Butyl Bis Research Articles

Polymerization behaviour of butyl bis(hydroxymethyl)phosphine oxide: Phosphorus containing polyethers for Li-ion conductivity

Synthesis of phosphorus containing polyethers and their lithium-ion conductivities for the potential use as solid polymer electrolyte (SPE) in high-energy density lithium-ion batteries have been described. Co-polymerization of butyl bis(hydroxymethyl)phosphine oxide with three different dibromo monomers were carried out to produce three novel phosphorous containing polyethers (P1–P3). These polymers were obtained via nucleophilic substitution reactions and were characterized by 1H, 31P NMR spectral data and gel permeation chromatography. SPEs were prepared using polyethers (P1 and P2) with various amounts of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The lithium-ion conductivity of SPE2 containing 40 wt% of LiTFSI was 2.1 × 10−5 S cm−1 at room temperature and 3.7 × 10−4 S cm−1 at 80°C. Solid polymer electrolytes having good ionic conductivity and possible flame retardant property for application in larger lithium-ion batteries were prepared using phosphorus containing polyethers wherein phosphorus atoms are present in the main polymer chain.

Synthesis and Photopolymerization of 2,2-Di((Acryloyloxy)Methyl)Butyl Bis(2-(Acryloyloxy)Ethyl)Carbamate

A low-viscosity monomer, 2,2-di((acryloyloxy)methyl)butyl bis(2-(acryloyloxy)ethyl)carbamate (DBAC), was synthesized using a non-isocyanate route. The photopolymerization kinetics were monitored by realtime infrared spectroscopy (RT-IR). The results indicated that the rate of polymerization and the final conversion of DBAC were high and influenced by light intensity, photoinitiator type and concentration. Dynamic mechanical analysis (DMA) results indicated that the glass transition temperature and molecular weight between cross-links of DBAC were higher than that of pentaerythritol tetraacrylate (SR 295).

Mechanism and rate of butyl phosphinate formation from reaction of phosphinic acid (Cyanex 272) and tributyl phosphate

An impurity species, butyl bis(2,4,4-trimethylpentyl)phosphinate (‘butyl phosphinate’), has recently been identified in the Murrin Murrin solvent extraction (SX) circuits. The present work established that this species is formed via direct reaction between tributyl phosphate (TBP) and the phosphinic acid extractant found in Cyanex 272 and that the reaction is first order relative to the concentration of each reactant. The observations are consistent with the reaction progressing via a bimolecular nucleophilic substitution (S N2) mechanism whereby nucleophilic attack of substrate TBP by the phosphinic acid anion occurs, resulting in cleavage of the C–O bond and ejection of dibutyl phosphate anion. The butyl phosphinate formation rate has been determined under synthetic extract, strip and aqueous-free conditions, the latter at temperatures between 40 and 75 °C. In the absence of an aqueous phase, the rate coefficient was found to be 0.43 ± 0.02 M −1 per annum (95% confidence interval) at 70 °C with an activation energy of 122 kJ/mol. Based on the present data and historical SX plant operating information, a model to estimate annual butyl phosphinate generation and its build-up in the Murrin Murrin SX circuits over the last decade was developed. The estimated accrued level of 31 g/L butyl phosphinate by June 2009 is comparable to the measured 32–35 g/L.

Extraction Properties of Butyl Bis(dibutoxyphosphinylmethyl)phosphinate in Nitric Acid Solutions

The extraction of HNO3 and microamounts of U(VI), Th(IV), Sc(III), REE(III), and Am(III) nitrates from HNO3 solutions with solutions of butyl bis(dibutoxyphosphinylmethyl)phosphinate in organic diluents was studied. The stoichiometry of the extractable complexes was determined, and the apparent extraction constants were calculated. The capability of the extractant to recover the examined elements from nitric acid solutions grows with an increase in the number of phosphoryl groups in its molecule. The recovery of the metal ions into the organic phase becomes more efficient in going to more polar organic diluents.

Metabolism of phosphoric acid triesters by goldfish, Carassius auratus.

The metabolic fate of phosphoric acid triesters in the goldfish (Carassius auratus) were clarified through some experiments in vitro and in vivo. Tributylphosphate (TBP) was converted to dibutyl 3-hydroxybutyl phosphate (TBP-OH) and dibutyl phosphate (DBP) by incubation with goldfish liver microsomes. This reaction was Nicotinamide Adenine Dinucleotide Phosphate (Reduced form) (NADPH)-dependent and presumed to be an oxidation by mixed function oxidase (MFO). The microsomes did not metabolize tris (2-chloroethyl) phosphate, tris (1, 3-dichloro2propyl) phosphate (TDCPP), and triphenylphosphate (TPP) as well as TBP. The soluble fraction of goldfish liver contained an enzyme that acted specifically on TDCPP. The enzyme was glutathione (GSH)-dependent and had an optimum pH at 8-9, and it was concluded to be glutathione S-transferase (GSTase), which was stable at 45°C. GSTase in the goldfish had higher activity than the rat enzyme only toward TDCPP in several substrates tested. The superiority of goldfish GSTase to the rat enzyme might come from the difference of their rate constants, Km values on TDCPP. The GSH contents in the liver and whole body of the goldfish were significantly decreased by exposure to diethyl maleate (DEM). Pretreatment with DEM increased the assumulation of TDCPP in the fish 6.6-fold but scarcely affected TBP and TPP contents. This results indicate that GSTase is concerned with in vivo metabolism of TDCPP. Killifish (Oryzias latipes) absorbed TBP from water and metabolized it to TBP-OH, butyl bis-(3-hydroxybutyl) phosphate and DBP, which are the same as the metabolites obtained with MFO in the goldfish liver.

Monothiocarbonates and their oxidation to disulphides

The preparation, properties, and oxidation of potassium methyl to hexyl mono-thiocarbonates and of dipotassium butyl bis(monothiocarbonate) are reported. The oxidation product of the latter is a dimer. Some nickel, lead, copper, and silver complexes were isolated. The ability of monothiocarbonates to form metal complexes lies between alkyl carbonates and dithiocarbonates. Copper(I) ethyl monothiocarbonate is a tetramer.

Organoboron compounds Communication 119. Action of boron tribromide on olefins

1. Boron tribromide adds to 1-octene, 1-hexene, and 3-hexene with formation of the corresponding bromobisbromoalkylboranes and trisbromoalkylboranes. 2. Boron tribromide does not add to 2,4,4-trimethyl-1-pentene, but the latter dimerizes in presence of boron tribromide. 3. When bromobis-2-bromooctylborane is treated with 1-butanethiol the successive replacement of bromine atoms of butylthio groups occurs. Reaction of tris-2-bromooctylborane with 1-butanethiol gives butyl bis[2-(butylthio)octyl]borinate. 4. When bromobis-2-bromooctylborane and tris-2-bromooctylborane are treated with alcohols or hydrogen bromide, octene is eliminated and, under the conditions of the experiment, dimerizes.