Tributylammonium Chloride Research Articles

Counterion-specific clouding in aqueous anionic surfactant: a case of Hofmeister-like series

Two ionic surfactants (sodium dodecylsulphate (SDS) and sodium dodecylbenzenesuphonate (SDBS)) are chosen, and effect of addition of quaternary bromide or chloride (tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, tetraphenylphosphonium bromide, tetra-npentylammonium bromide and benzyl tributylammonium chloride) has been studied on the cloud point (CP) behaviour in aqueous solution. CP behaviour was observed due to dehydration of headgroup region in presence of quaternary counterion. Order of counterion to decrease CP is as follows: TPeA+ > BTA+ > TBP+ > TPhP+ > TBA+ for SDS and TPeA+ > TPhP+ > BTA+ > TBP+ > TBA+ for SDBS. CP data have been used to select surfactant + salt system. Effect of additives (carbohydrate, amino acid or vitamin), on the CP, has been seen on above such selected systems. Additive may either decrease or increase the CP, depending upon the structure of counterion and/or the additive. Counterion (cations) can be arranged in an order like Hofmeister series.

Efficient Catalytic System Involving Molybdenyl Acetylacetonate and Immobilized Tributylammonium Chloride for the Direct Synthesis of Cyclic Carbonates from Carbon Dioxide and Olefins

An effective direct method for preparing of cyclic carbonates from CO2 and olefins in the presence of tert-butyl hydroperoxide as an oxidant was provided. The first stage, the epoxidation of olefins, was carried out using MoO2(acac)2 as a catalyst (1h, 100 °C), and the second stage, the cycloaddition of CO2 to the resulting epoxide, was proceeded in the presence of immobilized tributylmethylammonium chloride on a polystyrene cross-linked with divinylbenzene, and an aqueous solution of ZnBr2 (100 °C, 0.9 MPa of CO2, 4 h). The proposed method allowed to obtain cyclic carbonates with high yields (50–77%) under mild conditions. Moreover, the immobilized catalyst could be reused at least five times without significant loss of its catalytic activity.Graphical

ChemInform Abstract: Recyclable Polymer‐Supported Nanometal Catalysts in Water

Two types of polymer-supported nanometal catalysts with high catalytic activity and recyclability in water have been developed. One catalyst was composed of linear polystyrene-stabilized metal nanoparticles (PS-MtNPs). A palladium catalyst (PS-PdONPs) was prepared in water by the thermal decomposition of Pd(OAc)2 in the presence of polystyrene. The degree of immobilization of Pd, but not the size of the Pd nanoparticles, was dependent on the molecular weight and cross-linking of the polystyrene. The PS-PdONPs exhibited high catalytic activity for Suzuki, Heck, and Sonogashira coupling reactions in water and they could be recycled without loss of activity. Linear polystyrene was also suitable as a stabilizer for in situ generated PdNPs and PtNPs. The second catalyst was a polyion complex that was composed of poly[4-chloromethylstyrene-co-(4-vinylbenzyl)tributylammonium chloride] and poly(acrylic acid)-stabilized PdNPs (PIC-PdNPs). Aggregation and redispersion of PIC-PdNPs were easily controlled by adjusting the pH value of the solution.

Recyclable Polymer‐Supported Nanometal Catalysts in Water

Two types of polymer-supported nanometal catalysts with high catalytic activity and recyclability in water have been developed. One catalyst was composed of linear polystyrene-stabilized metal nanoparticles (PS-MtNPs). A palladium catalyst (PS-PdONPs) was prepared in water by the thermal decomposition of Pd(OAc)2 in the presence of polystyrene. The degree of immobilization of Pd, but not the size of the Pd nanoparticles, was dependent on the molecular weight and cross-linking of the polystyrene. The PS-PdONPs exhibited high catalytic activity for Suzuki, Heck, and Sonogashira coupling reactions in water and they could be recycled without loss of activity. Linear polystyrene was also suitable as a stabilizer for in situ generated PdNPs and PtNPs. The second catalyst was a polyion complex that was composed of poly[4-chloromethylstyrene-co-(4-vinylbenzyl)tributylammonium chloride] and poly(acrylic acid)-stabilized PdNPs (PIC-PdNPs). Aggregation and redispersion of PIC-PdNPs were easily controlled by adjusting the pH value of the solution.

Synthesis and characterization of poly(p-xylylene tetrasulfide) via interfacial polycondensation in the presence of phase transfer catalysts

Poly(p-xylylene tetrasulfide) was synthesized from 1,4-bis(chloromethyl)-benzene and sodium tetrasulfide using interfacial polycondensation technique to examine the effect of methyl tributyl ammonium chloride, tetrabutyl ammonium bromide, and benzyl triethyl ammonium chloride as phase transfer catalysts. The structure of the synthesized polysulfide was confirmed via elemental analysis, attenuated total reflectance Fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray diffraction techniques. Moreover, the thermal behavior of this polymer was characterized using differential scanning calorimetry and thermo gravimetric analysis methods. Beyond, Friedman method was applied to analyze the degradation kinetics of the prepared polymer. The synthesized polymer had a molecular weight of about 2584 g/mol.

