Dibutyl Phosphite Research Articles

Anticorrosive and antimicrobial efficiency of photopolymerizable phosphorus (meth)acrylate oligomers-based coating materials

Novel photopolymerizable phosphorus (meth)acrylate oligomers were verified as anticorrosive and antimicrobial coating materials. Oligomers containing P-atoms were prepared by a solution-free UV-initiated telomerization process of aliphatic (meth)acrylates and styrene in the presence of different organic phosphorus compounds (P-telogens). The influence of the P-telogen structure on the photoaging process of coatings, as well as their anticorrosion and antibacterial properties was investigated. Relatively the highest anticorrosive efficiency was revealed for a varnish based on a telomers syrup containing dibutyl phosphite (DBPh) and dibutyl phosphate (DBP) due to the relatively long alkyl chain. In turn, UV-photocurable coatings exhibited moderate antibacterial and good anti-yeast activity but the best properties were found for the coating with dimethyl phosphite (DMPh). The higher resistance to photodegradation was observed in the case of the diphenyl phosphite (DPPh) due to the large phenyl substituent. Regardless of the structure of the organophosphorus compound, all coatings showed excellent adhesion to the glass substrate.

Phosphorus-Containing Telomers as UV-Curable Binders of Solvent-Free Varnish Coatings.

The synthesis of novel phosphorus-containing telomers (P-telomers) was conducted via a solution-free UV-initiated telomerization process of butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and styrene, different phosphorus telogens (dimethyl phosphite (DMPh), dibutyl phosphite (DBPh), diphenyl phosphite (DPPh) or dibutyl phosphate (DBP)), and a radical photoinitiator-acylphosphine oxide (APO). The course of the UV-phototelomerization process was monitored by photo-DSC and the chemical structures of telomers were assessed by FTIR. Final UV-photocurable varnish compositions consisted of prepared P-telomer syrups, crosslinking monomer (pentaerythritol triacrylate; PETIA), and a radical UV-photoinitiator (α-hydroxyalkylphenone, HAP). The influence of P- telomers on the optical and mechanical features of coatings was investigated. Relatively the highest hardness and satisfactory scratch values, as well as water and solvent resistance, were observed for varnish based on DMPh-telomers. While the strongest adhesive bond to a glass substrate was reported for DPPh-telomers. It is worth pointing out that the P-telomers did not affect the gloss values of varnishes in comparison to the telomer-free reference sample.

Synthesis and antioxidant properties of bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propyl)phosphite

Bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propyl)phosphite was synthesized by reaction of 2,6-di-tert-butyl-4-(3-hydroxyproyl)phenol with dibutyl phosphite. The structure of bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propyl)phosphite was supported by IR and NMR (1H, 13C, 31P) spectroscopy; its composition was confirmed by elemental analysis. High antioxidant activity of the synthesized phosphite has been shown in a model reaction with the free chromogen-radical 2,2-diphenyl-1-picrylhydrazyl and under conditions of accelerated thermal oxidation of paraffinic and mineral oils.

Synthesis a novel family of phosphonate surfactants and their evaluation as corrosion inhibitors in formation water

Nine phosphonates surfactant were synthesized by two steps. The first step was condensation between acetaldehyde and butyl amine, dodecylamine or hexadecylamine individually to give three corresponding Schiff bases, and then the Schiff base products were added to dibutyl phosphite individually. The second step was reaction of the phosphonate products with polyethylene glycol 400, 600 and 1000 to get on the nine water soluble phosphonate corrosion inhibitors. The products were characterized by FTIR, 1HNMR and 13CNMR spectroscopic techniques. The surface active properties of this phosphonate were calculated and they were evaluated as corrosion inhibitors in formation water formulations using open circuit potential and potentiodynamic polarization. The quantum calculations of the structures were calculated and the data obtained were nearly closed with the experimental data. HMPA1 shows the best results as corrosion inhibitors (efficiency 94%) at lowest concentration 15 ppm. The corrosion inhibition mechanism was discussed on the basis of surface tension measurements and the electronic data.

