Synthesis of Polypropylene in the Liquid Monomer in the Presence of a Titanium—Magnesium Catalyst: Effect of Various Internal Donors

Russian Journal of Applied Chemistry - The influence of supported titanium-magnesium catalysts with various internal and external donors on the propylene polymerization in the liquid monomer medium...     

RAFT Polymerization of Styrene in the Presence of 2‐Nonyl‐benzoimidazole‐1‐carbodithioic Acid Benzyl Ester

A novel dithiocarbamate, 2‐nonyl‐benzoimidazole‐1‐carbodithioic acid benzyl ester ( 1a ), was synthesized and successfully used in RAFT polymerization of styrene in bulk with thermal initiation. The effect of molar ratio of styrene to RAFT agent on the polymerization was investigated. The linear relationship between ln([M]₀/[M]) and polymerization time indicated that the polymerization was first‐order with respect to monomer concentration. The molecular weights increased linearly with monomer conversion and were close to corresponding theoretical values. The molecular weight distributions (M _w /M _n ) kept very narrow (M _w /M _n <1.1) at a wide range of conversions of 14.2% to 73.3%. The obtained polymer had a strong ultraviolet absorption at 329 nm, which indicated that the 1a moiety remained at the end of polymer chain.     

Cationic Polymerization in the Presence of π-Electron Acceptors

The cationic polymerization of various vinyl and cyclic monomers was studied in the presence of strong electron acceptors (EA) such as tetracyanoethylene, chloranil, and syn-trinitrobenzene, added in quantities commensurate with the initiator concentrations. In all cases studied, the presence of EA brings about an increase both in the overall polymerization rate and in the molecular weights of the polymers obtained without changing the kinetic scheme of the reaction. The EA added also affects the monomer reactivities in the copolymerization reaction, the insertion of less reactive monomer being favored. The effect of EA was explained in terms of complexation with the counter-ion which causes a shift of the ionic equilibrium in the system.     

Synthesis of Polyvinylacetate‐Sodium Montmorillonite Hybrids by Emulsion Polymerization in the Presence of Anionic Surfactants

The emulsion polymerisation of vinyl acetate (VAc) in presence of sodium dodecylsulphate (SDS) and sodium montmorillonite (NaMMT) is used in order to achieve polymer‐clay hybrids. The influence of the polyvinylacetate (PVAc), SDS, and PVAc‐SDS complex on the NaMMT structure also was investigated. The VAc emulsion polymerization rate exhibits a maximum as the NaMMT concentration increases. The XRD patterns correspond to hybrids with intercalated structure. If a water soluble comonomer, ammonium sulphato ethylmethacrylate (ASEMA) is used for copolymerization with VAc, a exfoliated hybrid structure (from XRD spectra) is obtained. The solid materials were analysed by TGA, FTIR, XRD, SEM, and TEM.     

Preparation and Characterization of trans‐1,4‐Polybutadiene Nanocomposites Containing in situ Generated Silica

Abstract

trans‐1,4‐Polybutadiene (tPBD) networks crosslinked free radically with dicumyl peroxide (DCP) were reinforced by in situ silica formed in a two‐step sol–gel technique. Changing the degree of crosslinking by changing the amount of DCP, or changing the amounts of the sol–gel components [tetraethoxysilane (TEOS) and dibutyltin diacetate (DBTDA)], changed the silica generated with regard to the amount precipitated, particle size, and degree of dispersion. Stress–strain measurements in continuous extension indicated good reinforcement, even at relatively low amounts of silica. Differential scanning calorimetry (DSC) indicated decreases in heat of crystallization with increases in the amounts of silica, but thermogravimetric analysis showed initial decomposition temperatures (IDT) remained relatively constant. Suggestions are made regarding interpretation of these properties in terms of the composite morphologies.     

Mild Oxidation of Alcohols with o‐Iodoxybenzoic Acid (IBX) in a Water/CH2Cl2 Mixture in the Presence of Phase‐Transfer Catalyst

A mild oxidation of alcohols to the respective carbonyl compounds with o‐iodoxybenzoic acid (IBX) catalyzed by n‐Bu₄NBr in a water/dichloromethane (1:1) mixture is described. The method offers the advantage of a simple, inexpensive catalyst and the diminution of organic solvent employed in the reaction.     

Facile One‐Step Conversion of Ketones into α‐Azidoketones using [Hydroxy(tosyloxy)iodo]benzene and Sodium Azide in the Presence of a Phase‐Transfer Catalyst under Solvent‐Free Conditions

We have described a one‐step, solvent‐free synthesis of α‐azidoketones from the corresponding ketones that requires relatively benign [hydroxy(tosyloxy) iodo]‐benzene reagent, sodium azide, and phase‐transfer catalyst at room temperature. Generality of the protocol has been demonstrated by synthesizing various α‐azidoketones high in yield and purity within a short time.     

Polymerization of Methyl Methacrylate in the Presence of N-Acetyl-ε-aminocaproic Acid Acetylamide

The effect of N-acetyl--aminocaproic acid acetylamide on radical polymerization of methyl methacrylate initiated with lauroyl peroxide was studied.     

