Ozone interaction with conjugated polymers—I. Polyacetylene

Free-standing films of cis- and trans-rich polyacetylene (PA) obtained on a Rh(I) catalyst, were treated with ozonized oxygen (O₃ 1% by weight on average). The initial superficial charge-transfer complex formed between ozone and the polyene chain and the subsequent ozone accelerated cis-trans isomerization were studied by electronic and FT-IR spectroscopies. A peculiar mechanism of interaction between ozone and polyenic chain was proposed, and cation radicals were observed on the ozone doped surfaces of PA. Ozone treatment of PA films creates a superficial oxidized barrier that prevents subsequent thermo-oxidative destruction of the bulk portion of PA film. This treatment could be a way of protecting PA from degradative oxidation.     

Ozonization of electronic conducting polymers: II. Degradation or doping

The ozonization of poly[3-pentylthiophene], poly[3-heptylthiophene] and poly[3-nonylthiophene] was carried out in room temperature. The DC conductivity changes during the ozonization have been recorded, revealing significant conductivity increase (up to two orders of magnitude). Moreover, an analysis of electron microscopy images has shown that ozone related swelling of polymer bundles caused the granular structure of the samples to fade away. The analysis of FTIR spectra indicated the presence of physisorbed ozone as well as oxidative degradation products in the ozonized polymer samples.     

Degradation of lignin by ozone. III. The fate of the carbohydrate matrix during the degradation of spruce protolignin by ozone

Solvent-extracted spruce wood meal was ozonized in 45% aqueous acetic acid at room temperature. The ozone-treated wood meal was then extracted with dilute alkali at 65°C for 1 h. Lignin, α-cellulose, and hemicellulose content and the viscosities of the pulped wood-meal samples were measured as a function of the time of ozonization. Results indicate that although the attack on the wood components by ozone is not selective in this medium cellulose and hemicelluloses are degraded slowly compared with lignin. Lignin degraded approximately four times faster than the carbohydrates. At the fiber liberation point the pulp retained 78% of the original hemicelluloses and about 90% of the α-cellulose compared with 25% of the lignin. The pulp samples obtained during ozonization of the wood meal showed a slow decrease in the average degree of polymerization (DP); the limit reached near 350 was attributed to the inaccessibility of the ordered regions in native cellulose to ozone.     

Some aspects of the ozone degradation of poly(vinyl alcohol)

Poly(vinyl alcohol) (PVAL) forms a strong hydrogen-bond complex with ozone. The interaction energy is of the order of 47.3 kJ/mol as calculated from the blue shift undergone by the ozone absorption band in the UV after its complexation with PVAL. This fact may have many important practical implications in the application of PVAL in wastewater treatment both in terms of O₃ dissolution and persistence in water. Furthermore, PVAL is easily biodegradable but it is also slowly degraded by ozone. It is shown by viscometry, electrical conductimetry and by pH measurements that PVAL is degraded by ozone attack with extensive chain breaking. By FT-IR spectroscopy it has been shown that the final product is a PVAL oligomer with numerous ketonic groups along the main oligomer backbone and with carboxylic end groups. A mechanism of ozone degradation of PVAL has been presented and discussed. The chain scission is based on the ozone oxidation of the alcoholic groups of PVAL with formation of ketonic groups which in turn are the source of a keto-enol tautomerism which leads to random chain scission by further O₃ attack. Viscometric measurements show that the main viscosity drop of PVAL is achieved when a nominal stoichiometric ratio of O₃/PVAL < 0.05 is reached which means one ozone molecule for every >20 PVAL monomeric units. For comparison PVAL has been oxidized also with paraperiodic acid.Ozonized PVAL has been studied by thermal analysis (TGA, DTG and DTA) in comparison to a reference untreated PVAL under N₂. The oxidation of PVAL causes its complete amorphization since the crystalline melting point of PVAL at 235 °C is no longer detectable in the case of ozonized PVAL. In any case ozonized PVAL shows a better thermal stability which can be confirmed for instance by a higher maximum decomposition rate temperature as measured by DTG. This result is in agreement with theoretical calculations made by group increments according to Van Krevelen's method which predicts a higher decomposition temperature for a PVAL having ketonic groups in place of alcoholic moieties in the main polymer backbone.     

