PVC dehydrochlorination

Dehydrochlorinated PVC exhibits in the visual and ultraviolet range about 10 to 12 distinct, though only weakly resolved absorption maxima which can be considered as being caused by the overlapping of the individual spectra of polyene sequences of different length. 

Recently the pyrolysis of polymer mixtures has become a focus of interest due to the increasing role of plastics recycling. Many researchers have investigated the thermal decomposition of various polymers in the presence of PVC. Kniimann and Bockhom [25] have studied the decomposition of common polymers and concluded that a separation of plastic mixtures by temperature-controlled pyrolysis in recycling processes is possible. Czegfny et al. [31] observed that the dehydrochlorination of PVC is promoted by the presence of polyamides and polyacrylonitrile however, other vinyl polymers or polyolefins have no effect on the dehydrochlorination. PVC generally affects the decomposition of other polymers due to the catalytic effect of HCI released. Even a few per cent PVC has an effect on the decomposition of polyethylene (PE) [32], HCI appears to promote the initial chain scission of PE. Day et al. [33] reported that PVC can influence the extent of degradation and the pyrolysis product distribution of plastics used in the... 

PMMA with dehydrochlorinated PVC were found miscible and easy to foam for the cryogenic insulation in space vehicles Copolymer of ethylene, 1 - 60 % acrylic ester and 1-30 % COj or SOj Core crosslinked silicone rubber inner shell crosslinked acrylate elastomer outer shell and styrene-AN copolymers... 

PMMA with dehydrochlorinated PVC were found miscible and easy to foam for the cryogenic insulation in space vehicles Jayabalan 1982 Jayabalan and Balakrishnan 1985... 

It was found that the number of sp -hybridized carbons increases with the depth of dehydrochlorination in accordance with the decrease of the C—Cl absorption band in the infrared spectrum. It also appears that dehydrochlorinated PVC samples are rather unstable in air, as shown by FTIR, Raman, and NMR spectroscopy. 

The use of soluble precursor-polymers, which can subsequently be converted to a conjugated form, offers a route to pure materials with controlled morphology. It has been known for many years that poly(vinyl chloride) (PVC) can be thermally, chemically and photothermally dehydro-chlorinated to produce polyene (PA) chain sequences. Initiation occurs at random, and continuous conjugated-sequences are not obtained. As a result the maximum conductivity for iodine-doped dehydrochlorinated PVC is ca. 10 Scm" ... 

PVC was decomposed in tetralin and decalin at 300-400°C. In the first step, dehy-drochlorirration has occurred both in solvents and without their presence. Dehydrochlori-rration products differed. Without solverrt, oil and solid carbon were produced by degradation and condensation. In the presence of solverrt, dehydrochlorinated PVC was corrverted to oil. Decomposition was accelerated in tetralirr. ... 

Ultimately, as the stabilization reactions continue, the metallic salts or soaps are depleted and the by-product metal chlorides result. These metal chlorides are potential Lewis acid catalysts and can greatiy accelerate the undesired dehydrochlorination of PVC. Both zinc chloride and cadmium chloride are particularly strong Lewis acids compared to the weakly acidic organotin chlorides and lead chlorides. This significant complication is effectively dealt with in commercial practice by the co-addition of alkaline-earth soaps or salts, such as calcium stearate or barium stearate, ie, by the use of mixed metal stabilizers. 

There is a great deal of uncertainty as to the mechanism of PVC degradation but certain facts have emerged. Firstly dehydrochlorination occurs at an early stage in the degradation process. There is some infrared evidence that as hydrogen chloride is removed polyene structures are formed (Figure 12.18). 

As already indicated, the measurement of dehydrochlorination rates is not a practical way of assessing the effect of a stabiliser. Thus the congo red test sometimes specified in standards, in which a piece of congo red paper is held in a test tube above a quantity of heated PVC and the time taken for the paper to turn blue due to the evolution of a certain amount of hydrogen chloride, cannot be considered as being of much value. 

In addition to stabilisers, antioxidants and ultra-violent absorbers may also be added to PVC compounds. Amongst antioxidants, trisnonyl phenyl phosphite, mentioned previously, is interesting in that it appears to have additional functions such as a solubiliser or chelator for PVC insoluble metal chlorides formed by reaction of PVC degradation products with metal stabilisers. Since oxidation is both a degradation reaction in its own right and may also accelerate the rate of dehydrochlorination, the use of antioxidants can be beneficial. In addition to the phenyl phosphites, hindered phenols such as octadecyl 3-(3,5-di-tcrt-butyl-4-hydroxyphenyI)propionate and 2,4,6-tris (2,5-di-rcrt-butyl-4-hydroxybenzyl)-1,3,5-trimethylbenzene may be used. 

