Photodegradation of polypropylene in the presence of ferric chloride

The effect of ferric chloride (FeCl₃) on photodegradation of isotactic polypropylene (PP) was investigated using mainly ESR spectrometry. PP powder, its oxidized samples, and FeCl₃-adsorbing PP samples were irradiated under a nitrogen atmosphere at 77°K with ultraviolet light from a high-pressure mercury lamp and a superhigh-pressure mercury lamp modified by various filters. Methyl, polymerci alkyl, and peroxy radicals were observed in the ESR spectra of the irradiated samples, and it was found that FeCl₃ depresses the formation of alkyl radicals and accelerates the formation of peroxy radicals catalyzing the reaction. From infrared study of UV-irradiated film samples, it was also inferred that FeCl₃ accelerates the photodegradation the hydroperoxide and carbonyl groups.     

On the photooxidative behavior of TiO2 and PW12O403−: OH radicals versus holes

Parallel experiments under similar conditions, using various substrates (atrazine, fenitrothion, 4-chlorophenol and 2,4-D) and OH radical scavengers (Br⁻, isopropyl alcohol, tertiary butyl alcohol and acetone), have shown that the photooxidizing mode of PW₁₂O₄₀³⁻ and TiO₂, i.e., OH radicals and/or holes (h⁺), depends on the nature of substrate and the mode of investigation. This provides an explanation for the controversial results reported in the literature. Atrazine shows that both PW₁₂O₄₀³⁻ and TiO₂ operate, mainly, via OH radicals and to a lesser extent with holes (h⁺), whereas, fenitrothion suggests that both systems operate almost exclusively, via OH radicals. Differences in the action of the catalysts are encountered in the photodegradation of 4-chlorophenol (4-ClPh) and 2,4-dichlorophenoxyacetic acid (2,4-D). PW₁₂O₄₀³⁻ appears to operate essentially via OH radicals, whereas, h⁺ appear to be the major oxidant with TiO₂. Overall, though, the action of OH radicals relative to h⁺ appears to be more pronounced with PW₁₂O₄₀³⁻ than TiO₂.     

In situ preparation of N,N-dimethyl-n-butylamine for 2,6-dimethylphenol polymerization

2,6-Dimethylphenol (2,6-DMP) polymerization with a catalytic complex of Cu₂O/HBr/N,N'-di-tert-butylethylene diamine (DBEDA)/N,N-dimethyl-n-butylamine (DMBA)/dibutylamine (DBA) was studied, in which DMBA was prepared in situ from the methylation of n-butylamine over four different solid acid catalysts (two different γ-alumina, one silica-alumina, and one zeolite). The effectiveness of the unpurified methylation product solutions for promoting the 2,6-DMP polymerization was strongly dependent on the type of solid acid catalysts used. The performance of the best one (untreated product solution from the methylation reactor with Condea γ-alumina catalyst) was very similiar to that of the reagent grade DMBA. Infrared spectrum studies showed that DMBA acted as the external base for the 2,6-DMP polymerization catalyst system to neutralize the excess hydrobromic acid and to increase the polymerization rate. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of electrically conducting copolymers based on benzene and biphenyl

Poly(p‐phenylene) (H‐PPP), which is one of the firstly investigated conducting polymer, has the disadvantage of difficult processability because it is infusible and insoluble. The use of biphenyl instead of benzene leads to ortho‐, meta‐, para‐polyphenylenes (H‐PP) which are more soluble and easier to be processed, however their electrical conductivity is lower. Copolymers of polyphenylenes (C₁ and C₂) and corresponding homopolymers (H‐PPP and H‐PP) were produced by the oxidative cationic polymerization of benzene and/or biphenyl. The soluble (‐S) and the insoluble (‐I) in chlorobenzene polyphenylenes were separated (H‐PP‐I, H‐PP‐S, C₁‐I, C₁‐S, C₂‐I, and C₂‐S) and they were doped with a solution of FeCl₃. All polyphenylenes were studied by FTIR, XRD, TGA, and their electrical conductivity with constant current was determined. Pronounced differences between the copolymers and the homopolymers were observed, indicating the different structure of the former. The values of the electrical conductivity of doped insoluble copolymers (10^?4 and 10^?5 S/cm) are between that of H‐PPP (10^?3 S/cm) and H‐PP‐I (10^?6 S/cm). The values of the electrical conductivity of doped soluble copolymers (10^?5 S/cm) are considerably higher than that of H‐PP‐S (10^?9 S/cm). The new electrically conductive polyphenylenes that were produced differ significantly from the corresponding homopolymers and combine good electrical conductivity and solubility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Selective chlorination of 4-chlorotoluene to 2,4-dichlorotoluene over zeolite catalysts

