Photodegradation of Heterophasic Ethylene-Propylene Copolymers in the Solid State

The photodegradations of various heterophasic ethylene-propylene (E-P) copolymer films were studied at 30 and 55°C in air for varying time intervals. The photochemical behavior of E-P copolymers is quite different from amorphous polypropylene and polyethylene homopolymers but resembles that of isotactic polypropylene. The nonvolatile products in photooxidized copolymer films have been quantitatively identified by infrared analysis. The kinetics and general oxidation mechanism scheme for E-P copolymer are presented. The identification of γ-lactone is an indication of the importance of an intramolecular back-biting process. The overall functional group distribution is found to differ from that in polyethylene and E-P copolymers.     

Surface ozonation and photooxidation of polyethylene film

High-density polyethylene (HDPE) and low-density polyethylene (LDPE) films were oxidized by treatment with ozone and by photooxidation with a low-pressure mercury lamp. The changes that resulted in the surfaces of the films were followed by ESCA. On ozonation, the surface of LDPE initially is oxidized more rapidly than that of HDPE; however, extended ozonation produces a surface composition that corresponds to C₈O for HDPE and to C₁₈O for LDPE. The surface oxidation products are mainly carboxyl groups, with lower levels of carbonyl and C? O groups. For both polymers photooxidation provides more extensively oxidized surfaces than ozonation, although the surface of HDPE oxidizes slightly faster than that of LDPE treated under identical conditions. In both cases the surface stoichiometry after extensive photoxidation is C₆O. The functional groups formed are mainly carboxyl and C? O. The effects of ozonation and photooxidation on the polyethylene surfaces are compared with those produced by several other means of surface oxidation.     

PHOTOOXIDATION OF AROMATIC SULFIDES

Abstract

Dye sensitized photooxidation of sulfides proceeds by way of singlet oxygen to give sulfoxides and sulfones, and the evidence for several intermediates has been reported. We now report that photooxidation of aromatic sulfides gives the product of an unusual type; and the reaction may proceed by either superoxide or hydroperoxysulfurane. 9-Ethylthiofluorene was photooxidized in dichloromethane or acetone with methylene blue as sensitizer. Three main products were isolated and identified as fluorenone (15%), 9-fluorenyl ethyl sulfoxide (19%) and 1-hydroxyl-9-fluorenone (23%).     

Chain and photochain mechanisms of photooxidation of polymers

The mechanisms of photooxidation of the popular commercial polymers polystyrene (PS), polyethylene (PE), and an ethylene-carbon monoxide copolymer (polyketone, PK) differing in the polymer chain structure and the nature and concentration of chromophore groups are considered. In the case of the formation of photosensitive intermediates in polystyrene, taken as an example, the photochain oxidation mechanism was revealed and thoroughly studied, according to which the polymer “burns” into complete oxidation products (CO₂, H₂O) with a degree of conversion of ≥50% and a kinetic-chain length of l = 10³–10⁴ units. The hydroperoxide mechanism plays a minor role in the photooxidation of PS, it is a short-chain process (as in the case of thermal oxidation, l ∼ 10) and does not exceed 1.5% of the total amount of absorbed oxygen. Carbonyl groups, as weak photoinitiators, induce in PE and PK the conventional radical chain mechanism of photooxidation with degenerate branching of kinetic chains on hydroperoxide groups and other oxidations products.     

Biodegradation of packaging materials: composting of polyolefins

The compostability of LDPE, PP and heterophasic E-P Copolymers was studied for 5 months under normal and accelerated composting environments. Bio-susceptibility of pre-UV (290 nm) treated films (∼ 100μm, 5 X 5 cm) was measured by monitoring the weight loss, intrinsic viscosity [η], chain scission, functional group evolution (FT-IR) and surface morphology (SEM). It was found that with the increasing time of UV treatment, weight loss was increased in compost. Almost linear decrease in [η] was observed for irradiated and composted samples. The temperature of compost and extra addition of thermophilic microbes significantly influenced the biodegradation. In general, it was concluded that the composition of copolymer markedly affected the compostability and increased ethylene content, slowed down the microbial activity.     