Hjertberg and coworkers [38-41] were able to correlate the amount of labile chlorine, tertiary and internal allylic chlorine, to the dehydrochlorination rate. They studied PVC samples with increased contents of labile chlorine, which were obtained by polymerization at reduced monomer concentration. According to their results, tertiary chlorine was the most important defect in PVC. In agreement with other reports [42,43], the results also indicated that secondary chlorine was unstable at the temperatures in question, i.e., random initiation would also occur. 

Starnes and Plitz [51], in their studies of PVC stabilization with di( -butyl)tin bis ( -dodecyl mercaptide) or with mixtures of the mercaptide and di( -butyl)tin dichloride, found that the rate of dehydrochlorination was inversely related to the amount of sulphur content of approximately 0.9%. The following mechanism of allyl chloride substitution was proposed [Eq. (12)]. 

Millan (98) studied the effect of tacticity on the ionic dehydrochlorination and chlorination of PVC. For the dehydrochlorination reaction, both the reaction rate and the polyence sequence distribution depend markedly on the syndiotactic content. Chlorination appeared to be easier through heterotactic parts than through syndiotactic sequences as shown by C-NMR. 

Naqvi [134] has proposed an alternative model to the Frye and Horst mechanism for the degradation and stabilization of PVC. At room temperature, PVC is well below its glass transition temperature (about 81°C). The low thermal stability of the polymer may be due to the presence of undesirable concentrations of like-poles in the more or less frozen matrix with strong dipoles. Such concentrations, randomly distributed in the polymer matrix, may be considered to constitute weak or high energy spots in the polymer, the possible sites of initiation of thermal dehydrochlorination. 

On heating PVC, as the glass transition temperature is approached, the tensions within the concentrations of like-poles may be released by atoms being pushed apart to an extent that some break from the polymer backbone, resulting in the initiation of dehydrochlorination of the polymer. Unstabilized PVC is known to start degrading at approximately its glass transition temperature [135]. 

Thermal stabilities of modified PVC samples acet-oxylated to varying degrees (reaction temperature 46°C) were determined [45]. Rate of thermal dehydrochlorination at 1% degradation was taken as a measure of thermal stability. The log of the degradation rate is plotted against the acetate content of the polymer in Fig. 2. 

Wirth and Andreas [141] studied the effect of octyl-tin chlorides on the thermal stability of PVC. They were found to significantly retard the dehydrochlorination in the following order ... 

Jamieson and McNeill [142] studied the degradation of poIy(vinyI acetate) and poly(vinyI chloride) and compared it with the degradation of PVC/PVAc blend. For the unmixed situation, hydrogen chloride evolution from PVC started at a lower temperature and a faster rate than acetic acid from PVAc. For the blend, acetic acid production began concurrently with dehydrochlorination. But the dehydrochlorination rate maximum occurred earlier than in the previous case indicating that both polymers were destabilized. This is a direct proof of the intermolecular nature of the destabilizing effect of acetate groups on chlorine atoms in PVC. The effects observed by Jamieson and McNeill were explained in terms of acid catalysis. Hydrochloric acid produced in the PVC phase diffused into the PVAc phase to catalyze the loss of acetic acid and vice-versa. 

The mechanisms of degradation and the mode of action of the various PVC stabilisers have both been widely studied. Often at least one aspect of their operation is some sort of reaction with the first trace of hydrogen chloride evolved. This removes what would otherwise act as the catalyst for further dehydrochlorination, and hence significantly retards the degradation process. In addition, many stabilisers are themselves capable of reacting across any double bonds formed, thereby reversing the process that causes discoloration and embrittlement. 

Polyvinyl chloride has been modified by photochemical reactions in order to either produce a conductive polymer or to improve its light-stability. In the first case, the PVC plate was extensively photochlorinated and then degraded by UV exposure in N2. Total dehydrochlorination was achieved by a short Ar+ laser irradiation at 488 nm that leads to a purely carbon polymer which was shown to exhibit an electrical conductivity. In the second case, an epoxy-acrylate resin was coated onto a transparent PVC sheet and crosslinked by UV irradiation in the presence of both a photoinitiator and a UV absorber. This superficial treatment was found to greatly improve the photostability of PVC as well as its surface properties. 

In the present work, a somewhat different approach was chosen in order to produce conducting polymers the basic idea was to start with a cheap material, like PVC, and try to remove all the hydrogen and chlorine atoms from the polymer chain. The purely carbon material thus obtained was expected to exhibit the electrical conductivity of a semimetal, while being insensitive to the atmospheric oxygen. In this paper, we report for the first time how PVC can be completely dehydrochlorinated by simple exposure to a powerful laser beam that combines both the photochemical and the thermal effects. 

These quantum yield values appear to be much higher than unity and therefore demonstrate that carbonization occurs by a chain reaction process. The mechanism of the laser-induced dehydrochlorination of photodegraded C-PVC can be schematically represented by the follo-... 

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