Thermally Induced Protonation of Conducting Polyaniline Film by Dibutyl Phosphite Conversion to Phosphate.

The blue thin polyaniline base film changes its color to green after immersion of the film into dibutyl phosphonate. The green color of the film converts to a greenish-blue after heating to 200 °C in air, which is characteristic for the protonated conducting form of polyaniline. This is in contrast to the "standard" polyaniline hydrochloride, which is transformed into a cross-linked polyaniline base under such conditions. To explain this unexpected observation, the interaction of polyaniline base with dibutyl phosphonate at ambient conditions and after heating to 200 °C was studied using UV-visible, FTIR and Raman spectroscopies. On the basis of these studies, we propose that the dibutyl phosphite tautomeric form of dibutyl phosphonate, which interacts with polyaniline base at 20 °C, converts to the oxidized form, dibutyl phosphate, at 200 °C and subsequently protonates the film. Quantum-chemical modeling of the interaction of polyaniline base with dibutyl phosphite and dibutyl phosphate supports this explanation.

Magnesium Perchlorate Catalyzed Phospha-Michael Addition of Dialkyl Phosphite to Chalcone

Aim and Objective: Phosphonate possesses a broad range of applications ranging from agrochemistry to medicines. Because of the synthetic and biological importance of phosphonate, their chemistry has stimulated an increasing interest. Hence we developed an efficient and eco-friendly Mg(ClO4)2 catalyzed one pot, solvent free synthesis of phosphonate derivatives of chalcones. Materials and Methods: Magnesium perchlorate phosphonate derivatives of chalcones were synthesized. The reactions were executed at room temperature in the presence of Anhydrous Magnesium perchlorate Anhy. Mg(ClO4)2 under solvent free condition, affording high yield of the product. The cardinal significance of the method lies in its uncomplicated and eco- friendly experimental conditions. Results: The PMA method for P-C bond formation, using dialkyl phosphite with chalcone, was performed in the presence of Anhydrous Magnesium perchlorate under solvent free condition. Despite the solvent free condition, the methodology is efficient since it is required only in catalytic amount of Anhy. Mg(ClO4)2 in one pot reaction. Results demonstrated that the catalytic PMA of dimethyl phosphite, diethyl phosphite, diisopropyl phosphite and dibutyl phosphite with chalcone generates desired products with a percentage yield of 60-80%. Conclusion: We have developed a new efficient PMA method for P-C bond formation, using dialkyl phosphite with α,β-unsaturated ketone i.e. chalcone. To the best of our knowledge, Anhy. Mg(ClO4)2 catalyzed phosphamicheal addition of dialkyl phosphite with chalcones was found to be a new and efficient method for various biological applications.

Interaction of polyaniline film with dibutyl phosphonate versus phosphite: Enhanced thermal stability

Interaction between blue film of polyaniline base with dibutyl phosphonate yields green polyaniline film. This resembles the classical protonation of polyaniline base with acids but, in the contrast, there is no proton available in prevailing phosphonate tautomeric form. The character of interaction was studied by evolution of the infrared spectra of the film recorded during heating up to 200 °C. The experiments demonstrate that dibutyl phosphite, and not its phosphonate tautomeric form, interacts with polyaniline base. Above 140 °C, the original polyaniline base is recovered in dry air purged environment in spectrometer. The interaction with polyaniline base prevents dibutyl phosphite from the oxidation into dibutyl phosphate which occurs in case of heating of neat dibutyl phosphite, in which phosphonate form predominates. The thermal stability and the changes in molecular structure have been assessed by UV–visible, FTIR and Raman spectra. The model of the interaction based on the quantum-chemical optimization of the idealized structure is proposed.

