Acrylonitrile In Aqueous Solution Research Articles

Dispersion polymerization of N-vinylformamide and acrylonitrile in aqueous solution, amidinization, and flocculation performance

Dispersion polymerization of N-vinylformamide and acrylonitrile in aqueous solution, amidinization, and flocculation performance

3 + 2] Cycloaddition with photogenerated azomethine ylides in β-cyclodextrin.

Stability constants for the inclusion complexes of cyclohexylphthalimide 2 and adamantylphthalimide 3 with β-cyclodextrin (β-CD) were determined by 1H NMR titration, K = 190 ± 50 M−1, and K = 2600 ± 600 M−1, respectively. Photochemical reactivity of the inclusion complexes 2@β-CD and 3@β-CD was investigated, and we found out that β-CD does not affect the decarboxylation efficiency, while it affects the subsequent photochemical H-abstraction, resulting in different product distribution upon irradiation in the presence of β-CD. The formation of ternary complexes with acrylonitrile (AN) and 2@β-CD or 3@β-CD was also essayed by 1H NMR. Although the formation of such complexes was suggested, stability constants could not be determined. Irradiation of 2@β-CD in the presence of AN in aqueous solution where cycloadduct 7 was formed highly suggests that decarboxylation and [3 + 2] cycloaddition take place in the ternary complex, whereas such a reactivity from bulky adamantane 3 is less likely. This proof of principle that decarboxylation and cycloaddition can be performed in the β-CD cavity has a significant importance for the design of new supramolecular systems for the control of photoreactivity.

Development of a conductimetric biosensor using immobilised Rhodococcus ruber whole cells for the detection and quantification of acrylonitrile

A conductimetric biosensor for the detection of acrylonitrile in solution was designed and characterised using whole cells of Rhodococcus ruber NCIMB 40757, which were immobilised into a disc of dimethyl silicone sponge (ImmobaSil™). The biosensor described was capable of the detection and quantification of acrylonitrile in aqueous solution, having a linear response to concentrations between 2 and 50 mM (106–2650 ppm) acrylonitrile. The biosensor has been shown to be reproducible with respect to the data obtained over a number of days, and retains stability for a minimum period of at least 5 days before recalibration of the biosensor is required.

Analysis of acrolein and acrylonitrile in aqueous solution by membrane introduction mass spectrometry

Acrolein and acrylonitrile can be quantified directly at low levels in aqueous solution using membrane introduction mass spectrometry. Electron impact was used to generate positively charged ions and electron capture of the O-(2,3,4,5,6-pentafluorobenzyl)hydroxyl amine (PFBOA) derivative was used to generate negatively charged ions of acrolein in aqueous solutions. The origins of all ions in the mass spectra and product MS/MS spectra recorded using both ionization methods were assigned and a reaction scheme is given which accounts for the fragmentation of the PFBOA derivative. Detection limits were measured using multiple reaction monitoring in both the methods. With electron capture detection, acrolein could be detected without preconcentration at 10 ppb levels. Electron impact ionization and multiple reaction monitoring both allowed the measurement of acrylonitrile at levels as low as 10 ppb.

Determination of sub-parts-per-billion levels of acrylonitrile in aqueous solutions

Determination of sub-parts-per-billion levels of acrylonitrile in aqueous solutions

Peroxodiphosphate‐ascorbic acid redox couple as an initiator for vinyl polymerization

AbstractPrimary radical termination is found to be significant in the P2O84− ‐ascorbic acid redoxinitiated polymerization of acrylonitrile in aqueous solution at low converstions. Degradative chain transfer involving the P2O84− ‐ascorbic acid complex is invoked to explain the monomer exponent of unity and the initiator exponent of zero at high conversions (>10%) of the monomer.