The performance of various zeolites in the liquid phase chlorination of 4-chlorotoluene (4-CT) with gaseous chlorine at a moderate temperature and normal pressure has been examined. A comparison under the same conditions with Lewis acid catalyst FeCl₃, is also carried out. It is found that zeolite K-L exhibits higher selectivity for 2,4-dichlorotoluene (2,4-DCT/3,4-DCT = 3.54) compared to the other zeolites studied and also FeCl₃ catalyst (2,4-DCT/3,4-DCT = 3.18), while the rate of 4-CT conversion (75.8 mmol g^–1 h^–1) is found to be comparable on K-L and FeCl₃ catalysts. The highest rate of 4-CT conversion, among the catalysts studied is obtained over K-beta (101.4 mmol g^–1 h^–1). FeCl₃ catalyst produces higher amounts of tri- and tetra-substituted products due to its non-shape-selective character. Mainly the side-chain chlorinated product (,4-dichlorotoluene) is obtained over K-X, amorphous SiO₂ and in the absence of catalyst. Solvents influence the rate of 4-CT conversion as well as the 2,4-DCT/3,4-DCT isomer ratio. 1,2-dichloroethane appears to be the best solvent in enhancing the 2,4-DCT/3,4-DCT isomer ratio when the reaction temperature is raised from 313 to 353 K.     

Influence of type and positioning of N-aryl substituents on vinyl polymerization of norbornene by Ni(II) α-diimine complexes

Effects of structural variations of the diimine ligand on catalyst activities for vinyl polymerization of norbornene (NB) have been investigated by a series of Ni(II) α-diimine catalysts of the general formula: [{ArN=C(Ac)-C(Ac)=NAr}]NiBr₂ (Ac=acenaphthyl) (Cat(H), Ar=C₆H₅; Cat(2,6-Me), Ar=2,6-C₆H₃Me₂; Cat(2,6-Et), Ar=2,6-C₆H₃Et₂; Cat(2,6- i Pr), Ar=2,6-C₆H₃ i-Pr₂; Cat(2,3-Me), Ar=2,3-C₆H₃Me₂; Cat(2,4-Me), Ar=2,4-C₆H₃Me₂; Cat(2,5-Me), Ar=2,5-C₆H₃Me₂; Cat(3,5-Me), Ar=3,5-C₆H₃Me₂; Cat(2,4,6-Me), Ar=2,4,6-C₆H₂Me₃). In situ reactions with methylaluminoxane generated the active catalysts, and they showed good activity towards NB polymerizations. As indicated by relatively higher activities of Cat(H) and Cat(3,5-Me), it can be generalized that catalysts having 2,6-substituents are less active due to steric interaction between monomer and substituents. In addition, electron donating methyl groups at 2-, 4-or 6-position on the N-aryl have a con effect and that at 3,5-position has a pro effect. This paper was presented at the 11th Korea-Japan Symposium on Catatysis held at Seoul, Korea, May 21–24, 2007.     

Reaction of α-tocopherol with alkyl and alkylperoxyl radicals of methyl linoleate

α-Tocopherol was reacted with alkyl and alkylperoxyl radicals at 37°C in bulk phase. The lipid-free radicals were generated by the reaction of methyl linoleate with the free radical initiator, 2,2′-azobis(2,4-dimethylvaleronitrile) (AMVN) under air-insufficient conditions. The products were isolated by high-performance liquid chromatography. Their structures were identified as 2-(α-tocopheroxy)-2,4-dimethylvaleronitrile (1), a mixture of methyl 9-(8a-peroxy-α-tocopherone)-10(E),12(Z)-octadecadienoate and methyl 13-(8a-peroxy-α-tocopherone)-9(Z),11(E)-octadecadienoate (2), methyl 9-(α-tocopheroxy)-10(E),12(Z)-octadecadienoate (3a), methyl 13-(α-tocopheroxy)-9(Z),11(E)-octadecadienoate (3b), α-tocopherol spirodiene dimer (4) and α-tocopherol trimer (5). When methyl linoleate containing α-tocopherol was oxidized with AMVN under airsufficient conditions, the main products were 8a-alkyl-peroxy-α-tocopherones (2). In addition to these compounds, 6-O-alkyl-α-tocopherols (1, 3a and 3b) were formed when the reaction was carried out under air-insufficient conditions. The results indicate that α-tocopherol can react with both alkyl and alkylperoxyl radicals during the autoxidation of polyunsaturated lipids.     