Preparation and Action Mechanism of Inclusion Complex of β-Cyclodextrin and Dibutyl Phosphite as Additives in Solution of Polyethylene Glycol-600

The inclusion complex of β-cyclodextrin (β-CD) and dibutyl phosphite (T304) was prepared by trituration. The tribological properties of the complex with different concentrations were investigated by a four-ball tester in the solution of polyethylene glycol-600 (PEG-600). The tribological test results showed that the complex exhibited better anti-friction and anti-wear properties than β-CD under different loads, and it was noted that the tribo-system showed the least friction coefficient when the concentration of the complex was 0.9%. It was proposed that the complex was decomposed into various molecular fragments and the T304 molecules were released under the friction condition. The XPS analytical results on the worn surfaces revealed that phosphide film formed by the released T304 played a major role and the iron alkoxide and carbon deposition films formed by the β-CD fragments had better anti-friction effect on the phosphide film surface. The interactions of different films resulted in the formation of a mixed boundary lubrication film.

Aerobic granular sludge mediated biodegradation of an organophosphorous ester, dibutyl phosphite.

Dibutyl phosphite, an organophosphorous compound, finds applications in different chemical industries and processes. Here, we report an efficient approach of biodegradation to be eventually used in bioremediation of dibutyl phosphite. Aerobic granules capable of dibutyl phosphite biodegradation were cultivated in a sequencing batch reactor (SBR). The SBR was operated with a 24-h cycle by feeding with dibutyl phosphite as a cosubstrate along with acetate. During the course of the SBR operation, aerobic granules of 0.9 ± 0.3 mm size were developed. Complete biodegradation of 1.4, 2 and 3 mM of dibutyl phosphite was achieved in 4, 5 and 8 h, respectively, accompanied by stoichiometric release of phosphite (H3 PO3). Phosphatase activity in the dibutyl phosphite-degrading granular biomass was 3- and 1.5-fold higher as compared to the activated sludge (seed biomass) and acetate-fed aerobic granules, respectively, indicating involvement in the hydrolysis of dibutyl phosphite. Microbial community analysis by t-RFLP showed the presence of 12 different bacterial types. Two bacterial strains capable of growth on dibutyl phosphite as sole carbon source were isolated and characterized as Acidovorax sp. and Sphingobium sp. The results show that aerobic microbial granules based process is suitable for the treatment of dibutyl phosphite contaminated water.

Biodegradation of dibutyl phosphite by Sphingobium sp. AMGD5 isolated from aerobic granular biomass

In the present study, cultivation of aerobic granular biomass capable of biodegradation of dibutyl phosphite, an organophosphite, and isolation of dibutyl phosphite degrading bacterial strains, are reported for the first time. The strain AMGD5, identified as Sphingobium sp., based on 16S rRNA sequencing, degraded dibutyl phosphite efficiently and utilised it as the sole source of carbon and phosphorus. Microbial degradation of dibutyl phosphite caused a significant decrease in medium pH, leading to cessation of growth and further degradation of dibutyl phosphite. Under buffered conditions, complete degradation of up to 3 mM of dibutyl phosphite was achieved within 60 h. The strain showed almost similar growth pattern when either phosphite or dibutyl phosphite was used as the phosphorous source. A 4-fold enhancement in phosphatase activity was evident in dibutyl phosphite fed cells, implying their role in dibutyl phosphite degradation. Sphingobium sp. AMGD5 can be a potential candidate for bioremediation of dibutyl phosphite contaminated waters or sites.

Anticorrosion imidazolium ionic liquids as the additive in poly(ethylene glycol) for steel/Cu–Sn alloy contacts

3-((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-1-methyl-1H-imidazolium hexafluorophosphates ([BTAMIM][PF6]) ionic liquids (ILs) were evaluated as friction reduction, antiwear (AW) and anticorrosion additives in poly(ethylene glycol) (PEG) for steel/Cu-Sn alloy contacts at 100 degrees C. The physical properties of PEG with the additive were measured. The anticorrosion properties of [BTAMIM][PF6] was assessed via the accelerated corrosion test, which reveals the excellent anticorrosion properties in comparison with selected conventional ILs that have no benzotriazole group. Tribological results indicated that [BTAMIM][PF6] as additives could effectively reduce the friction and wear of sliding pairs in PEG. The tribological properties were generally better than the normally used dibutyl phosphite (T304) and conventional ILs L-P108 in PEG. The wear mechanisms are tentatively discussed according to the morphology observation of worn surfaces of Cu-Sn alloy discs by scanning electron microscopy (SEM) and surface composition analysis by X-ray photoelectron spectroscopy (XPS), which revealed complex tribochemical reactions during the sliding process leading to a surface protective film composed of [Cu(-C6H5N3-R)], Cu20, CuF2 and C-O bond containing compound is formed. A strong interaction between benzotriazole and the surface of the Cu alloy was proposed to account for the excellent friction reduction, anti-wear and anti-corrosion capability improvement.