Influence of ozonized kraft lignin on the crystallization of CaCO3

Results are reviewed from a study examining how structural modifications introduced by ozonization enhance the influence of kraft lignin on the crystallization of CaCO(3). Ozone treatment of kraft lignin in an aqueous environment is shown to increase its carboxylic acid and overall oxygen content and reduce its molecular weight. Calcium concentration and temperature were monitored in heated supersaturated solutions containing ozonized kraft lignins to gauge their influence on CaCO(3) crystallization processes. The presence of kraft lignin raises the temperature necessary to induce crystallization. This effect is shown to level off at relatively low lignin concentrations and be dependent on the extent of ozone treatment the kraft lignin has undergone. A linear correlation is found between crystallization temperatures and the carboxylic acid content of ozonized lignin samples indicating the introduction of these functional groups plays an important role in enhancing its inhibitory effect. Scanning electron microscopy images of crystals grown in the presence of kraft lignins show significant morphological modifications. These are consistent with specific or pseudo specific interactions between the lignin and crystal faces of calcite to inhibit growth parallel to its c axis. The influence over crystal morphology demonstrated by modified kraft lignin increases with increasing ozonization. Also presented here are crystallization temperature data for a range of kraft lignin ultrafiltration fractions, which indicate that the optimal (nominal) molecular weight of kraft lignin for inhibiting the crystallization of CaCO(3) lies between 5000 and 10000.     

Synthesis of polyphenylacetylene by radiation-induced polymerization in deoxycholic acid clathrate

Phenylacetylene was polymerized as inclusion compound (clathrate) inside deoxycholic acid (DOCA) crystals. The polymerization was initiated by γ radiation and a total dose of 320 kGy was employed. The resulting polyphenylacetylene (PPA) was isolated by dissolution of deoxycholic acid in boiling ethanol. PPA high polymer was accompanied by a series of phenylacetylene oligomers, which were detected by liquid chromatographic analysis (HPLC). PPA was characterized by electronic absorption spectroscopy and by FT-IR spectroscopy in comparison to a reference PPA prepared by a stereospecific catalyst. The microstructure of PPA from inclusion polymerization was highly trans type, similar to that observed on PPA prepared by bulk radiolysis. No optical activity was detected by polarimetry on PPA prepared by inclusion polymerization.The host–guest complex PPA/DOCA was studied by differential thermal analysis (DTA) and by thermogravimetry (TGA). DTA provided evidences of the host–guest complex formation from the shift of the melting point of DOCA while the TGA confirmed the identity – in terms of thermal behaviour – of the PPA from inclusion polymerization with that from stereospecific polymerization.     

Synthesis of ion exchange membranes from ozonized high density polyethylene

The synthesis and the characterization of graft copolymers prepared from ozonized high density polyethylene (HDPE) are described. The powder of HDPE was treated with ozone in well defined conditions and then copolymerized with monomers, such as, acrylic acid (AA), N,N-dimethylamino-2 ethylmethacrylate (MADAME) and vinyl phosphonic acid (VPA). Cationic exchange membranes were prepared from the grafted copolymers of AA and VPA and anionic exchange membrane from the grafted copolymer of MADAME. The obtained copolymers were characterized by the grafting rate, FTIR spectroscopy, scaning electronic microscopy, thickness, exchange capacity and electrical resistance.     

Radiation-cured polyisoprene/C60 fullerene nanocomposite. Part 1: Synthesis in hexane and in toluene

Fullerene C₆₀ can be grafted onto polyisoprene chains by γ irradiation in n-hexane or in toluene. The resulting polyisoprene/C₆₀ nanocomposites can be easily recovered from the solutions and have been characterized by electronic absorption and Fourier transform-infrared (FT-IR) spectroscopy. The electronic absorption spectroscopy clearly shows that C₆₀ undergoes addition reaction from the polyisoprene macroradicals formed by γ radiolysis. FT-IR spectroscopy supports the grafting reaction of polyisoprene on C₆₀ and additionally it shows that C₆₀ acts as a sensitizer for the partial cis–trans isomerization of the polyisoprene monomeric units. Relatively high levels of C₆₀ lead the polyisoprene-based nanocomposite to a crosslinked gel.The thermal behaviour of the polyisoprene/C₆₀ nanocomposites has been studied by the thermogravimetric analysis (TGA-DTG). It is shown that the radical adducts polyisoprene/C₆₀ are thermally reversible and regenerate free C₆₀ during the pyrolysis under N₂.     