1H nuclear magnetic resonance study of polyurethane prepolymers from toluene diisocyanate and polypropylene glycol

Polyurethane prepolymers prepared from toluene 2,4‐diisocyanate, toluene 2,6‐diisocyanate, and polypropylene glycol with a ratio between the isocyanate and hydroxyl groups equal to 2 were analyzed by ¹H nuclear magnetic resonance (NMR) spectroscopy in acetone‐d₆. Different temperatures and concentrations were used. Toluene 2,4‐dimethylurethane and toluene 2,6‐dimethylurethane were synthesized and used as model compounds to assign prepolymers signals. Measurements of spin–lattice relaxation time T₁ by “inversion recovery” experiments were carried out on toluene 2,4‐diisocyanate, toluene 2,6‐diisocyanate, toluene 2,4‐dimethylurethane, toluene 2,6‐dimethylurethane, and polyurethane prepolymers. Differences in T₁ times were used to interpret prepolymers spectra, by means of the strong observed effect on protons due to the presence of adjacent isocyanate groups. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 347–357, 2003     

Photooxidation of polypropylene under natural and accelerated weathering conditions

The environmental and accelerated photodegradation of two polypropylene (PP) films (high and low crystallinity) were investigated. FT-IR measurements coupled with derivatization reactions (NO and SF₄), elongation at break tests and gel permeation chromatography technique were used to monitor the degree of oxidation during the UV exposure. No stoichiometry changes were observed under both UV conditions for the PP films. The dominant photoproduct, i.e., ketone, was suggested to be produced from peroxy radicals. The low concentration of tert-alcohol detected questioned the validity of its formation from hydroperoxide decomposition as suggested by several authors. Under natural exposure, the effect of degradation on mechanical property was different for high and low PP. High PP was useless after a short exposure time; low PP retained its physical property for a longer period of time. In the latter case, the analysis of the changes in elongation at break, the polydispersity P = M_w/M_n, the number of chain scissions N_t, and the kinetic accumulation of photoproducts provided strong indications on the mechanisms of acid and ester production and shed some light on the competition between crosslinking and chain scission reactions. The estimated acceleration factors were 7.5 and 8.5 for high and low PP, respectively, values that were much lower than those obtained for linear low-density polyethylene. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2497–2503, 1997     

Reaction of Aryl Iodides with (PCP)Pd(II)—Alkyl and Aryl Complexes: Mechanistic Aspects of Carbon—Carbon Bond Formation

The reaction of the PCP-type complex Pd(Me){2,6-(ⁱPr₂PCH₂)₂C₆H₃}( 3 ) with phenyl iodide results in the formation of Pd(I){2,6-(ⁱPr₂PCH₂)₂C₆H₃} ( 5 ), methyl iodide, toluene, and biphenyl. Formation of Pd(Ph){2,6-(ⁱPr₂PCH₂)₂C₆H₃}( 4 ) is observed during the reaction by ³¹P NMR. Reaction of 4 with aryl iodides results in the formation of 5 and Ph–Ph, Ph–Ar, and Ar–Ar, products indicative of a radical reaction. Under pseudo-first-order conditions, the rates of the reactions follow the order p-OMe > p-Me > H > p-NO₂ > m-Cl. The reaction is likely to involve electron transfer from 4 to the aryl iodide followed by fast decomposition of a postulated radical cation [Pd(Ph){2,6-(ⁱPr₂PCH₂)₂C₆H₃}]^+. ( 4 ^+.) to give a phenyl radical and [Pd{2,6-(ⁱPr₂PCH₂)₂C₆H₃}]⁺ ( 6 ⁺). Facile decomposition of the aryl iodide radical anion generates an aryl radical and I⁻. Recombination of aryl radicals gives rise to mixed biaryls, and 6 ⁺ combines with I⁻ to give 5 .     