Effect of particle size on the mechanical properties of polystyrene and poly(butyl acrylate) core/shell polymers

The effects of particle size and polymer location (core or shell) on the mechanical properties of core/shell materials composed of polystyrene (PST) and poly(butyl acrylate) (PBA) made by a two-stage emulsion or microemulsion polymerization process are reported. Low-seed content (LSC) latexes were made by batch polymerization in microemulsions stabilized with DTAB in the presence of an organic salt (dibutyl phosphite). High-seed content (HSC) latexes were produced by microemulsion or emulsion polymerization in semi-continuous process. These latexes were subsequently used to form core/shell particles of PST/PBA or PBA/PST and their mechanical properties were examined and compared. Our results indicate that core/shell particle size and the location of the polymers have important effects on the mechanical properties.

Copper‐Catalyzed C—P Bond Construction via Direct Coupling of Secondary Phosphines and Phosphites with Aryl and Vinyl Halides.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Copper-catalyzed C-P bond construction via direct coupling of secondary phosphines and phosphites with aryl and vinyl halides.

A general method for the coupling of aryl and vinyl halides with diaryl and dialkyl phosphines, as well as with dibutyl phosphite, is reported. This highly efficient transformation is realized through the use of copper(I) iodide as a catalyst, N,N'-dimethylethylenediamine as a ligand, and Cs(2)CO(3) as a base. A variety of sterically hindered and/or functionalized substrates were found to react under these reaction conditions to provide products in good to excellent yields. [reaction: see text]

Tribological properties of P‐ and N‐containing organic compounds as potential extreme‐pressure and antiwear additives

AbstractAn amine salt of an alkoxylphosphate (a P‐ and N‐containing organic compound, PN) was synthesised. Its extreme‐pressure, antiwear, and friction‐reducing properties were evaluated as an additive in liquid paraffin and a mineral oil. Tests were performed on a four‐ball friction and wear tester with an AISI 52100 steel ball self‐mated pair and the results were compared with those of sulphurised olefin (SO), zinc di‐n‐butyldithio‐phosphate (ZDDP), and dibutylphosphite (DBP). The morphologies of the worn steel surfaces were observed using a scanning electron microscope, while the binding energies of some typical elements on the worn surfaces were determined using X‐ray photoelectron spectroscopy. The additives were found to increase the load‐carrying capacity and to reduce wear and friction coefficient considerably. PN as an additive exhibits better load‐carrying, antiwear, and friction‐reducing properties than SO, ZDDP, and DBP under the same test conditions.

ADDITION PRODUCTS OF DIBUTYL PHOSPHITE TO SCHIFF BASES

1,4-Bis[N-methyl(dibutoxyphosphonyl)-1-(2-furyl)]diaminobenzene and 4,4'-bis[N-methyl (dibutoxyphosponyl)-1-phenyl]benzidine have been synthesized through addition of dibutyl phosphite to Schiff bases (N,N'-difurfurylidene-p-phenylenediamine and N,N'-dibenzylidene-benzidine, respectively) in the presence of sodium butoxide or triethylamine. The compounds have been characterized by elemental analysis, TLC and IR spectra. A detailed analysis of their 1H-NMR spectra (1D and COSY) has been carried out.