Surface oxidation of rubber crumb with ozone

Rubber crumb derived from the grinding of used truck tread and tyres is used as a low cost filler in rubber compounds based on diene rubber. In order to expand its application to other fields, the surface modification of the rubber crumb could be an interesting and feasible solution. In fact, the surface modification of rubber crumb may be used as a tool to expand its use in applications to compounds with polar rubber matrices or where hydrophilic surface of the rubber crumb could be desirable, for example in water-based dispersion or as filler for asphalt. In the present work, ozone has been used as the active agent to cause surface oxidation and functionalisation of rubber crumb in a fluidized bed reaction. The rubber crumb reacts swiftly with ozone producing CO₂ in the initial stages of reaction and then leading to the desired surface oxidized product. The rate constant of the reaction between ozone and rubber crumb has been determined by FT-IR spectroscopy, monitoring the consumption of ozone in the gas phase in the presence of the crumb. A rate constant value of 5.03 × 10⁻³ s⁻¹  g⁻¹ of rubber crumb was determined. The degree of the surface oxidation of the rubber crumb can be determined by FT-IR spectroscopy using as reference the intensity of the ketone band at about 1710 cm⁻¹. Additionally the nominal ratio between the amount of ozone (in mg) reacted with rubber crumb (in g) can be used as a parameter for the degree of the surface oxidation. The surface oxidized rubber crumb shows surface acidity and hydrophilicity. Thermogravimetric analysis, differential thermal analysis and pyrolysis-GC clearly demonstrate that the ozonization of the rubber crumb is directed exclusively to the surface of the crumb and does not affect the bulk properties at all.     

Kinetics and mechanism of selenium-catalyzed isomerization of some cis-diarylacrylonitriles

The kinetics of the cis-trans isomerization of some ,β-diarylacrylonitriles has been investigated in decahydronaphthalene at 150–190° with selenium as a catalyst. The reaction is first order with respect to olefin and 1/2 apparent order with respect to catalyst. Isomerization rate is increased by electron donating groups in the -phenyl and by electron withdrawing ones in the β-phenyl. Satisfactory correlations between log k and substituent σ⁺ values are observed. Evidence is obtained for a free radical mechanism. The results are consistent with a reaction path involving the formation of a σ-complex between the -C atom and selenium diradical, followed by a free rotation around the single bond and removal of the catalyst. The effects of heteroaromatic nuclei linked to -C atom on the isomerization rate (phenyl>2-furyl>2-thienyl) indicate the lack of conjugation from heteroatom to the side chain in the rate determining step.     

Photo-oxidation and ozonization of poly(3-hexylthiophene) thin films as studied by UV/VIS and photoelectron spectroscopy

The kinetics and the mechanisms of degradation of thin P3HT layers have been investigated quantitatively for ozonization and photo-oxidation. Both, decay kinetics and product evolution of the polymer degradation are monitored by in situ UV/VIS and X-ray photoelectron spectroscopy (XPS). The degradation pathways of ozonization and photo-oxidation of P3HT turn out to be significantly different. Ozone attacks the thiophene units mainly by direct addition to the double bonds, leading to the loss of UV/VIS absorption, while the aliphatic side chains [1] are hardly affected. During photo-oxidation, the polymer is primarily attacked at the alkyl side chain which leads to the formation of reactive peroxide species. These subsequently cause the oxidation of sulfur and concomitantly the destruction of the thiophene ring, resulting in the loss of absorption. From the kinetics of the blue shift of the optical absorption it is concluded that the polymer is mainly attacked at the terminal thiophene rings the case of photo-oxidation whereas ozone attacks positions more or less randomly distributed along the chain. The rate of photo-oxidation under AM 1.5 conditions is at least one order of magnitude faster than the decomposition of P3HT by ozone.     

