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Mechanism of thermal dehydrochlorination

o-Hydroxyacetophenone Girard-P hydrazone transition metal cation chloride complexes

Journal of Thermal Analysis and Calorimetry
Authors: M. M. Abou Sekkina and M. R. Salem

Co(II), Ni(II), Cu(II) and Zn(II) complexes ofo-hydroxyacetophenone Girard-P hydrazone were prepared by using the organic ligand and the corresponding transition metal chlorides. The protonation and formation constants were evaluated for the organic ligando-hydroxyacetophe-none Girard-P hydrazone and its transition metal complexes, respectively. The thermal behaviour of the test materials was established by means of DTA. Their semiconducting parameters were evaluated through DC-conductivity measurements, and their thermodynamic parameters were evaluated, assigned and interpreted. The mechanism of thermal dehydrochlorination of the metal chloride complexes was proposed.

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Abstract  

Vinylidene chloride copolymers containing a predominance of vinylidene chloride (85-90%) have long been important barrier polymers widely used in the plastics packaging industry. These materials display excellent barrier to the ingress of oxygen and other small molecules (to prevent food spoilage) and to the loss of food flavor and aroma constituents (to prevent flavor scalping on the supermarket shelf). While these polymers have many outstanding characteristics, which have made them commercial successes, they tend to undergo thermally-induced degradative dehydrohalogenation at process temperatures. The dehydrochlorination occurs at moderate temperatures (120-200C) and is a typical chain process involving initiation, propagation and termination phases. Defect structures, namely internal unsaturation (allylic dichloromethylene groups), serve as initiation sites for the degradation. These may be introduced during polymerization or during subsequent isolation and drying procedures. If uncontrolled, sequential dehydrohalogenation can lead to the formation of conjugated polyene sequences along the polymer mainchain. If sufficiently large, these polyenes absorb in the visible portion of the electromagnetic spectrum, and give rise to discoloration of the polymer. The dehydrochlorination process may be conveniently monitored by thermogravimetric techniques. Both initiation and propagation rate constants may be readily obtained.

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Abstract  

The thermo non-oxidative degradation of PVC and the effects of alkaline earth metal (Be, Mg, Ca, Ba) stearates were studied by thermogravimetry in the temperature range 150 to 500°C. The alkaline earth metal stearates were observed effectively reduce the dehydrochlorination of PVC. The synergistic effects of combinations of these salts with lead stearate were also studied and are discussed. Kinetic parameters such as the activation energy, order of reaction and Arrhenius factor were calculated by the Coats and Horowitz methods. The results showed that these metal stearates increase the activation energy required for the dehydrochlorination of PVC.

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The thermal dehydrochlorination and decomposition in air and in nitrogen of films made of PVC and blends of PVC and VC/VAC, MBS, MMA/MA or ABS were studied. Both processes take place at higher temperature in air than in nitrogen. In air, ABS and MMA/MA cause an apparent increase in the decomposition temperature of PVC, whereas in nitrogen these copolymers accelerate its decomposition.

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modifying effects, the changes in mechanical and chemical properties of adding different polyethylenes (PEs). The thermal stability of PVC is limited, it requires special care during processing because thermal degradation by dehydrochlorination [ 4 ]. The

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Abstract  

The thermal degradation of a sort of polyvinyl chloride was investigated. Complex processes for polyvinyl chloride degradation were evidenced. The kinetic analysis of dehydrochlorination and of subsequent processes was carried out. A change of mechanism was detected when dehydrochlorination goes to completion. The values of non-isothermal kinetic parameters determined by various methods are in a satisfactory agreement. The obtained results allowed some clarifications concerning the thermal degradation steps.

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Abstract  

Vinylidene chloride polymers are prominent in the barrier plastics packaging industry. They display good barrier to the transport of oxygen (to prevent spoilage of food items) and flavor and aroma constituents (to prevent 'scalping' on the supermarket shelf). However, these polymers undergo thermal dehydrochlorination during processing. This can lead to a variety of problems including the evolution of hydrogen chloride which must be scavenged to prevent its interaction with the metallic walls of process equipment. Such interaction leads to the formation of metal halides which act as Lewis acids to facilitate the degradation. A potentially effective means to capture hydrogen chloride generated might be to incorporate into the polymer a mild organic base. Accordingly, copolymers of vinylidene chloride and 4-vinylpyridine have been prepared and subjected to thermal aging. Results suggest that the pyridine moiety is sufficiently basic to actively promote dehydrochlorination in the vinylidene chloride segments of the polymer.

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Fe(III) chloride hydrate (FeCl3·xH2O) undergoes simultaneous dehydration and dehydrochlorination from its molten phase in the temperature range 100–200‡C. The kinetics of these two parallel thermal processes has been studied by both isothermal and non-isothermal methods. Whereas for the dehydration reaction at temperature below 125‡C a second order rate model (F2) fits well, a three-dimensional diffusion (D3) model is found to fit better at temperature above 135‡C. For the dehydrochlorination reaction an interface growth controlled model of 1/3 order (F 1/3) appears to be the most suitable over a wide range of reaction. Dynamic thermogravimetry reveals two major steps in the temperature range 50–250‡C. The first step which corresponds to the loss of about 4 mols of H2O, invariably follows second order kinetics (F2). The second step which is predominantly a process of dehydrochlorination, generally fits mixed diffusion controlled models due to the overlapping with the dehydration process. There is an excellent agreement in results among the isothermal and non-isothermal methods of determining kinetic parameters.

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Abstract  

The exfoliated poly(vinyl chloride) (PVC)/montmorillonite (MMT) nanocomposites were synthesized by in situ intercalated polymerization of vinyl chloride (VC) in the presence of organic-intercalated montmorillonite (OMMT). Their structures and thermal properties were characterized. The results showed that layered silicates are well exfoliated and uniformly distributed in PVC matrix during in situ intercalated polymerization of VC in the presence of OMMT. The glass transition temperatures of PVC phases in the PVC/MMT nanocomposites are all lower than that of pristine PVC due to the incorporation of the exfoliated silicate layers in PVC matrix. The 5% mass loss temperature (T 5%), the dehydrochlorination temperature (T max1) of the PVC matrix decreased due to the free and interlayer water in MMT, the low thermal stability, and the enhanced dehydrochlorination of the PVC matrix by alkyl ammonium pre-treated MMT. However, the thermal decomposition temperature of the dehydrochlorinated PVC (T max2) and char at 600C are slightly increased in the presence of silicate layers.

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Abstract  

The thermooxidative degradation of poly(vinyl chloride) (PVC), chlorinated polyethylene (CPE) and PVC/CPE blend 50/50 was investigated by means of dynamic and isothermal thermogravimetric analysis in the flowing atmosphere of air. To estimate the thermooxidative stability of the samples the characteristics of thermogravimetric (TG) curves were used. Kinetic parameters (the apparent activation energy E and preexponential factor Z) were calculated after isoconversional method for the first stage of dynamic degradation where dehydrochlorination (DHCl) of PVC and/or CPE is the main degradation reaction. Despite the chemical resemblance, the degradation mechanisms of CPE and PVC are different, as a consequence of differences in microregularity of the corresponding polymer chains. The addition of Ca/Zn carboxylates as well as the ratio of Ca and Zn carboxylates have considerably different influence on the investigated polymers.

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