Expedient Method for Oxidation of Alcohol by Hydrogen Peroxide in the Presence of Amberlite IRA 400 Resin (Basic) as Phase‐Transfer Catalyst

Amberlite IRA 400 (strongly basic), a classical polymer imparts phase‐transfer catalysis in the oxidation of primary and secondary alcohols by hydrogen peroxide to give excellent yields of the corresponding carbonyl compounds or carboxylic acids in acetonitrile solvent at reflux temperature in 4–6 h. The catalytic system is inert to other susceptible oxidation sites such as carbon–carbon double bonds     

Study on Chemisorption, Catalytic Behavior, and Stability of Supported Au Catalyst for the Propylene Epoxidation Reaction

The supported Au/TiO2 and Au/TiO2-SiO2 catalysts were prepared by deposition precipitation method. The TPD study reveals that propylene oxide competes with propylene to be adsorbed on the same adsorptive center-Tin site on the surface of the catalyst and that the adsorbing capacity of the catalyst for propylene oxide is larger than that for propylene. Catalytic behavior for propylene epoxidation with H2 and O2 was tested in a micro-reactor. Under typical conditions, the selectivity for propylene oxide is over 87%. The TG curves show that PO successive oxidation cause carbon deposition on the active center and deactivation of the Au catalysts. Because the amounts of Tin site decrease significantly, and consequently the separation between Tin sites increases, the Au/TiO2-SiO2 catalyst is more stable than Au/TiO2.     

De‐agglomeration of Silica Nanoparticles in the Presence of Surfactants

The effect of the type of surfactant and pH on de‐agglomeration of a hydrophilic silica nano‐powder in a high shear mixer was investigated. It has been found that the presence of surfactant does not affect the general pattern of de‐agglomeration characterized by the transition of a single modal aggregates size distribution with the median of 10 µm, through a bi‐modal distributions with the second median of the order of 100 nm to a single modal distribution with the median of the order of 100 nm. None of the investigated surfactants enabled de‐agglomeration of the nano‐powder into a primary nanoparticle.

At pH=4, breakage of large secondary aggregates was enhanced by the addition of PEG and PVP, whereas the addition of SDS slowed down de‐agglomeration. The final aggregates were larger in all suspensions containing surfactant than in surfactant free suspensions. At pH=9 all surfactants drastically reduced de‐agglomeration rate without affecting the size of the primary aggregates. PEG induced bridge flocculation of the primary aggregates leading to a drastic change of the rheology of suspension.     

Solvent‐Free Synthesis of Benzothiazolines in the Presence of Alumina

o‐Aminothiophenol reacted with ketones and β‐keto esters in the presence of alumina under mild and solvent‐free conditions to afford the corresponding benzothiazolines in high yields. Alumina can be reused for subsequent reactions without any loss of the activity.     

Lipase Catalyzed Chemoselective Ring‐Opening Polymerization of ϵ‐Caprolactone in Presence of γ‐Hydroxy‐α‐methylenebutyric Acid

The ring‐opening polymerization (ROP) of ?‐caprolactone (CL) using γ‐hydroxy‐α‐methylenebutyric acid (HMBA) as the initiator was studied. The use of stannous octoate (Sn(Oct)₂) and Novozym 435 (Lipase B from Candida Antarctica) as catalysts was compared. Under enzymatic conditions, poly(?‐caprolactone) (PCL) with well‐defined end group functionalization was obtained. In contrast, under Sn(Oct)₂ catalysis, the lactonization of HMBA was observed as a side reaction which lead to an insufficient end group functionalization of the prepared polyesters.     

Studies on Acrylic Emulsion Polymerization Containing Hydrophilic Hydroxyl Monomer in the Presence of Nano‐SiO2 Particles

Emulsion polymerization with nano‐scale SiO₂ particles as seeds composed of methyl methacrylate (MMA), butyl acrylate (BA), hydroxyethyl methacrylate (HEMA), and acrylic acid (AA) was studied from varying reaction temperatures, level of SiO₂ particle, HEMA, and emulsifier. The morphology of the emulsion particle was examined with a transmission electron microscope (TEM). The results showed that the addition of nano‐SiO₂ particles decreased the coagulum greatly when its level was lower than 7%. The coagulum also decreased with the increasing of temperature from 65°C to 75°C. The level of HEMA and emulsifier had little influence on the coagulum in the presence of nano‐SiO₂. The particle size of the emulsion increased with the increase of level of nano‐SiO₂ and HEMA. Part of the emulsion particles connected together due to the existence of HEMA, and yet some of the nano‐SiO₂ particles were not covered with polymer.     

One‐Pot Preparation of Unsymmetrical Biaryls via Suzuki Cross‐Coupling Reaction of Aryl Halide using Phase‐Transfer Catalyst in a Biphasic Solvent System

A one‐pot synthetic method of unsymmetrical biaryls was developed via the Suzuki cross‐coupling reaction of aryl halide using a phase‐transfer catalyst in a biphasic solvent system.     

Efficient Synthesis of β‐Acetylamino Ketones using Silica‐Supported Sodium Hydrogen Sulfate as a Heterogeneous Catalyst

Silica‐supported sodium hydrogen sulfate (NaHSO₄ · SiO₂) efficiently catalyzes the four‐component reaction of aryl aldehydes, enolisable ketones, acetyl chloride, and acetonitrile to form the corresponding β‐acetylamino ketones at room temperature. The catalyst is inexpensive and ecofriendly and works under heterogeneous conditions.The present methodology offers several advantages such as excellent yields, simple procedure, short reaction times (1–3 h), and mild conditions.     

Synthesis of Substituted 1,4‐Dihydropyridines in Water Using Phase‐Transfer Catalyst Under Microwave Irradiation

Abstract

The synthesis of various substituted 1,4‐dihydropyridines has been achieved by the reaction of aldehydes, ethyl/methyl acetoacetates, and ammonium acetate in water using phase‐transfer catalyst under microwave irradiation. Compared to the classical Hantzsch's reaction conditions, this new method consistently has the advantage of good yields and short reaction times. Bifunctional compounds containing two units have been synthesized using dialdehyde as precursor in good yields.