Thermal Dehydrochlorination Of PVC Research Articles

Thermal dehydrochlorination of PVC in the presence of rubber seed oil

AbstractDehydrochlorination rates of PVC in nitrogen atmosphere were determined in the presence of rubber seed oil (RSO), epoxidized rubber seed oil (ERSO), barium soap of rubber seed oil fatty acids and barium soap of epoxidized fatty acid of rubber seed oil. The initial rates of dehydrochlorination and the time required for the degradation to attain 1% conversion showed that the rubber seed oil derivatives exert a stabilizing effect on the degradation of PVC. The order of the stabilizing effect was found to be metal soaps of ERSO < metal soaps of RSO < ERSO < RSO.

Dehydrochlorination of Poly(vinyl chloride) in Isotactic Systems

The dehydrochlorination of isotactic, low-molecular-weight models of PVC, dimers to pentamers, was studied using the semiempirical MNDO method. The results obtained lead to the conclusion that the thermal dehydrochlorination of PVC can occur through either a radical or an ionic mechanism, depending on the reaction conditions. The arising conjugated polyene structures do not grow by the generally accepted "zip" mechanism, but rather through the "alternating growth" mechanism. A comparison was also made to the reactivity of isotactic and syndiotactic sequences from the point of view of kinetic and thermodynamic factors. It follows from the computations that the splitting off of the first HCl molecule is easier in the isotactic sequence, but that subsequent growth of the polyene chain occurs more readily in syndiotactic systems.

Medium effects on the thermal dehydrochlorination of poly(vinyl chloride)

Abstract In the light of polaron theory it is shown that, in the thermal dehydrochlorination (TDHC) of poly(vinylchloride) (PVC), the medium can, by its interaction with the double bonds existing in PVC, control the rate, the mechanisms of TDHC, the cis/trans configuration and the length distribution of conjugated polyene sequences developed in the polymer backbone. It also shows that the propagation of elimination of HCl in the TDHC of PVC can occur via allylic, as well as normal chlorine atoms.

The Mathematical Models of the Initial Stage of the Thermal Degradation of Poly(Vinyl Chloride)

Abstract The mathematical models of the initial stage of the thermal dehydrochlorination of PVC are proposed. It is shown that abnormal unstable fragments having constants of rates of degradation equal to 10−3–10−4sec−1 have the greatest influence on the thermal degradation of PVC at 180–200°C. The groups having chlorine near tertiary carbon and chloroallylic groups may be such fragments.

Thermal and photochemical stability of polystyrene and its blends with polyvinyl chloride

The influence of some irregularities in PS and PVC chains on their thermal stability was investigated. UV irradiation caused an increase in the content of these irregularities in the polymers. It was found that the presence of carbonyl groups and crosslinking of the polymer chains hamper the thermal dehydrochlorination of PVC and the total decomposition of both polymers. Weak peroxy linkages and conjugated double bonds decrease the temperature of total decomposition of PS and PVC blends

Thermal dehydrochlorination of poly(vinyl chloride), 2. Transiently and permanently acting structural defects

AbstractSamples with an increased content of chloroallyl structures were prepared by chemical degradation of poly(vinyl chloride) (PVC) using potassium tert‐butoxide. The samples were thermally dehydrochlorinated in an inert atmosphere, and their dehydrochlorination curves were determined by the continuous potentiometric method. The results show that the chloroallyl structures affect the dehydrochlorination of PVC only transiently. The same conclusion is obtained by an analysis of experimental data of the dehydrochlorination of PVC samples enriched in structures with the chlorine atom bound to the branching site (structures with the chlorine atom at the tertiary carbon atom). A general conclusion is that all structural defects, which facilitate the elimination of hydrogen chloride along the polymer chain and exist in the polymer before its heat stress, play only a transient role in the thermal dehydrochlorination of PVC. These structural defects initiate the splitting‐off of hydrogen chloride during the induction period of dehydrochlorination and form conditions for a gradually increasing effect of the basic initiation mechanism, which in the course of dehydrochlorination gives rise to chloroallyl structures. The formation of chloroallyl structures is brought about by a reaction between regular structural PVC units and s‐cis‐enone, dienone, or polyenone structures. A possible mechanism of this reaction, consisting in an interchain syn‐elimination of hydrogen chloride, is suggested.

Study of the effect of the chloroallyl group content on the thermal dehydrochlorination of PVC

Abstract The chloroallyl group contents of PVC and its low molecular weight fractions, soluble in chloroform or acetone, have been determined on the assumption that the reaction of AgNO 3 with labile chlorine atoms occurs only with the allylic chlorines. Their amount is highest in the low molecular weight fractions. The thermal stability of the polymer in inert atmosphere increases if these groups are removed. Neither the labile chlorine content nor the dehydrochlorination rate (in the subsequent degradation) of the initial polymer, or the fractions insoluble in the two solvents, is affected by heat treatment at 180 for 60 min, whereas the amount of labile chlorine in the low molecular weight fractions increases on heat treatment exceeding 30 min. No direct dependence of the dehydrochlorination rate on the amount of labile chlorine in the polymers under study has been established.

Thermal degradation of graft copolymers of PVC prepared by mastication with styrene and methyl methacrylate, and of further PVC mixtures and vinyl chloride copolymers

Abstract Graft copolymers prepared by mastication of PVC in the presence of styrene or of a styrene/ methyl methacrylate mixture, have been studied by thermogravimetry, estimation of hydrogen chloride, thermal volatilization analysis, and flash pyrolysis/g.l.c. The degradation behaviour of PVC/ polystyrene mixtures, vinyl chloride/styrene random copolymers, a random copolymer of methyl methacrylate and styrene, and PVC/poly-α-methylstyrene mixtures has also been studied. The graft copolymers resemble the PVC/methacrylate graft copolymers previously studied in showing retardation of the dehydrochlorination reaction, but contrast with them in yielding chain fragments but no monomer during HCl production. Some stabilization of the second component at higher temperatures is also found. PVC/polystyrene mixtures behave in the same way as the corresponding graft copolymers, but vinyl chloride/styrene copolymers show reduced stability towards both dehydrochlorination and monomer production compared with the homopolymers. PVC/poly-α-methylstyrene mixtures yield some monomer concurrently with HCl loss, and display marked retardation of the latter reaction. Stabilization of the second polymer at higher temperatures is again observed. Many of these results add further strong support to the view that chlorine atoms are involved as chain carriers in the thermal dehydrochlorination of PVC.

Investigations on thermal dehydrochlorination of poly(vinyl chloride)

AbstractThe thermal dehydrochlorination of PVC has been examined on some samples prepared by fractionation of a commercial PVC, and some other samples obtained by polymerization at different temperatures. The results disagree with the concept of a continuous dehydrochlorination from one side to the other of the chain, that necessitates initiating structural anomalies in the macromolecule itself.