ChemInform Abstract: PULSE RADIOLYSIS STUDY OF ACRYLONITRILE IN AQUEOUS SOLUTION

Chemischer InformationsdienstVolume 10, Issue 28 Preparative Organic Chemistry ChemInform Abstract: PULSE RADIOLYSIS STUDY OF ACRYLONITRILE IN AQUEOUS SOLUTION G. V. BUXTON, G. V. BUXTONSearch for more papers by this authorP. G. ELLIS, P. G. ELLISSearch for more papers by this authorT. F. W. MCKILLOP, T. F. W. MCKILLOPSearch for more papers by this author G. V. BUXTON, G. V. BUXTONSearch for more papers by this authorP. G. ELLIS, P. G. ELLISSearch for more papers by this authorT. F. W. MCKILLOP, T. F. W. MCKILLOPSearch for more papers by this author First published: July 10, 1979 https://doi.org/10.1002/chin.197928141Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume10, Issue28July 10, 1979 RelatedInformation

Pulse radiolysis study of acrylonitrile in aqueous solution

The following rate constants have been determined for the reaction of acrylonitrile (AN) with e–aq, H, OH and O–: k(e–aq+ AN)=(1.3 ± 0.2)× 1010 dm3 mol–1 s–1; k(H + AN)=(4.0 ± 0.5)× 109 dm3 mol–1 s–1; k(OH + AN)=(2.9 ± 0.3)× 109 dm3 mol–1 s–1; k(O–+ AN)=(2.0 ± 0.3)× 109 dm3 mol–1 s–1. The transient species which result from these reactions exhibit weak absorption bands between 240 and 300 nm. Some of these bands have been characterised and assigned to the radicals CH3ĊHCN (λmax∼ 285 nm, Iµmax∼ 270 dm3 mol–1 cm–1), HOCH2ĊHCN (λmax∼ 285 nm, Iµmax∼ 330 dm3 mol–1 cm–1), CH2CHCHN (λmax∼ 270 nm), ĊH2CHCNH (λmax∼ 255 nm). Reaction of e–aq with ClCH2CH2CN to generate ĊH2CH2CN showed that this radical does not absorb above 240 nm.Analysis of the permanent products of repetitively pulse irradiated solutions of acrylonitrile showed that the major products are NC(CH2)4CN, CH3CH(CN)CH2CH2CN and CH3CH(CN)CH(CN)CH3, indicating that the radicals react predominantly by coupling.Comparison of e.s.r. spectra obtained by reaction of mobile electrons with acrylonitrile and chloro-substituted propionitriles in neutral and alkaline glasses at 77 K showed that the radical anion AN–• protonates to give CH3ĊHCN. In solution at 300 K, however, protonation is believed to occur at all positions, though with varying probabilities.

Rate of Precipitation Polymerization of Acrylonitrile in Aqueous Solution

Rate of Precipitation Polymerization of Acrylonitrile in Aqueous Solution

Acrylonitrile polymerization in aqueous solution

AbstractThe polymerization of acrylonitrile in aqueous solution in the presence of an anionic soap was examined, particular attention being paid to the size of the latex particles as a function of the extent of the reaction. It was found that in some systems the rate of polymerization became irreproducible at conversions higher than about 25%. A tendency to gel formation in systems of quite low solids content was also noted.For one system the size of the latex particles at various conversions was determined by light scattering using the dissymmetry method. The average particle size was found to be essentially constant up to about 20% conversion and to increase slowly at higher conversions.A mechanism of particle formation and growth is proposed to account for these observations.

γ-Radiation-Initiated Polymerization of Acrylonitrile in Aqueous Solution and in Emulsion

Abstract The γ-radiation-initiated polymerization of acrylonitrile (AN) at 25[ddot] C has been studied, both in aqueous solution and in emulsion, at dose rates between 70 and 175 krad/hr. The effect of added emulsifier, sodium lauryl sulfate (SLS), on reaction rates, Rp, and on polymer molecular weight, Mn, has been investigated. G (monomer polymerized) values ranged from 7,500 in aqueous solution to 20,000 in bulk to 45,000 in emulsion, all based on the total energy absorbed. In the aqueous solution polymerization, where Rp is approximately first order in initial monomer concentration over the range 0.15 ± [AN]o ± 1.06 moles/liter, addition of SLS increases Rp but does not influence the order of the reaction with respect to [AN]o. In the emulsion system at 70 krad/hr and at a phase volume ratio AN/H2O of 1/2, (PR = 1/2), Rp varies as [SLS]0.1 over the concentration range 0.01 ± [SLS] ± 2.5± wt/vol of aqueous phase. At the same PR value, and at 80 krad/hr, Mn of the polymer (measured by viscometry in dime...