MECHANICAL PROPERTIES OF OZONIZED HDPE FILLED WITH SERICITE-TRIDYMITE-CRISTOBALITE

The mechanical properties of ozonized high density polyethylene (HDPE) blended with sericite-tridymite-cristobalite (STC) were studied in this paper. The experimental results show that some oxygen containing polar groups are introduced on the molecular chain of HDPE through ozonization, the compatibility between HDPE and STC is thus improved, the mechanical properties of the blend are markedly enhanced. Compared with untreated HDPE/STC (60/40) blend, the yield strength and notched impact strength of ozonized HDPE/STC (60/40) blend are increased from 27.0MPa to 29.5MPa and from 2.8kJ/m^2 to 13.3kJ/m^2, respectively, the notched impact strength is close to that of HDPE (13.6kJ/m^2),the yield strength is in excess of 3.9MPa of that of HDPE. The yield strength and notched impact strength will be further increased to 30.7MPa and 32.4kJ/m^2 in case the ozonized HDPE is blended with STC pretreated with silane coupling agent.     

Adsorbent-adsorbate interactions in the adsorption of organic and?inorganic species on ozonized activated carbons: a?short?review

This objective of this work was to summarize the main results obtained in previous papers related to the adsorbent-adsorbate interactions involved in the adsorption of naphthalenesulphonic acids and heavy metals (Cd(II) or Hg(II)) by modified activated carbons. The adsorption of organic compounds (1-naphthalenesulphonic acid, 1,5-naphthalenedisulphonic acid and 1,3,6-naphthalenetrisulphonic acid) and inorganic species (Cd(II) and Hg(II)) was studied on a series of ozonized activated carbon in aqueous phase. Commercial activated carbon (Filtrasorb 400) was treated with different ozone doses to study the effect of ozone treatment on its surface properties and investigate the behavior of the treated carbon samples in the above adsorption processes. After ozonation, carbonyl- and carboxyl-type groups were generated on the carbon surface. The action of ozone also affected the textural characteristics of the carbon; thus, the surface area diminished due both to the ozone attack and to the increase in oxygenated groups, which prevented the diffusion of nitrogen by obstructing micropore entrances. The capacity of activated carbon to adsorb naphthalenesulphonic acids sharply decreased with a greater number of sulphonic groups in the aromatic rings of these acids. As the concentration of oxygenated electron-withdrawing groups on the carbon surface increased, a significant reduction in adsorption capacity was observed. In all cases, the adsorption uptake decreased with higher solution pH. The adsorption of metallic ions, Cd(II) and Hg(II), by this series of ozonized activated carbons was also studied. In the case of Cd(II), the adsorption capacity and affinity of the adsorbents increased with a higher concentration of acid oxygenated groups on the activated carbon surface. In the case of Hg(II), the adsorption diminished with an increase in the degree of oxidation of the activated carbon. The adsorption of 1,3,6-naphthalenetrisulphonic acid on the ozonized carbons was also studied in the presence of Cd(II) and Hg(II). The presence of Cd(II)) in the medium enhanced the sulphonic acid uptake, mainly for the most ozonized activated carbon sample, whereas the presence of Hg(II) had no significant effect on the adsorption.     

Molecular addressing? Studies on light-induced reorientation in liquid-crystalline side chain polymers

Polarized light leads to an effective reorientation of the optic axis in the glassy state of liquid-crystalline side chain polymers containing azobenzene mesogenic groups, via a trans-cis and cis-trans isomerization. Using a combination of U V and IR dichroitic studies it is shown for copolymers consisting of chromophores (azobenzene) and non-chromophores (phenylbenzoate) that only the chromophores are reoriented by light as far as the glassy state is concerned. Individual chromophores are thus addressed by photoselection. Photoselection in the fluid nematic state, on the other hand, leads also to a reorientation of the non-chromophores.     

Low-temperature oxidative modification of lignites and lignite-based cokes

The kinetics of oxidation of lignites and cokes with ozone in the gas and liquid phases and the composition of oxidation products were studied. The surface area and porosity were measured before and after ozonization. Ozonization increased the surface area largely because of the growth of micro-and mesopores. Changes in the composition of functional groups on the surface of lignites and cokes were determined IR spectroscopically. Adsorbents with the required properties can be prepared by varying the concentration of ozone and ozonization duration.     

