Reaction of poly(vinyl chloride) with magnesium and grignard reagents

Reaction of poly(vinyl chloride) with magnesium under various conditions was attempted, but poly(vinyl chloride) did not react with magnesium. The reactions of poly(vinyl chloride) with benzylmagnesium chloride and allylmagnesium chloride as Grignard reagents were carried out in tetrahydrofuran at reflux temperature. It was found that the chlorine atoms in the poly(vinyl chloride) were replaced by benzyl and allyl groups by the coupling reaction, and a small amount of Grignard reagent of poly(vinyl chloride) was formed by the magnesium–halogen exchange reaction. The extent of the substitution increased with increasing reaction time and concentration of the Grignard reagent.     

Modification of poly(vinyl chloride). XIII. Crosslinking of poly(vinyl chloride) with dithiols and properties of the crosslinked products

PVC was crosslinked by immersing PVC–dithiol blends in ethylenediamine at 30°C. Properties of the products depended on the chain length and chemical structure of the crosslinkage and on the molecular weight of the polymer chain between crosslinks M_c. Crosslinking by the agent of soft structure and long molecular chain resulted in high tensile strength at break and impact strength and low brittle temperature. The use of the crosslinking agent of short molecular chain gave high yield strength, Young's modulus, and heat distortion temperature. The relation of M_c and the chemical structure of the crosslinks to the properties of the crosslinked rigid polymer was discussed in regard to the crosslinking effect and plasticizing effect.     

Photo-oxidation of poly(vinyl chloride)

Hydrogen chloride is evolved at an increasing rate in the light-induced oxidation of poly(vinyl chloride) films. These accelerated kinetics were shown to result from an increased absorption of light by the polyenes formed, since the quantum yield of dehydrochlorination (Φ_HCl = 0·015) is independent of the extent of the reaction in the dose range investigated. Determination of the quantum yields of the different processes involved indicate that, for each scission of the polymer backbone, 11 molecules of hydrogen chloride are evolved while three carbonyl groups, two hydroperoxides and 0·4 intermolecular crosslinks appear on the polymer chain. A mechanism that involves β-scissions of the tertiary alkoxy radicals, resulting from non-terminating interactions of α-chloro-peroxy radicals, is suggested to explain the observed increase of the polymer degradation in the presence of oxygen.     

Radiolysis of poly(vinyl chloride)

Allyl free-radical intermediates are detected by ultraviolet absorption at 255 mu in poly(vinyl chloride) irradiated at ?196°C and stored at 25°C. In vacuum at 25°C, allyl radicals are converted into polyenyl free radicals and polyenes. From the nature of allyl radical decay in vacuum, radical chain transfer between polyenyl radicals and poly(vinyl chloride) is inferred. Allyl and polyenyl free radicals are scavenged by oxygen on post-irradiation storage in air.     

Pyrolysis of poly(vinyl chloride)

A pyrolysis–gas chromatography–mass spectrometric technique has been developed to study the thermal degradation of poly(vinyl chlorides) polymerized at different temperatures. Hydrogen chloride and benzene evolution during successive stages of pyrolysis have been quantitatively determined and correlated to the tacticity and molecular weight of the polymer. It was found that lowering the temperature of polymerization and molecular weight depresses benzene evolution and increases char weight but does not affect the HCl yield. It is suggested that the syndiotactic trans microstructure favored at low temperature of polymerization yields polyenes which cannot cyclize to form benzene. As the molecular weight decreases, the increase in number of vinyl chain ends facilitates pyrolytic crosslinking and char formation.     

Photo-oxidation of poly(vinyl chloride)

The photo-oxidation of PVC has been studied over the temperature range 30–150°C. Initiation with ultraviolet (2537A) radiation has been correlated with the presence of minute amounts of ozone. The contribution of atomic oxygen and singlet oxygen (¹Δ_g) molecules to the initiation mechanism is discussed. The β-chloroketones probably formed in the photo-oxidation of PVC, decomposed according to a Norrish type I reaction without loss of chlorine atoms. The gaseous products of the photo-oxidation of PVC at 30°C were carbon dioxide, carbon monoxide, hydrogen, and methane. Hydrogen chloride was obtained only when PVC was heated at high temperatures. When PVC was photo-oxidized and then heated at high temperature, benzene was obtained in addition to hydrogen chloride. The gaseous products from the photo-oxidations of model compounds, such as 4-chloro-2-butanone and 2,4-dichloropentane, were also compared with those from PVC. Hydrogen chloride was detected only after photo-oxidation at temperatures of 25°C or higher. Therefore, it was concluded that hydrogen chloride is mainly a product of thermal decomposition. Since unsaturation was not observed in photo-oxidized PVC films, the cause of discoloration is unclear. When PVC was modified by stabilizers or additives, the oxidative degradation was further complicated by side reactions with the additives.     