Photooxidative behaviour of polyethylene/polyamide-6 blends

The photochemical behaviour of several polyethylene/polyamide-6 blends was studied under conditions of artificial accelerated weathering. Particular attention was paid to five different compositions ranging from pure polyethylene to pure polyamide with blends of PE/PA-6 of various compositions: 75/25, 50/50 and 25/75 wt/wt%. Analysis by infrared spectroscopy of the chemical modifications caused by photooxidation showed that exposing the polyethylene/polyamide-6 blends to UV-light irradiation led to the formation of oxidation photoproducts in both polymer phases. In agreement with both the mechanical and spectroscopic analyses, the photooxidation rate of the blends was observed to be much higher than that of the homopolymers. The results given in this paper suggest that photooxidation of the PE/PA blends starts in the polyamide phase and that the subsequent photooxidation of the polyethylene phase may be initiated by the radicals coming from the oxidation of PA.     

Photooxidation of Selected Polycyclic Aromatic Hydrocarbons in Aqueous Organic Media in The Presence of Ti(IV)Oxide

Abstract

We have studied the photooxidation of selected polycyclic aromatic hydrocarbons (PAH) in the presence of Ti(IV)oxide in a mixed solvent system consisting of N-methylpyrrolidinone (NMP) and water. Reaction rates for the photooxidation of acenaphthylene and pyrene were investigated by monitoring the disappearance of the PAH substrate from the reaction mixture as a function of time. For both compounds plots of In C_o/C_t, as a function of time yielded straight lines, indicating first order kinetics with respect to the substrate. With an initial acenaphthylene concentration of 1.0 gL^?1 the first order reaction rate constant was 0.19 hr^?1 and the half life was 3.7 hr. With an initial pyrene concentration of 0.2 gL^?1 the first order reaction rate constant was 0.0285 hr^?1 and the half life was 24 hr. The photoproducts were characterized by high performance liquid chromatography with diode-array detection (HPLC/DAD) and by liquid chromatography/atmospheric pressure chemical ionization mass spectrometry (APCI/LC-MS). Although a number of simple oxidation products were identified the bulk of the photoproducts consisted of the parent PAH substituted with one or more solvent (NMP) molecules. The product mixtures from the photooxidation of the non-mutagens acenaphthylene and pyrene were found to be also non-mutagenic in our Salmonella typhimurium forward mutation assay.     

Photocatalyzed reaction of indole in an aqueous suspension of titanium dioxide

The photocatalyzed oxidation of indole (1) in an aqueous suspension of titanium dioxide has been investigated and an attempt has been made to identify the products formed during the photooxidation process by gas chromatographic–mass spectrometric (GC–MS) analysis. Photolysis of an aqueous solution of indole (1) in the presence of titanium dioxide and oxygen led to the formation of 2,3-dihydroindole-2-one (6) and 1H-indole-2,3-dione (7). A probable pathway for the formation of these products has been proposed.     

PREPARATION AND CHARACTERIZATION OF POLYSULFONE AND POLYETHERSULFONE MEMBRANES FOR CALCIUM (Ca2+) AND MAGNESIUM (Mg2+) SEPARATION BY COMPLEXATION ULTRAFILTRATION

ABSTRACT

Asymmetric ultrafiltration membranes were synthesized from locally available polysulfone and polyethersulfone polymers using aprotic solvents and organic additives by the phase inversion method. The membranes were characterized in terms of pure water permeability, separation behavior with respect to polyethylene glycols of various molecular weights and electrolytes. The suitability of using polyethyleneimine (PEI) for selective removal of calcium and magnesium salts by an ultrafiltration process was studied in terms of optimum polymer loading at reasonable permeate flux, irreversible adsorptive fouling of the macromolecular ligand on the polymer as functions of solution pH and ionic strength, and metal ion separation as a function of concentration and pressure. Direct electron microscopic observation of fresh, as well as fouled, membranes are presented.     

Acquired biodegradability of polyethylenes containing pro-oxidant additives

Biodegrability of high density polyethylene film (HDPE) and low density polyethylene film (LDPE) both containing a balance of antioxidants and pro-oxidants was studied with defined microbial strains particularly with Rhodococcus rhodochrous and Nocardia asteroides in mineral medium. After an abiotic pre-treatment consisting of photooxidation and thermo-oxidation corresponding to about 3 years of outdoor weathering the samples were inoculated, incubated up to 200 days and during the period their metabolic activities were followed by measuring adenosine triphosphate content. Simultaneously the cultures were also monitored by optical microscopy and FTIR spectroscopy. The first initial phase of fast growth caused by the presence of low molecular extractable compounds was followed by a long period of stabilized metabolic activity suggesting that microorganisms continued to gain energy from the substrate but evidently at a much slower rate. Complementary analysis performed at the end of incubation revealed that during the experiment time biodegradation processes probably affected surface layer of materials only.     

