Fire performance of poly(vinyl chloride) and its relation to fire hazard

This paper discusses the most important parameters in terms of fire hazard and shows how PVC fares in relation to other polymers. The fire properties specifically addressed are: ignitability, flammability, flame spread, rate and amount of heat release, mass loss rate, smoke release and toxicity. Hydrogen chloride decay is also commented on, because it affects the toxicity of PVC smoke. The individual parameter most relevant to fire hazard is heat release. The two most useful tools for measuring rate of heat release (viz. the OSU and Cone calorimeters) are described. Results obtained from them are discussed. Smoke can best be measured by combined parameters from rate of heat release calorimeters, rather than in the traditional static NBS smoke chamber. Toxic hazard is being addressed by recognition that most smokes are of similar toxicity, so that the mass loss rate will, generally, govern the toxicity of smoke. Not all fire tests are equally good representations of the probable consequences of a full-scale fire. Fire hazard assessment is best carried out based on those test results most relevant to real fires; they can be obtained from small and full-scale experiments and fire models. The fire performance of PVC is excellent; PVC products generally represent low fire hazard in a scenario.     

Calculated properties of some possible vinyl chloride metabolites

There is considerable evidence indicating that the carcinogenic action of vinyl chloride involves metabolic conversion to the epoxide (chlorooxirane) as the initial step. In order to learn more about its subsequent behavior, we have computed structures, energies and other properties for two different protonated forms of the epoxide, and also for two possible rearrangement products, chloroacetaldehyde and acetyl chloride. An ab initio SCF -MO procedure (GAUSSIAN 70) was used. Oxygen protonation is found to weaken both C? O bonds, the effect being greater for the bond involving the carbon bearing the chlorine. Chlorine protonation leads to a marked weakening of the C? Cl bond; this suggests a possible loss of HCl, leaving behind a carbonium ion (and possible alkylating agent or rearrangement precursor). Thus, while C? O bond breaking is doubtless an important reaction pathway for chlorooxirane, our results indicate that attention should also be focused upon the C? Cl bond; its rupture may conceivably be a key step in the biological action of vinyl chloride.     

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.     

Some optical and mechanical properties of poly(vinyl chloride)

The optical and mechanical properties of poly(vinyl chloride) film were examined by observing both the stress and birefringence during stretching at constant rate, during relaxation at constant length and during a dynamic birefringence experiment. Experiments were also done by varying the temperature at constant length. The changes in birefringence are interpreted in terms of changes in negative distortional birefringence, changes in positive orientation birefringence, and possible reversible changes in birefringence with temperature arising from conformational changes in the polymer chain and changes in the contribution of birefringent crystals.     

Structure and properties of poly(vinyl chloride)/graphene nanocomposites

The goal of the paper was to investigate the influence of graphene (GN) on properties and structure of suspensive poly(vinyl chloride) (PVC). PVC/GN nanocomposites were obtained by the solvent evaporation method, and their structures were evaluated using optical microscopy, SEM, FT-IR, XRD and Raman spectroscopy methods. Thermal properties of the obtained materials were studied by TGA. Electrical properties and swelling behaviour were also determined.The microscopic observations confirm a uniform distribution of graphene in the PVC matrix. The investigations carried out indicated an effect of graphene on a decrease in resistivity to a value which enabled to include the PVC/GN nanocomposites into anti-static materials group. On the basis of swelling studies, it has been found that the PVC/GN nanocomposites have a higher chemical resistance against acetone while compared to pure poly(vinyl chloride). The properties of the obtained materials depend significantly on content and dispersion level of graphene in the PVC matrix. An impact of GN on the acceleration of the PVC degradation process was found.     

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.     

Thermal properties of poly(vinyl chloride)/polyurethane blends

Blends of poly(vinyl chloride) and a polyurethane elastomer were investigated by DSC and tensile testing. Up to 30 wt% single glass transition was found. It was concluded that the polyurethane forms partly a true blend and is partly disperged in the continuous blend phase.     

