioselective Azidolysis of Epoxides Catalyzed by Multi‐Site Phase‐Transfer Catalyst

A facile synthesis of 1,2‐azidoalcohols from their epoxides using α,α',α”‐N‐hexakis(triethylammoniummethylene chloride)‐melamine as a multi‐site phase‐transfer catalyst in water was developed. By this eco‐friendly and highly atom‐economic method, a variety of 1,2‐azidoalcohols was obtained in high yields with excellent regioselectivity and in short reaction times. Application of this six‐site PTC in the ring opening of epoxides by cyanide, acetate and chloride anions was also studied. The catalyst can be recovered after completion of the reaction and can be recycled without affecting the catalytic property.     

Synthesis of palladium nanoshell using a layer-by-layer technique

Complete palladium nanoshells were prepared by reducing palladium ions in a one-step reaction onto preformed silica cores of ca. 90 nm, which had been coated with successive layers of poly(diallyldimethyl ammonium chloride), poly(sodium styrenesulfonate) and finally poly(diallyldimethyl ammonium chloride) to reverse the zeta potential of the silica cores. This constitutes the first reported method for complete palladium nanoshell formation without the use of other metals as nucleation sites. The morphology of the nanoshell is of the rough discrete particle type rather than the smooth continuous type.     

A 3-D bonding perspective of the factors influencing the relative stability of the S1/S0 conical intersections of the penta-2,4-dieniminium cation (PSB3)

A balanced treatment of the covalent and ionic contributions to the ground and excited states originating from torsion about double bonds is known to be strongly dependent on the presence of dynamic electron correlation. We undertake an analysis of the minimum energy pathways corresponding to deactivation of the first excited singlet state of PSB3. In doing so we consider torsion about the three double bonds including other intramolecular degrees of freedom, such as the bond length alternation. The 3-D bond-path analysis provides a new ‘bond-localized orbital-like’ directional interpretation of bonding. Therefore, we present a more sophisticated method of determination of the degree of covalent and ionic contributions known to be responsible for altering the relative stability of the S₁/S₀ conical intersections. The results presented suggest that the commonly used simplified multi-reference methodologies that often result in incorrect predictions for the excited state deactivation reaction mechanism.