Photo- and thermal-oxidation of polyethylene: Comparison of mechanisms and influence of unsaturation content

The behaviour of polyethylene with different contents in vinyl and t-vinylene groups have been studied by photooxidation with λ ≥ 300 nm light or by thermooxidation at a temperature of 100 °C. The oxidation was studied by infrared spectroscopy and it was shown that the same oxidation products were obtained, but with different relative concentrations depending on the conditions of ageing, i.e. photochemical or thermal conditions. The mechanisms by which the oxidation products are formed were recalled. The differences between photo- and thermo-oxidation were evidenced on the basis of the stability of ketones that do not accumulate in photochemical conditions, as a result of Norrish reactions. The influence of the initial amount of unsaturated groups on the rates of oxidation was characterized. It was shown that the concentration of unsaturations had no effect on the rate of photooxidation but dramatically influenced the stability in thermooxidative conditions.     

Ethylene-propylene copolymerization initiated with solubilized ziegler-natta macromolecular complexes. II. Characterization of [styrene]-b-[ethylene-co-propylene] copolymers

Copolymerization of ethylene (E) with propylene (P) initiated with soluble (polystyrene)₁₀₀-butadiene₃-Li/TiCl₄ complexes leads to [St]-b-[E-co-P] diblock copolymers with a random [E-P] block. GPC and ¹³C-NMR analyses of copolymers with various compositions and block lengths disclose well-defined linear structures. From DSC measurements of such materials, three different endothermal transition regions are observed: two glass transition regions corresponding, respectively, to the T_g of styrenic and olefinic blocks, and one [E-P] block melting region in which propylene units play a primary role. Furthermore, an additional endotherm is observed, depending on the thermal history of the sample.     

On the CO2 permeation of uniaxially drawn polymers

The CO₂ permeation coefficient and the difficient were measured using the permeation time-lag method for films of atactic polystyrene and high-density polyethylene, each as a function of uniaxial draw ratio. The reduction of permeability with draw ratio is observed for polystyrene and for polyethylene. In the latter it is associated with an increase in crystallinity. In both cases the premeability decreases and the solubility constant remains unchanged. The reduction of permeability is thus caused only by the reduction in diffusion of CO₂ in the drawn polymers. The mechainism is different for the two polymers, as is confirmed by measurements of birefringence, glass transition temperature, and crystallinity.     

Applicability of Silicone Membrane Passive Samplers for Monitoring of Indoor Air Quality

ABSTRACT

A series of experiments were conducted to investigate the permeability of membranes made of silicone foil with respect to selected volatile organic compounds such as butanol, benzene, toluene, butyl acetate, ethylbenzene, m- xylene, styrene, m- dichlorobenzene. On the basis of model experiments the calibration constants k for 18 passive samplers were determined (with respect to each compound present in the gaseous standard mixture).

The obtained calibration constants found are characterised by good precision (except for butanol, relative standard deviation are not greater than 9%). The comparison of the calibration constants for the samplers with silicone membrane of 50 μm thick with those obtained for samplers with polyethylene membrane of 15.5 μm shows that silicone membrane samplers will give higher enrichment factors for the compounds studied.     

Energy transfer processes involving ultraviolet stabilizers. Quenching of singlet oxygen

The role of electronically excited singlet (¹Δ_g) oxygen molecules in the photooxidation of polymers has received increased attention in recent years. Little information regarding the interaction of ultraviolet stabilizers with singlet oxygen is known, however. In this study, singlet oxygen was produced by a microwave discharge in a flow system and rate constants were obtained for quenching by ultraviolet stabilizers. It was found that some nickel chelate stabilizers are effective quenchers of singlet oxygen and their quenching behaviors can be correlated with ultraviolet stabilization effectiveness in thin polypropylene and polyethylene films. The best oxygen quenchers of those examined are nickel chelates with sulfur donor ligands.     

A Cyanine Photooxidation/β‐Elimination Sequence Enables Near‐infrared Uncaging of Aryl Amine Payloads

Uncaging strategies that use near‐infrared wavelengths can enable the highly targeted delivery of biomolecules in complex settings. Many methods, including an approach we developed using cyanine photooxidation, are limited to phenol‐containing payloads. Given the critical role of amines in diverse biological processes, we sought to use cyanine photooxidation to initiate the release of aryl amines. Heptamethine cyanines substituted with an aryl amine at the C4′ position undergo only inefficient release, likely due electronic factors. We then pursued the hypothesis that the carbonyl products derived from cyanine photooxidation could undergo efficient β‐elimination. After examining both symmetrical and unsymmetrical scaffolds, we identify a merocyanine substituted with indolenine and coumarin heterocycles that undergoes efficient photooxidation and aniline uncaging. In total, these studies provide a new scheme—cyanine photooxidation followed by β‐elimination—through which to design photocages with efficient uncaging properties.     