A study of the interaction of mechanically generated polypropylene radicals with phenolic antioxidant in the absence of oxygen using ESR spectroscopy

Polypropylene (PP) was mechanically degraded in the absence and in the presence of a phenolic antioxidant, 2,6-di-t-butyl-p-cresol. The interaction of macroradicals of PP with the antioxidant was studied by ESR spectroscopy in the temperature region between 77 and 303 K and at antioxidant concentrations of 0.1, 0.5, and 1.5 wt % in the absence of oxygen. In the absence of the antioxidant, the end macroradicals of PP are formed which decay with increase in temperature. In the presence of antioxidant both macroradicals of PP and phenoxy radicals are generated. The PP macroradicals are very stable up to the temperature close to T_g of the polymer. Beyond this temperature they decay via bimolecular mechanism—according to the second-order kinetics. The rate constants for PP macroradicals decay were determined, and the apparent activation energies for the regions of slow and fast decay were calculated.     

Photocatalyzed Degradation of Phenol, 2,4-Dichlorophenol,Phenoxyacetic Acid and 2,4-Dichlorophenoxyacetic Acid over SupportedTiO2 in a Flow System

The photodegradation of phenol, 2,4-dichlorophenol, phenoxyacetic acid and 2,4-dichlorophenoxyacetic acid using TiO₂ as photocatalyst is investigated. The photodegradations of these compounds have been conducted in a continuous mode by means of a flow system, in which TiO₂ remains fixed onto glass pearls. The use of this system gives high yields of degradation for the chemicals tested, except for 2,4-dichlorophenol for which a slow dechlorination process is observed. The rate of photodegradation depends on the pH of the solution, the point of zero charge of TiO₂ and the pK_a of the chemicals being the key parameters. The main aromatic intermediates detected have been hydroquinone,paraquinone and hydrohydroquinone during phenol degradation; phenol and hydroquinone during phenoxyacetic acid degradation; chlorohydroquinone and chlorophenol during 2,4-dichlorophenol degradation; and dichlorophenol during 2,4-dichlorophenoxyacetic acid degradation. Finally, some long term irradiations with phenol as model compound have been performed, showing high degrees of photodegradation. It has been observed that only a periodic evacuation of the effluent out of the reactor is needed to sustain high percentages of photodegradation.     

Novel copolymers of trisubstituted ethylenes with styrene — 7. Methyl 2-cyano-3-dihalophenyl-2-propenoates

Summary Methyl 2-cyano-3-dihalophenyl-2-propenoates, R₂C₆H₃CH=C(CN)CO₂CH₃ (R₂= 2,4-difluoro, 2,5-difluoro, 2,6-difluoro, 3,4-difluoro, 3,5-difluoro, and 2-chloro-6-fluoro), were prepared by the piperidine catalyzed Knoevenagel condensation of corresponding disubstituted benzaldehydes and methyl cyanoacetate. Novel copolymers of the propenoates and styrene were prepared at equimolar monomer feed by solution copolymerization in the presence of a radical initiator. The order of relative reactivity (1/r ₁) was 2,5-difluoro (2.11) > 2,6-difluoro (1.84) > 3,5-difluoro (1.71) > 2,4-difluoro (1.4) > 3,4-difluoro (0.65) > 2-chloro-6-fluoro (0.59). The copolymers were characterized by IR, ¹H and ¹³C NMR, GPC, DSC and TGA. High glass transition temperatures of the copolymers compared that of polystyrene indicates a substantial decrease in chain mobility of the copolymers due to the high dipolar character of the trisubstituted ethylene monomer unit. Received: 12 June 2000/Revised version: 12 September 2000/Accepted: 12 September 2000     

Radiation Chemistry of Ethylene Glycol,Meso-Erythritol, 2-Deoxy-D-Ribose and Alkyl Phosphates as DNA Model Compounds