Polyion complex stabilized palladium nanoparticles for Suzuki and Heck reaction in water

Palladium nanoparticles stabilized by a polyion complex composed of poly{4-chloromethylstyrene- co-(4-vinylbenzyl) tributylammonium chloride} and poly(acrylic acid) were easily recovered by filtration after pH treatment. The polyion complex stabilized palladium nanoparticles have high catalytic activity for the Suzuki and Heck reactions in water.

Synthesis and Characterization of Polysulfide Rubber Using Phase Transfer Catalyst

AbstractSummary: Poly(alkyltetrasulfide) is prepared via reaction of ethylene dichloride with sodium tetrasulfide (Na2S4) in the presence of methyl tributyl ammonium chloride as phase transfer catalyst (PTC). The polysulfide polymer is characterized by CHN analysis, FT‐IR, TGA, DTA and DSC techniques.

Chemical kinetics of carbon dioxide with glycidyl methacrylate using immobilized tributylamine supported on poly(styrene-co-vinylbenzyl chloride) as a catalyst

A soluble copolymer-supported catalyst containing pendant tributylammonium chloride was synthesized by the radical copolymerization of p-chloromethylated styrene followed by the addition reaction of the resulting copolymer with tributylamine. The absorption rate of carbon dioxide was measured from the absorption experiment into glycidyl methacrylate (GMA) solutions containing the catalyst in a semi-batch stirred tank with a plane gas–liquid interface at 0.1013 MPa. The reaction rate constants of the reaction between carbon dioxide and GMA were obtained by the analysis of the mass transfer mechanism accompanied by chemical reactions based on the film theory.Solvents such as toluene, N-methyl-2-pirrolidinone, and dimethyl sulfoxide influenced the reaction rate constants. Furthermore, this catalyst was compared to the monomeric tetrabutyl-ammonium chloride under the same reaction conditions.

‘Green’ Synthesis of Nitro Alcohols Catalyzed by Solid-Supported Tributylammonium Chloride in Aqueous Medium

A series of 1-aryl-2-nitroalkan-1-ols (5a-m; Table 2) was prepared in yields of 64-94% by Henry reaction between aromatic aldehydes and nitroalkanes in the presence of a dual catalytic system of KOH and polystyrene-supported tributylammonium chloride (PsTBAC; 2). The reactions were performed either in H2O containing 10% of THF or, in the case of liquid reagents (aldehydes and nitroalkanes), in neat H2O at room temperature. The immobilized phase-transfer catalyst, designed to be used for large-scale industrial processes, could be easily separated from the products, and effectively re-used several times, basically without loss in activity.

Improving the cooperation of co-catalysts by locating them on different units of a copolymer

Linear bifunctional copolymers were prepared by the free radical copolymerization in solution of a phosphine ligand (3- and 4-vinylbenzyl-biphenylphosphine (VBBP) or 3,4-bis(diphenylphosphine)-1-butene (BDPB) with an excess amount of a quaternary onium salt (vinylbenzyl tributyl ammonium chloride (VBAC)). The copolymer bicatalysts P(VBBP-Pd-VBAC) or P(BDPB-Pd-VBAC) were prepared by attaching palladium complexes to the pendant phosphine ligands. The Heck coupling reactions of iodobenzene with acrylate esters in DMF were employed to investigate the cooperation of the catalysts located on the copolymer by comparing their catalytic activities to those obtained with systems in which the two catalytic groups are not assembled together. It was found that the former exhibit higher catalytic activities than the latter, and that the P(VBBP-Pd-VBAC) system provides a higher product yield than P(BDPB-Pd-VBAC). The results also suggest that the polymer blocks of quaternary ammonium groups in the copolymers constitute receptors for the reactants. The amounts of phosphine, onium salt and palladium in the copolymer catalysts were determined by elemental analysis; 31P NMR experiments were carried out to investigate the distribution of phosphine in the copolymer chain.

Thermal analysis study of heat of dehydration of tributylammonium smectites

The dehydration of laponite and montmorillonite treated with tributylammonium chloride was studied by DSC, TG and X-ray diffraction. Dehydration of the organo-laponite took place in one stage at 320–475 K, whereas that of the organo-montmorillonite occurred in two stages, at 320–435 and 435–485 K. The first stage was attributed to loss of water of the hydrophobic hydration zone. The second stage was specific for montmorillonite and was attributed to water molecules forming hydrogen bonds with the oxygen planes of the silicate layers. Hydrogen bond formation was attributed to the tetrahedral substitution of Al for Si. The organo-laponite has a lower molar heat of dehydration than laponite, indicating that the interlayer water clusters of the organo-clay are smaller than those of the untreated clay. The molar heat of dehydration of untreated montmorillonite is less than that of untreated laponite, indicating that water clusters in the interlayer of the former are smaller. The molar heat of dehydration of organo-montmorillonite is higher at the second dehydration stage than at the first, because at this stage water molecules which form hydrogen bonds with atoms from the oxygen plane are evolved. In organo-montmorillonite, water molecules from the non-structured zone form water bridges between adjacent oxygen planes, thus preventing crystalline swelling. In organo-laponite, non-structured water molecules do not form strong hydrogen bonds with atoms from the oxygen plane, water bridges between adjacent oxygen planes are weak, and crystalline swelling is thus prevented to a limited extent only.