Compatibility mechanisms between EVA and complex impact heterophasic PP-EPx copolymers as a function of EP content

Compatibility mechanisms between EVA and complex heterophasic iPP-EPx copolymers have been studied as a function of EP content. Systematic studies were made in order to characterize the thermal, morphological and mechanical behavior, before and after blending a series of PP-EPx/EVA concentrations. Multiple melting, proportional to the EP content, was observed for the neat copolymers and an explanation was given for its evolution in terms of rejection-like secondary crystallization. After blending with EVA, the generation of a single T_g was taken as an indication of compatibility between both polymers. A morphological transition toward compatibility was first determined at 20 wt.% EVA which was in correlation with a morphological change from isolated spherical domains to interconnected voids. A second morphological transition from interconnected voids to fibrous crystals was observed above 40 wt.% EVA. This last transition marked the beginning of compatibility. Overall, the evolution of blends was explained in terms of the nature of the complex heterophasic copolymers. Tensile mechanical studies were also consistent with morphological changes. Increases in the x content in EPx and in EVA concentration worked in favor of impact resistance.     

Titanium-dioxide-mediated photocatalysis reaction of three selected pesticide derivatives

The photocatalysis reaction of three selected pesticide derivatives, namely methoxychlor (1), chlorothalonil (2) and disulfoton (3), has been investigated in an acetonitrile/water mixture in the presence of titanium dioxide and oxygen. The change as a function of irradiation time has been monitored using the UV spectroscopic analysis technique. An attempt has been made to identify the product formed during the photooxidation process through GC/MS analysis technique. The photolysis of methoxychlor (1) led to the formation of methoxychlor olefin (4) and 4,4-dimethoxybenzophenone (9), whereas chlorothalonil (2) gave rise to 2,3,4,5-tetrachlorophenol (17) as the only product. On the other hand, the photolysis of disulfoton (3) under analogous conditions gave disulfoton sulfoxide (25) and phosphorodithioic acid (21). All the products have been identified by comparing the molecular ion and mass fragmentation peaks of the products with those reported in the library. A probable mechanism for the formation of the products has been proposed.     

Novel Preparation of Polyethylene from Nano‐extrusion Polymerization Inside the Nanochannels of MCM‐41/MgCl2/TiCl4 Catalysts

The MCM‐41 and SiO₂ supported TiCl₄ and TiCl₄/MgCl₂ catalysts with different molar ratios of Mg/Ti were synthesized and used for ethylene polymerization under atmospheric pressure. The nanochannels of MCM‐41 serve as nanoscale polymerization reactor and the polyethylene nanofibers were extruded during the reaction. The nanofibers were observed in SEM micrographs of resulting polyethylene. The effect of MgCl₂ on catalytic activity and thermal properties of resulting polyethylene is investigated too. In the presence of MgCl₂, the catalytic activity increased and more crystalline polyethylene with higher melting points were formed. However, no fibers could be observed in the polyethylene prepared by SiO₂ supported catalysts.     

Regularities of the photodestruction of acridine dyes in aqueous media

Acridine dyes were found to exhibit a low light fastness in oxygen-containing aqueous solutions because of photooxidation with the participation of molecular oxygen. The values of the quantum yield for the photooxidation of Acridine Yellow, Acridine Orange, and proflavin acetate at their initial concentration 2 × 10^?5 mol/l were determined to be 1.8 × 10^?3, 1.5 × 10^?3, and 0.8 × 10^?3, respectively. It was concluded that the photooxidation of these acridine dyes in dilute solutions results in the formation of primary photoproducts of peroxide nature. For proflav in acetate, as an example, it was demonstrated that the increase of the substrate concentration to 6 × 10^?4 mol/l results in a fourfold increase in the quantum yield, a behavior indicative of a change in the photodecomposition mechanism. The rate of the interaction between exited and unexcited proflavin molecules, the process responsible for the photodecomposition of this compound, was found to be ～4 × 10⁷ l/(mol s). The quantum yield for the photooxidation of the proflavin base was estimated to exceed that for the photooxidation of the proflavin monocation by more than an order of magnitude.