Study of the influence of dodecyl mercaptan, tert-butyl perbenzoate, and surface-active substances on the joint spectrophotometric determination of styrene and acrylonitrile in aqueous solutions

Study of the influence of dodecyl mercaptan, tert-butyl perbenzoate, and surface-active substances on the joint spectrophotometric determination of styrene and acrylonitrile in aqueous solutions

過硫酸アンモニウム-ヒドロキシルアミン系触媒によるアクリロニトリルの水系重合について

過硫酸アンモニウム-ヒドロキシルアミン系触媒によるアクリロニトリルの水系重合について

17] アクリロニトリルの均一系重合の研究

The polymerizations of acrylonitrile in aqueous solution of zinc chloride initiated by ammonium persulfate were investigated by using dilatometric technique under homogeneous conditions. The following results were obtained.1) The rate of polymerization was given by _??_This abnormal kinetic equation suggested that the complex between acrylonitrile and zinc chloride might behave as a reducing agent and accelerated the rate of decomposition of ammonium persulfate.2) The degree of polymerization of the polymer obtained in this system was several times larger than that of the polymer obtained in organic solvents. This results were interpreted in terms of complex formation between acrylonitrile and zinc chloride which produced an increase in kp2/kt.3) In this system, a, a-diphenyl-β-picryl hydrazyl, iodine+potassium iodide (1: 1), ferric chloride or cupric chloride behaved only as a retarder (or inhibitor), where p-benzoquinone, hydroquinone, hydroquinone monomethylether, p-tert-butyl pyrocatechol, pyrogallol or methylene blue behaved as both a retarder (or inhibitor) and a reducing agent.

Effects of cupric salts on the polymerization of acrylonitrile in aqueous solution

AbstractThe polymerization of acrylonitrile in aqueous solution initiated by ammonium persulfate in the presence of cupric salts was studied by a dilatometric method. The presence of cupric sulfate, nitrate, or acetate has a pronounced effect on polymerization, leading to an increase in the rate, and both cupric chloride and bromide retard or inhibit polymerization beyond certain salt concentrations. The increased rate is explainable by the following reactions: equation image The polymerization of acrylonitrile can be initiated by an oxidizing agent such as cupric sulfate, ferric sulfate, stannic chloride, nitric acid, or periodic acid. The decreased rate can be explained by assuming that the complexes of Cu+ ion with a halide ion X− such as CuX2−, CuX3=, CuX4≡, or Cu2X3− shows lower reactivity in the reaction with S2O8=. The cupric‐terminated reaction depends on the coexisting anion. The effect of sulfate, nitrate, acetate, phosphate, chlorate, or fluoride anions is negligible, while that of the chloride is marked, and that of the bromide is overwhelming. The CuX+(X = Cl, Br) ion appears to terminate polymer chains more efficiently than does Cuaq++. Apparent transfer constants of cupric sulfate in the presence of sodium chloride or bromide and the transfer constant of CuCl+ are given. It is suggested that the possibility of the termination reactions by halogen atom transfer is large under conditions of high halide ion concentration: magnified image and magnified image

Vinyl polymerization photosensitized by uranyl ions

AbstractA systematic investigation of the kinetics of polymerization of the vinyl monomers methyl methacrylate, methyl acrylate, and acrylonitrile in aqueous solution, photosensitized by uranyl ions, was undertaken. Light of wavelengths 300–450 mμ was used for irradiation. Complex formation and ion‐pair formation was kept to the minimum. The course of the reactions was followed in terms of rates of monomer disappearance, rates of uranous ion formation, and the chain length of the polymer formed. Under controlled conditions of acidity and ionic strength, quantitative correlations between the various rates and chain length, and the variables (1) fractional light absorption, (2) uranyl ion concentration, (3) wavelength of incident radiation, (4) monomer concentration, (5) light intensity, and (6) temperature of the reaction were obtained. The influence on the reaction of uranous ion present initially in the system was studied. The quenching of the fluorescence of uranyl ions by vinyl monomers and by other standard quenchers was compared. The tentative mechanism proposed for the overall reaction is discussed in the light of these experimental results. Ratios of specific rate constants and activation energies for the various steps have been evaluated.