Preparation of polymer-supported catalysts containing phosphorus palladium complexes and quaternary onium groups, and their application to the vinylation reaction

Micron-sized crosslinked polystyrene [poly(ST-DVB)] particles prepared by the concentrated emulsion polymerization method were coated with nonuniform layers of the following functionalized polymers: (I) poly(3- and 4-vinylbenzyl chloride) [poly(VBC)]; (II) a copolymer of VBC and 4-chlorosytrene [poly(VBC)-(CST)] and; (III) a composite of poly(VBC) and poly(3,4-dichloro-1-butene) [poly(VBC)-poly (DCB)]. A fine powder composed of small aggregates of such particles was obtained by grinding. The polymers thus prepared were converted to three types of reactive substrates containing both organophosphorus ligands and quaternary onium groups: (1) (m-sulfonate phenyl) diphenyl phosphine and poly(vinylbenzyl tributyl ammonium chloride) bound to poly(ST-DVB); (2) diphenyl ethylene phosphite and benzyl methyl diethanol ammonium groups bound to poly(ST-DVB); and (3) phosphine oxide and quaternary benzyl tributyl ammonium or phosphonium groups bound to poly(ST-DVB). The polymer-supported catalysts containing phosphorus palladium complexes and quaternary onium groups were then employed in the vinylation reaction of iodobenzene with methyl acrylate. These supported bicatalysts displayed a cooperative effect that increased the yield of vinylation by a factor greater than two when compared to its homogeneous counterpart. The relative locations of palladium complexes and quaternary onium groups are found to influence the yield.

Triple ion formation by the hydrogen-bonding force in protophobic aprotic solvents

A large deviation was observed between the observed value of the equivalent conductivity (Λ obsd ) and the calculated value (Λ calcd ) only with ion-pair formation constant (K 1 ) for tributylammonium chloride (n-Bu 3 NHCl, (0.4-6.0)×10 -3 M) in nitrobenzene and benzonitrile

The Use of Silica Gel-Supported Ionenes as Reagents and Catalysts for Several Substitution Reactions in Toluene

Abstract Several ionene bromides were used as reagents for the displacement of decyl methanesulfonate into 1-bromodecane. They were very reactive when adsorbed by silica gel. The enhanced activities of the ionenes were hardly dependent on their structures and molecular weights but decreased gradually with increasing the amount of ionene adsorbed by silica gel. Ionene chlorides exhibited a similar enhancement of reactivity when adsorbed by silica gel. However, unlike the ionenes, a large increase in activity due to adsorption was not observed with pendant-type polycations such as poly(4-vinylpyridinium bromide) and poly[(4-vinylbenzyl)tributylammonium chloride]. The silica gel-supported ionenes also exhibited excellent catalytic activities for solid–liquid–solid triphase substitution reactions, particularly for the reactions between 1-bromodecane and such inorganic salts as consisted of relatively hard-basic nucleophilic anions.

Selected Growth Regulators Increase Yield of Snap Beans1

Abstract A Single foliar spray of 5-chloro,-2-thenyl, tri-n-butyl-phosphonium chloride (CTBP), 90% soluble powder; tetrahydrofur-furyl isothiocyanate (CHE 8570), 47% emulsifiable concentrate; 5-bromo,2-thenyl,tributyl-ammonium chloride (CHE 9064), 50% wettable powder; or 2,3,5-triiodobenzoic acid (TIBA), 14.2% emulsifiable concentrate, was applied when first flowers opened of ‘Salem’ and ‘Top Crop’ snap beans (Phaseolus vulgaris L.). Treatments of CHE 9064 at 8.72 g/ha and TIBA at 2.32 g/ha significantly increased yield of spring-planted ‘Salem’ in 1971. Treatments of CHE 8570 and CHE 9064 at 11.62 g/ha significantly increased yields of spring-planted ‘Top Crop’ in 1972 due to increased pod set Foliage samples at harvest showed no physiologically significant increase in P, K, Ca, Mg, Fe, or Zn for the treated plants compared with the controls.

Conductance of Mixtures of Lead Abietate and Tributylammonium Chloride in Toluene

Conductance of Mixtures of Lead Abietate and Tributylammonium Chloride in Toluene