Addition Products of Dibutyl Phosphite to Schiff Bases

1,4-Bis[N-methyl(dibutoxyphosphonyl)-1-(2-furyl)]diaminobenzene and 4,4'-bis[N-methyl (dibutoxyphosponyl)-1-phenyl]benzidine have been synthesized through addition of dibutyl phosphite to Schiff bases (N,N'-difurfurylidene-p-phenylenediamine and N,N'-dibenzylidene-benzidine, respectively) in the presence of sodium butoxide or triethylamine. The compounds have been characterized by elemental analysis, TLC and IR spectra. A detailed analysis of their 1H-NMR spectra (1D and COSY) has been carried out.

Friction and wear behaviour of liquid paraffin containing an S‐P type additive and amine

AbstractSulphurised olefin (SO) and dibutyl phosphite (DBP) are two popular antiwear and extreme‐pressure additives for gear oils. Investigation of the effects of the weight ratio of SO to DBP in liquid paraffin, and the effects of dodecyl amine, on the friction and antiwear properties of oil, were conducted with a four‐ball wear tester. The chemical composition of the film, formed was examined using X‐ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and reflecting infrared spectro‐scopic (IR) microscopy.The four‐ball test results indicate that the weight ratio of SO to DBP affects the friction and wear behaviour of the oil and, with a weight ratio of SO to DBP of 20:1, a stable friction coefficient, and the smallest wear scar, were observed. Wear tests also showed that dodecyl amine improves or reduces the antiwear ability of the oil at certain concentrations. AES profile analyses demonstrate a thick boundary film formed on the rubbed surface with the weight ratio of SO to DBP at 20:1. Both AES and IR results indicate that the addition of dodecyl amine to an S‐P type oil results in competitive adsorption, and hinders the reaction of SO and DBP with the steel surfaces.

Friction and wear of the film formed in an oil immersion test under a nitrogen atmosphere

The oil immersion test is a useful method to investigate the interaction between steel bearings and oil additives. In this work, oil immersion tests of steel blocks with sulfurized olefin (SO), dibutyl phosphite (DBP), and the combination of SO and DBP with various weight ratios in liquid paraffin were conducted at a temperature of 180°C for a test time of 60 min under a N 2 atmosphere. The relative thicknesses of the films formed were examined using Auger electron spectroscopy (AES). The friction coefficient and wear life of the film formed in oil immersion tests were evaluated using a one-way reciprocating friction tester under dry friction conditions against a steel ball at room temperature, and the results were compared with the wear results of films formed under an air atmosphere. AES analyses indicate that under N 2 atmosphere, a thicker chemical reacted surface film on the steel block was formed as compared with the film formed at the same immersion test conditions but under an air atmosphere. Friction and wear tests show that films formed under a N 2 atmosphere exhibit a longer wear life than that of the films formed under air atmosphere. This investigation demonstrates that the film thickness is affected by the weight ratio of SO to DBP, while the antiwear behaviour of the film formed in an S/P weight ratio of 80 oil seems to be the best in terms of the wear life per unit thickness of the film.

Friction and wear of the film formed in the immersion test of oil containing antiwear and extreme pressure additives

The oil immersion test is a useful method to investigate the interaction between steel-bearing and oil additives. In this work, oil immersion tests of steel blocks with sulfurized olefin (SO), dibutyl phosphite (DBP), and the combination of SO and DBP in various weight ratios in liquid paraffin were conducted at a temperature of 180 °C for a test duration of 60 min. The chemical composition of the film formed was examined using both X-ray photoelectron spectroscopy and Auger electron spectroscopy. The friction coefficient and wear life of the films formed in the oil immersion tests were evaluated using a one-way reciprocating friction tester under dry friction conditions against a steel ball at room temperature. The performance of the liquid paraffin containing SO, DBP or the combination of SO and DBP was also investigated with a four-ball wear tester. Results indicate that with the S P weight ratio at 55, a lower friction coefficient and longer wear life of the film formed in the immersion test can be observed. Test results demonstrate that the wear life of the film formed in the oil immersion tests are in good agreement with the wear results of the conventional four-ball wear test.