Electrical conductivity of poly(vinyl chloride) obtained by photodehydrochlorination from laminated poly(vinyl chloride)/polypyrrole films

Poly(vinyl chloride) (PVC) has been converted to an electrically conductive structure by combined electrochemical and photochemical methods. PVC was cast on a polypyrrole (PPy) film electrode which had been electrochemically prepared. The PVC layer in the laminated PVC/PPy films was first dehydrochlorinated under the illumination of UV light, and the generated polyenes were subsequently doped with I₂ and FeCl₃. The maximum electrical conductivity achieved for such PVC film was 2.51 X 10^?2 and 8.63 10^?2 S cm^?1 after I₂ and FeCl₃ doping, respectively. The temperature dependence of the electrical conductivity showed different behavior in higher and lower temperature ranges. In the former (T > 243 K), the T^?1 law held, and the activation energy and bandgap were estimated as 0.25 and 0.49 eV, respectively. In the latter (T < 243 K), the conductivity mechanism followed the variable range hopping model (T^?1/4 law) in which the radius of the localized state wave function and the density of the localized states at the Fermi level were 1.25 × 10³ Å and 1.03 X 10¹⁵ eV^?1 cm^?3, respectively. © 1995 John Wiley & Sons, Inc.     

用DSC研究线形多嵌段聚氨酯与聚氯乙烯、氯化聚氯乙烯共混相容性

用示差扫描量热法（DSC）研究了线形多嵌段聚氨酯（PU）与聚氯乙烯（PVC）、氯化聚氯乙烯（CPVC）共混相容性，说明了PU／VC、PU／CPVC的相容是由于共混物中形成了新的氢键的缘故．聚酯型聚氨酯与PVC、CPVC的相容性要好子聚酸型聚氨酯，CPVC与PU的相容性又要好于PVC．聚氨酯中硬段的引入不利于PU／PVC、PU／CPVC的相容性．     

Novel preparation of electrically conducting poly (vinyl chloride) by photo-dehydrochlorination from poly (vinyl chloride)/polypyrrole composite film

Polypyrrole (PPy) was deposited electrochemically on a platinum plate from a nitric acid solution of pyrrole. The PVC/PPy composite film was finally obtained by casting poly(vinyl chloride) (PVC) onto the PPy electrode from a tetrahydrofuran solution of PVC. The prepared composite film was irradiated at 90°C with a low-pressure mercury lamp in the stream of hydrogen gas saturated with steam, and the PVC film was dehydrochlorinated, leading to the formation of conjugated polyene. The electrical conductivity (σ) of the PVC film in the irradiated composite film was reveled: σ=2.51 × 10^?5S cm^?1. By iodine doping, σ was further enhanced up to 5.04 X 10^?3 S cm^?1. The tensile strength of the irradiated composite film became larger than that of the original PVC film; i.e., the stress at break was: 461 (composite film); 401 kg cm^?2 (PVC). These results were brought about by the doping of radical species to the conjugated polyene. The anion, NO^?₃, doped during the electrodeposition of PPy was photodecomposed to generate radical NO₂ and this species was doped to the polyene, resulting in the formation of electrically conductive PVC and mechanically improved composite film. © 1994 John Wiley & Sons, Inc.     

Retardation of discoloration of poly(vinyl chloride) and decolorization of discolored poly(vinyl chloride) with diimide

Retardation of discoloration of poly(vinyl chloride) with diimide was studied in dimethylformamide at 130°C. with the use of p-toluenesulfonylhydrazide (PSH) as a source of diimide. A process was proposed that involved prolonging the induction periods of discoloration by inhibiting the development of conjugated polyene structure. The optimum proportion of PSH was one fourth of the poly(vinyl chloride), the best results. Furthermore, poly(vinyl chloride) discolored by thermal degradation in o-dichlorobenzene or gamma-ray irradiation under vacuum was decolorized in solution at 130°C. by addition of PSH. The decolorized poly(vinyl chloride) thus obtained was thermally stable compared with that obtained by oxidative methods.     

Antioxidative stabilization of poly(vinyl chloride)

Halogenated resins such as poly(vinyl)chloride undergo rapid degradation when exposed to heat. Such degradation is significantly increased by oxygen, and it is believed that the induction of the process of decomposition is caused by autoxidation of the polymer, followed by extensive dehydrohalogenation. Sulfur-containing peroxide decomposers allow primary stabilization of PVC with organic compounds which are not HCl acceptors but prevent free radical cross-linking of the polymer. This implies a discolored polymer melt (due to loss of HCl and formation of polyenes) which nonetheless exhibits good long term stability (no cross-linking). The stabilization of labile chlorine atoms results from the oxidation of various chain irregularities, and thus the elimination of the early discoloration can be achieved by the use of small quantities of monohydrocarbyltin co-stabilizers. The relative performance of various antioxidant systems are reported and possible stabilization mechanisms are discussed.     