Photoinduced rotational isomerization mechanism of 2-chlorobenzaldehyde in low-temperature rare-gas matrices by vibrational and electronic spectroscopies

Rotational isomerization of 2-chlorobenzaldehyde in low-temperature rare-gas matrices has been investigated by vibrational and electronic spectroscopies with aids of the density functional theory (DFT) and configuration interaction single (CIS) calculations. Infrared spectrum of the less stable O-cis isomer, produced from the more stable O-trans isomer upon UV irradiation, is measured with an FT-IR spectrophotometer. The enthalpy difference between the O-cis and O-trans isomers is estimated to be 9.7±0.2 kJ mol⁻¹ from the temperature dependence of the infrared band intensities. Analyses of the infrared and electronic absorption spectral changes after UV irradiation and the phosphorescence spectra measured at various excitation wavelengths suggest that the rotational isomerization occurs via the intersystem crossing from S₁ to T₁.     

Interactions of ozone with organic surface films in the presence of simulated sunlight: impact on wettability of aerosols

Heterogeneous reactions between organic films, taken as proxies for atmospheric aerosols, with ozone in presence of simulated sunlight and the photosensitizer 4-carboxybenzophenone (4-CB) were observed to alter surface properties as monitored by contact angle during the reaction. Attenuated total reflectance Fourier transform infrared spectroscopy (FTIR-ATR) was used in addition for product identification. Two types of model surfaces were systematically studied: 4-CB/4-phenoxyphenol and 4-CB/catechol. Solid organic films made of 4-CB/catechol were observed to become hydrophilic by simultaneous exposure to ozone and simulated sunlight, whereas organic films made of 4-CB/4-phenoxyphenol become hydrophobic under the same conditions. These changes in contact angle indicate that photo-induced aging processes involving ozone (such as oligomerisation) not necessarily favour increased hygroscopicity of organic aerosols in the atmosphere. The ratio between hydrophobic and hydrophilic functional groups should reflect the chemical property of organic films with respect to wettability phenomena. Contact angles and surface tensions of the exposed organic film made of 4-CB/4-phenoxyphenol were found to correspond to the hydrophobic/hydrophilic ratios obtained from the FTIR-ATR spectra.     

Synthesis of graft polymers from an ozonized ethylene vinyl acetate copolymer (EVA). I. Study of the radical polymerization of styrene initiated by an ozonized EVA

Polymers can be ozonized with an ozone/oxygen mixture to create peroxides and hydroperoxides on the polymer chain. These heat-sensitive functional groups can be used to initiate radical polymerization of vinyl monomers and give graft copolymers. The properties of these copolymers are well described in literature; however, we notice that available data concerning decomposition rate constants are inconsistent. Decomposition rate measurements, time of assay of free radicals and stability of the ozonized polymers do not give the same results. In this work, we studied the kinetics of the styrene polymerization initiated by an ozonized ethylene vinyl acetate copolymer. Consequently, the f·kd product can be calculated (f is the efficiency and kd the decomposition rate constant). The ozonized copolymer is not similar to usual radical initiators. The initial viscosity of the solution has an important effect on the calculation of the kinetic values. Activation energy and Arrhenius coefficient are different than the one obtained for the usual initiators. © 1994 John Wiley & Sons, Inc.     

Spectroscopic investigation of several uranium(IV) polyoxometalate complexes

Summary Six sandwich-type uranium(IV)-polyoxometalates (U^IV-POM) were prepared and investigated by FT-IR and UV-VIS spectroscopy. Changes in position and shape of antisymmetric stretching vibration bands in the 640-1000 cm^-1 region were identified in all U^IV-POM FT-IR spectra. These changes are related to coordination of U(IV) to the trilacunary Keggin units. Visible electronic spectra of aqueous solutions of U^IV-POM complexes correspond to uranium ³H₄ electronic ground state, having a quasicubic configuration. Presence of electronic transitions were identified by UV spectroscopy of U^IV-POM complexes in aqueous solutions.     

Degradability of composites of low density polyethylene/polypropylene blends filled with rape straw

Composites of LDPE/PP blends and comminuted rape straw as a filler were obtained and characterized. The aging performance of these composites has been investigated. The composites were aged using various types of wet soil and selected species of mould fungi as aging environment as well as using Atlas UV 2000 apparatus as simulation of abiotic conditions. The changes between non-aged and partially degraded composites were evaluated by measuring their mechanical properties and mass change and using FT-IR spectroscopy, FT-IR/PA spectroscopy and scanning electron microscopy. The highest extent of degradation was observed after aging in compost. The band corresponding to cellulosic fibres is no longer recorded in the FT-IR spectra.