Dynamic mechanical properties of plasticized poly(vinyl chloride)

The complex compliance in extension of gels of poly(vinyl chloride) (PVC) in di(2-ethylhexyl) phthalate (DOP) and in tricresyl phosphate (TCP) was measured over the frequency range from 0.6 to 0.006 cps and the temperature range from ?66 to 65°C: the weight fractions of DOP and TCP in the gels were 0.32, 0.40, 0.49, and 0.59. Measurements were carried out in an apparatus using forced low-frequency longitudinal osillations. Data for the gels could not be combined by the method of reduced variables, since there were gradual changes with decreasing temperature, attributable to an increase in crystallinity. Application of the reduction method of Ninomiya and Ferry for solutions of crystalline polymers was found to be successful. The apparent melting temperatures (T′_m) were obtained from the temperature dependence of the vertical shift factors. An apparent heat of fusion of ca. 120 cal/mole of monomer unit was found. This melting range was in agreement with that of secondary crystallinity in plasticized PVC reported in calorimetric studies by Juijn. With decreasing temperature, two phenomena occurred in the temperature range from T_g + ca. 80°C to T_g: the vitrification of a concentrated amorphous solution and the slight crystallization of the polymeric component. The larger the difference between T_g and T′_m the broader the primary dispersion zone on the frequency scale. This broadening effect was explained as due to the difference in dependence of T_g and T′_m on plasticizer concentration, without any need to consider any specific interaction between plasticizer and PVC.     

Polymerization of vinyl chloride with organolithium compounds. V. Fractionation and solution properties of high molecular weight poly(vinyl chloride)

A sample of high molecular weight poly(vinyl chloride) (PVC) was fractionated by classical precipitation fractionation and gel-permeation chromatography (GPC) on a preparative scale. The fractions thus obtained were characterized by light scattering, viscometry, and by the GPC method. The measured weight-average molecular weights M?_w, intrinsic viscosity [η], and polydispersity index M?_w/M?_n values were used for the determination of the Mark-Houwink equation, [η] = KM^a, for PVC in cyclohexanone (CHX) at 25°C valid for molecular weights from 100,000 to 625,000.     

Thermal and burning properties of wood flour-poly(vinyl chloride) composite

The present study deals with the effects of wood flour on thermal and burning properties of wood flour-poly(vinyl chloride) composites (WF-PVC) using thermogravimetric (TG), cone calorimetry (CONE), and pyrolysis?Cgas chromatography/mass spectrometry (Py?CGC/MS). TG tests show that an interaction occurred between wood flour and PVC during the thermal degradation of WF-PVC. Wood flour decreased the temperature of onset of decomposition of PVC. However, the char formation could be increased by adding wood flour to PVC. CONE test indicates that wood flour had positive effects on heat release and smoke emission of PVC. Comparing with PVC, WF-PVC reduced average heat release rate and the peak HRR by about 14 and 28%, respectively; smoke production rate was also decreased. The degradation mechanism was studied by Py?CGC/MS. The results show that the volatile pyrolysis products of WF-PVC are very different from PVC. The yields of HCl and aromatic compounds decreased dramatically, and the aliphatic compounds increased by the incorporation of WF.     

Relaxation properties of plasticised poly(vinyl chloride) and PVC blends

The temperature-frequency dependence of dielectric parameters for several PVC-plasticizer systems and PVC blends was obtained. Kinetic and activation parameters and α-relaxation spectra were estimated. The increase of the polar group number and size in the plasticizer molecules results in the narrowing of the relaxation spectra and in the increase of inner mobility of PVC segments. It was found for PVC-ABS and PVC-Paraloid blends that all relaxation characteristics depend on the miscibility of components. The results were also confirmed by the cloud point data.     