Photosensitized dehydrochlorination of poly(vinyl chloride)

The mechanism of the benzophenone-photosensitized degradation of films of poly-(vinyl chloride) was studied, both under vacuum and in the presence of oxygen. Initial rapid increases in absorption in the 340 nm region strongly implicate the ketyl radical in the initiation process which involves the abstraction by triplet benzophenone of a methylenic hydrogen from poly(vinyl chloride). Dehydrochlorination then occurs by a chain mechanism, and the conjugated polyene structure produced photosensitizes further initiation and, in the presence of oxygen, photo-oxidation of the polymer.     

Properties of poly(vinyl chloride) blends with polycarbonates and chlorinated polyethylene

The miscibility of polycarbonates derived from Bisphenol A or 2,5,2′,5′-tetramethyl-Bisphenol A with poly(vinyl chloride), chlorinated poly(vinyl chloride), and vinyl chloride-vinylidene chloride copolymers has been investigated. In miscible blends a shift of the position of the carbonyl absorption in the IR spectra indicates dipolar interactions between the polymers. The miscibility of chlorinated polyethylenes and reduced poly(vinyl chloride)s among each others demonstrates besides the importance of polar groups the influence of their distribution within the polymer chains for the compatibility of the polymers. The investigations on the miscibility have been carried out by differential scanning calorimetry, and by casting films with microscopical observation of the resulting structures.     

Thermal degradation of poly(vinyl chloride)

This paper presents an initial attempt at describing poly(vinyl chloride) (PVC) thermal degradation through a semi-detailed and lumped kinetic model. A mechanism of 40 species and pseudocomponents (molecules and radicals) involved in about 250 reactions permits quite a good reproduction of the main characteristics of PVC degradation and volatilization. The presence of the two step mechanism—the first step of which corresponds to dehydrochlorination and the second to the tar release and residue char formation—are correctly predicted both in quantitative terms and in the temperature ranges. The model was validated by comparison with several thermo gravimetric analyses, both dynamic at different heating rates, and isothermal. When compared with the typical one step global apparent degradation models, the approach proposed here spans quite large operative ranges, especially when it comes to predicting product distributions. The initial results of these product predictions, even though quite preliminary, are encouraging and confirm the validity of the model.     

NMR spectrum of poly(vinyl chloride)

The 100-MHz proton NMR spectra of commercial and laboratory-prepared poly(vinyl chloride) (PVC) have been measured in various solvents at high temperature (80–150°C). Tacticity in PVC was determined by the analysis of the β-proton spectrum. The spectrum was calculated assuming that the PVC chain consists of tetrad sequences of monomer units and that their distribution in the chain is described by a simple Bernoulli-sequence statistics with a P_m (the probability of isotactic placement) of 0.45 for commercial PVC polymerized at 50°C. Tacticity calibration curves based on measurements made for the polymer in pentachloroethane and β-dichlorobenzene were established, and they provide a simple method for the measurement of tacticity in PVC directly from the observed spectra. Excluding samples prepared in butyraldehyde solution, the formation of syndiotactic structures in PVC (prepared by free-radical polymerization) was found to be favored by lowering the polymerization temperature. This preference is due to an increase in the activation enthalpy of 510 cal/mole which is required for forming an isotactic placement in the chain during the propagation step.     

Suspension polymerization of vinyl chloride and the processibility of poly(vinyl chloride)

The most important technological procedure in the production of PVC is the suspension polymerization of vinyl chloride, as processibility of the polymer may be influenced to a considerable extent by the choice of polymerization conditions. Structure heterogeneities in PVC powders manifest themselves in plasticized PVC by the occurrence of “fish eye” particles. This review concerns the formation and properties of these particles and discusses the causes of their difficult processibility. Also, the relation between polymerization process and PVC dehydrochlorination is discussed and a new mechanism of its initiation based on the reactivity of cisoid enone structures is proposed. These structures catalyze elimination of hydrogen chloride from regular units of PVC by an interchain enzyme-like mechanism giving rise to chloroallyl structures.     

Structure of chlorinated poly(vinyl chloride). V. Molecular parameters of chlorinated poly(vinyl chloride)

The molecular parameters of samples of chlorinated poly(vinyl chloride) (CPVC) and chlorinated β,β-dideuterated poly(vinyl chloride) (β,β-d₂-CPVC) were determined by gel permeation chromatography (GPC), light scattering, osmometry, and viscometry. Comparison of GPC, light scattering, osmometric, and viscometric data resulted in a discussion of the possibility of degradation and the causes of changes in the solution properties in chlorination of PVC and ββ-dideuterated poly(vinyl chloride) (ββ-d₂-PVC). The results obtained are discussed in relation to the mechanism of chlorination of PVC.