The γ-radiolysis of ethylene glycol, meso-erythritol, 2-deoxy-ribose, and alkyl phosphates has been studied in diluted (10^?2 M), N₂ O-saturated, deoxygenated aqueous solutions. Products and their G values have been determined. Reaction schemes were derived from complete material balances. In the polyols the primary attack of the radiolytically formed OH radicals and H atoms leads to α, β-dihydroxyalkyl radicals (A) which eliminate water to give substituted α-carbonyl-methyl radicals: (B) Disproportionation reactions of the radicals A and B yield products having the structural units ? CO? CHOH? and ? CO? CH₂ —. In ethylene glycol a chain reaction is induced, radical B abstracts a hydrogen from ethylene glycol to give acetaldehyde and radical A. In 2-deoxy-ribose the major attack is at C-1. Products from this radical are 2-deoxy-ribonic acid and 2,5-dideoxy-ribonic acid. In the formation of the latter a rearrangement is involved. With trimethyl phosphate, the reaction of the solvated electron is only small (2 × 10^s 1/mole sec), as shown by pulse radiolysis. Dimethyl and methyl phosphates do not react with the solvated electron to a measurable extent. The attack of the OH radical apparently leads to a cleavage of the alkyl phosphate linkage.     

Synthesis and spectroelectrochemistry of dithieno(3,2‐b:2′,3′‐d)pyrrole derivatives

New π‐conjugated polymers containing dithieno(3,2‐b:2′,3′‐d)pyrrole (DTP) were successfully synthesized via electropolymerization. The effect of structural differences on the electrochemical and optoelectronic properties of the 4‐[4H‐dithieno(3,2‐b:2′,3′‐d)pyrrol‐4‐yl]aniline (DTP–aryl–NH₂), 10‐[4H‐dithiyeno(3,2‐b:2′,3′‐d)pirol‐4‐il]dekan‐1‐amine (DTP–alkyl–NH₂), and 1,10‐bis[4H‐dithieno(3,2‐b:2′,3′‐d)pyrrol‐4‐yl] decane (DTP–alkyl–DTP) were investigated. The corresponding polymers were characterized by cyclic voltammetry, NMR (¹H‐NMR and ¹³C‐NMR), and ultraviolet–visible spectroscopy. Changes in the electronic nature of the functional groups led to variations in the electrochemical properties of the π‐conjugated systems. The electroactive polymer films revealed redox couples and exhibited electrochromic behavior. The replacement of the DTP–alkyl–DTP unit with DTP–aryl–NH₂ and DTP–alkyl–NH₂ resulted in a lower oxidation potential. Both the poly(10‐(4H‐Dithiyeno[3,2‐b:2′,3′‐d]pirol‐4‐il)dekan‐1‐amin) (poly(DTP–alkyl–NH₂)) and poly(1,10‐bis(4H‐dithieno[3,2‐b:2′,3′‐d]pyrrol‐4‐yl) decane) (poly(DTP–alkyl–DTP)) films showed multicolor electrochromism and also fast switching times (<1 s) in the visible and near infrared regions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40701.     

Synthesis of Methylene‐Bridge Polyarenes through Palladium‐Catalyzed Activation of Benzylic Carbon‐Hydrogen Bond

In the presence of palladium(II) acetate [Pd(OAc)₂] and an N‐heterocyclic carbene (NHC) ligand, fluorene derivatives can be generated in good to excellent yields from 2‐halo‐2′‐methylbiaryls through the benzylic C H bond activation (14 examples; 81–97% yields). The scope and limitations of this protocol have been examined. A wide range of functional groups, such as alkyl, alkoxy, ester, nitrile, and others, is able to tolerate the reaction conditions herein. The cyclization of an isotope‐labelled biphenyl gave the corresponding product with a primary kinetic isotope effect (k_H/k_D=4.8:1), which indicates that the rate‐determining step of this reaction is the activation of the benzylic C H bond. Moreover, indenofluorenes were also accessed in excellent results from terphenyls (3 examples; 91–92% yields). The cascade reaction of 2,6‐dichloro‐2′‐methylbiphenyl with diphenylacetylene produced 8,9‐diphenyl‐4H‐cyclopenta[def]phenanthrene in 60% yield through the activation of an aryl and a benzylic C H bond.     