On suspension polymerization of vinyl chloride. Polymerization of vinyl chloride in the presence of epoxidized oil

A study has been made on the suspension polymerization of vinyl chloride in the presence of epoxidized cottonseed oil. Inclusion of the additive into the polymer chain was proved by i.r. spectrophotometry. The effects of epoxidized cottonseed oil on polymerization rate and K-value were slight, but plasticizer absorption by the polymer was reduced. Thermogravimetric curves of the product have been obtained, and show that epoxidized cottonseed oil improves the thermostability of the polymer.     

Polymerization of vinyl chloride

Polymerization of vinyl chloride (VC) was studied. natural evolution of HCl from VC occurred in the polymerization. VC, VC-αd₁, VC-β,βd₂ and VC-d₃ were used to study the reactivities of the hydrogen atoms in the polymerization and the β-hydrogen atoms contributed to the chain transfer. Chemical and physical methods were used to observe irregular structures, such as branching, double bonds, and head-to-head or tail-to-tail addition, and also to confirm the relation between conversion and the irregular structures.     

Telomerization of vinyl chloride by benzyl chloride

Conclusions The systems Fe(CO)₅ + hexamethylphosphotriamide and Fe(CO)₅ + DMF are efficient initiators for the telomerization of vinyl chloride by benzyl chloride involving the C-Cl bond of the benzyl chloride, in which connection both the conversion of the telogen and yield of telomers is high. Telomers of general formula C₆H₅CH₂-(CH₂CHCl)_nCl (n=1–3) were isolated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2541–2546, November, 1980.     

Dynamic mechanical properties of plasticized poly(vinyl chloride). Linear free energy relationship in the poly(vinyl chloride)–ester system

A considerable number of quantitative attempts have been made to predict the properties of solutions containing polar polymers and polar solvents. Thermodynamic approaches have generally failed to accurately describe these systems. This can be be ascribed to the difficulty in determining structural characteristics arising from the variety of secondary interactions present in these highly complex solutions. A linear free energy relationship has been used here to explore changes encountered in solutions of monofunctional esters in poly(vinyl chloride) undergoing mechanical deformation. This treatment appears valid only for the rubbery region of the viscoelastic spectrum of this polymer. The data indicate that the observed changes are a function of corresponding changes in polymer intramolecular interactions.     

Henry's law and diffusion constants of vinyl chloride in poly(vinyl chloride) at high temperature

The Henry's law and diffusion constants of vinyl chloride in poly(vinyl chloride) were determined at temperatures of 24, 90, 120, 150, and 170°C for weight fractions of vinyl chloride between 0.2 × 10^?3 and 0.8 × 10^?3. Above 90°C, Henry's law applies; values of the constant increase with temperature from 1.8 × 10² to 5.5 × 10² atm per unit weight fraction of dissolved vinyl chloride. The heat of desorption is about 15 kJ/mole. At 24°C, the nominal Henry's law constant was smaller than would have been obtained by extrapolating the values found at higher temperature. The diffusion constants increase with temperature from about 2 × 10^?13 to 3 × 10^?7 cm²/sec. The activation energy for diffusion is about 110 kJ/mole between 90 and 170°C. Although all values were determined in the absence of air, it is likely that they apply to polymer in air. They may, therefore, be used to calculate the vinyl chloride content in the gas above poly(vinyl chloride) under specific processing conditions.     

Elastic and viscoelastic properties of sugarcane bagasse-filled poly(vinyl chloride) composites

Elastic and viscoelastic properties of sugarcane bagasse-filled poly(vinyl chloride) were determined by means of three-point bending flexural tests and dynamic mechanical and thermal analysis. The elastic modulus, storage modulus, loss modulus, and damping parameter of the composites at fibre contents of 10, 20, 30, and 40% in mass were determined, as well as those of the unfilled matrix. There was a correlation between the elastic modulus and storage modulus of the composites. Moreover, the elastic and viscoelastic properties of the composites were highly influenced by fibre content.