Kinetics of the polymerization of acrylonitrile

AbstractIt is shown in this paper that the rate of polymerization of acrylonitrile in aqueous solution is lowered by the action of (i) a centrifugal field and (ii) stirring.The experimental results agree with the assumption of simultaneous occurrence of homogeneous and heterogeneous polymerization reactions.

Kinetic features of γ-ray initiated graft polymerization of acrylonitrile to polydimethylsiloxanes

A study was made of the effect of 60Co γ-rays on solutions of acrylonitrile in polydimethylsiloxane. The kinetics of the reaction were studied dilatometrically, and it was found that the results are in many ways similar to those obtained by other workers for the polymerization of acrylonitrile in aqueous solution. A theoretical interpretation similar to that given for the aqueous solution reaction is offered.

The polymerization of acrylonitrile in aqueous solution. Part I. The reaction catalyzed by Fenton's reagent at 25°C.

AbstractAn apparatus is described for following dilatometrically the polymerization of acrylonitrile in aqueous solution initiated by ferrous salts and hydrogen peroxide. A steady rate (Rp) is rapidly established which ultimately decreases rapidly but does not fall to zero after the initiator is consumed. From measurements of the concentration of the ferrous ion surviving the reaction, the effect of cupric, fluoride, and ferric ions on this, on Rp, on the final phases of this reaction, and on the corresponding reaction with methyl methacrylate, it is concluded that polyacrylonitrile radicals are oxidatively terminated by cupric and ferric ions, but polymethyl methacrylate radicals are not. When this linear termination is suppressed, Rp is proportional to [m1]2 at low monomer concentrations and linearly dependent on [m1] at high concentrations. The transition from one state of affairs to the other occurs at a monomer concentration which first decreases and then increases as the initiation rate (Ri) increases. These results are believed to be general for all modes of initiation and include all previous data, reconciling conflicting information. A qualitative interpretation of these results is given in terms of the fairly rapid attainment of a constant number of polymer particles on which monomer is weakly adsorbed, a proportion of which are at any given moment inert, the remainder growing by consuming adsorbed monomer. Initiation, propagation, and mutual termination in the aqueous phase all play a significant part.

The polymerization of acrylonitrile in aqueous solution. Part II. The reaction photosensitized by Fe3+, Fe3+OH−, Fe2+, and I− ions

AbstractThe polymerization of acrylonitrile in aqueous solution photosensitized by Fe2+, Fe3+OH−, and I− has been determined dilatometrically at 25°C. After an acceleratory phase caused partly by increasing intensity of absorbed light due to light‐scattering by the insoluble polymer particles, a steady rate Rp is established and continues up to ∼10% conversion. Rp is proportional to Iabs[m1]1.0, where x is slightly greater than 0.5 unless ferric ions are present which may oxidize and terminate polyacrylonitrile radicals and cause x to be greater than 0.5. In accordance with earlier measurements, ϕ for the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm Fe}^{3 +} {\rm OH}- {{{3130\ {\rm A}.} \atop {-\hskip-4pt-\hskip-4pt-\hskip-4pt-\hskip-4pt-\hskip-4pt-\hskip-4pt-\hskip-5pt\longrightarrow}}\atop{}}{\rm Fe}^{2 +} + {\rm OH}$$\end{document} is found to be 0.15. Propagation occurs by addition (a) of dissolved monomer molecules to polymer radicals S* (kp = 1.45 × 104 l. mole−1 sec.−1) and (b) of adsorbed monomer molecules to the radical in suspended polymer particles P* which contain several polymer molecules and one growing radical. S* radicals are subject to mutual termination (kt = 2 × 109 l. mole−1 sec.−1) and oxidative termination by ferric ion (k4 = 1.3 × 104 l. mole−1 sec.−1). As soon as the steady state is established [P*] is constant, but after stopping irradiation [P*] decays slowly and bimolecularly and therefore gives rise to a small aftereffect. Agitation causing the polymer suspension to coagulate (a) reduces Rp due to changes in Iabs and a decrease in the number of particles and (b) decreases the half‐life of the aftereffect by increasing the rate of mutual destruction of P* particles.