Solvent effects on polymerization of functionalized monomers in presence of alkyl halide/CuBr without a ligand

A modified system of atom transfer radical polymerization was used to perform polymerization of sodium o-methacryloylaminophenylarsonate (o-MAPHA-Na). The reaction was carried out without ligand at 48 °C for 45 h with methyl 2-chloro-propionate (MCP) as the initiator, copper bromide (CuBr) as the metal, and different mixtures of polar solvents, including: dimethylformamide (DMF):H₂O (60:40), dimethylsulfoxide (DMSO):H₂O (20:80), and DMSO. The ¹H NMR spectra showed that MCP was covalently attached as end group of the resulting polymers. Unexpectedly, we found that o- and p-MAPHA-Na could polymerize in the presence of alkyl halides without any initiation method to produce free radicals from alkyl halide. Further experiments suggested that radicals could be generated from the used monomer by initiation methods such ultraviolet radiation of environmental light or temperature. Thus, it was possible that the monomer generated phenyl radicals by breaking its C-As bond. Reactions of o-MAPHA-Na and o-MAPHA with MCP and different ratios of H₂O:DMF and H₂O:Metanol (MeOH) showed that water was necessary for polymerization to proceed. Finally, we found that o-MAPHA underwent self-initiated polymerization when water was present in the reaction media.     

Polypropylene plasticization and photodegradation with a TiO2/poly(ethylene oxide)/methyl linoleate paint photocatalyst system

The photodegradation of polypropylene (PP) film was performed by a TiO₂/polyethylene oxide (PEO)/plant oil paint photocatalyst system. The photodegradation underwent two stages of development as follows: Initially PP reacted with linoleic acid radical originated from the photoreaction of plant oil component. Second, the linoleic acid graft‐polymer was decomposed, and then PP chain scission was caused. The process was studied using methyl linoleate (ML) in detail. The melting point of the 24 h‐photodegraded PP slightly decreased, and those of the 48 h‐ and 96 h‐ones drastically did as compared with the pristine PP. The crystallinity (χ_c) decreased at the 48 h photodegradation time and drastically increased at the 96 h one. The 24 h‐photodegraded PP showed the 77% Young's modulus, 88% tensile strength, and 103% strain at break values to those of the pristine PP. The ML graft‐polymerization and decomposition brought about the PP plasticizing and chemi‐crystallization, causing the PP degradation. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39909.     

The Di-t-butylation of p-cresol with t-butanol in Supercritical CO2 over Tungstophosphoric Acid Supported on Ordered Mesoporous Silica

Tungstophosphoric acid (HPW) supported on MCM-41 was an excellent catalyst for the t-butylation of p-cresol to 2,6-di-t-butyl-4-methylphenol (2,6-DTBPC) in supercritical CO₂; however, zeolites, H-Y and H-Beta, only gave 2-t-butyl-4-methylphenol (2-TBPC) because of their limitation in pore size. The yield of 2,6-DTBPC was maximized at 110 °C, and further increase in temperature rather decreased the yield. The yield of 2,6-DTBPC was maximized at 10–11 MPa CO₂ pressure, and further increase of the pressure decreased in the conversion of phenol and the yield of 2,4-DTBC. The thermogravimetric analysis of used catalysts showed that the coke-formation was minimized in supercritical CO₂ compared to the other reaction media such as in liquid phase and in N₂ atmosphere.     

An ecologically effective water treatment technique using electrochemically generated hydroxyl radicals for in situ destruction of organic pollutants: Application to herbicide 2,4-D

The electrochemical production of Fenton's reagent by simultaneous reduction of dioxygen and ferric ions on a carbon felt electrode, permits a controlled, in situ generation of hydroxyl (OH^·) radicals. The possibility of using electrochemically produced OH radicals for solving environmental problems is investigated. Continuous and controlled production of hydroxyl radicals was achieved by electrochemical reduction of O₂ in the presence of a catalytic amount of ferric or ferrous ion. These radicals are used for remediation of water containing toxic-persistent-bioaccumulative organic pollutants through their transformation into biodegradable compounds or through their mineralization into H₂O and CO₂. A widely used herbicide, 2,4-dichlorophenoxyacetic acid (2,4-D), was selected as a model for a toxic organic pollutant. High pressure liquid chromatography (HPLC) was used to quantify the distribution of the hydroxylated products obtained. Rate constants for the hydroxylation reactions of 2,4-D, 2,4-dichlorophenol (2,4-DCP), 2,4-dichlororesorcinol (2,4-DCR) and 4,6-dichlororesorcinol (4,6-DCR) were determined. The mineralization of 2,4-D and its derivatives was followed by total organic carbon (TOC) measurements. More than 95% of 2,4-D and the intermediates generated during the electrolysis can be mineralized.