Measurement of molecular weight of poly(vinyl chloride)

Molecular weights of six bulk-process and five suspension-process PVC samples have been measured as part of a study aimed at developing a technique for gel permeation-chromatographic analysis of this polymer in tetrahydrofuran at room temperature. Osmometric M?_n values measured in cyclohexanone appear to be valid; the results are insensitive to thermal history or ultrasonic irradiation of the solution. Corresponding measurements in tetrahydrofuran changed with measurement temperature and indicated the presence of stable supermolecular PVC aggregates in this solvent. Such aggregates can be dispersed by ultrasonic treatment of the solution for brief periods. Simultaneous degradation of PVC molecules appears to be prevented by addition of small concentrations of nonionic surfactant to the tetrahydrofuran solutions. Treated solutions are suitable for GPC analyses at ambient temperatures. The results of osmometry, light scattering, and GPC agreed well.     

Influences of molecular weight on photodegradation of poly(vinyl chloride)

2-Dicyanomethylene-1,3-indandione forms colourless adducts with higher molecular derivatives of N,N-Diethanolaniline which thermally decompose to dark blue dyes. The rate of the dye formation is determined UV-photometrically and is compared with rates for monomeric model compounds. It is shown that reaction rates can be correlated with the solvent polarity parameter E_T′ (r = 0,928). Due to kinetic data a carbanionic mechanism is suggested.     

Correlation between some solution and mechanical properties of poly(vinyl chloride) and chlorinated poly(vinyl chloride)

Correlations have been found between solubility parameters and some mechanical properties of a series of vinyl polymers containing 56.6–69.9% chlorine when tested below their glass transition temperature. It is shown that stress at yield increases similarly with chlorine content and with the volume occupied by a monomer unit in the polymer. Using the Reiner-Weissenberg theory of the dynamic strength of materials as a criterion and a rheological model based on a pair of Maxwell bodies in parallel with a Hooke spring, the amount of dissipated and conserved work to yield point was calculated. A parameter, defined as the ratio of work to cohesive energy density, describes the efficiency of the system. The overall efficiency of the system, based on work to break, and proportional efficiency, based on work to yield point, are affected by chlorine content and strain rate. In addition, a potential energy parameter is defined which describes the cohesive energy per volume occupied by monomer unit of the polymer. This parameter is proportional to the total work to break as well as to the ratio of the residual work after yield to total work at all strain rates tested. The major portion of work is conserved up to yield; only a small portion is dissipated. From the yield point to break, after the onset of viscous flow, the major part of this work is dissipated.     

Influence of molecular weight of poly (methyl methacrylate) on its miscibility with poly (vinyl chloride) in the solution

In this work, the molecular weight effect on miscibility between poly(vinyl chloride) (PVC) and poly(methyl methacrylate) (PMMA) in cyclohexanone(CH) solutions at 30 °C was examined by the viscometric method. Three samples of PMMA were prepared by emulsion polymerization, which molecular weights were changed by tert-dodecyl-mercaptan (TDDM) content. The parameter Δb is used to predict polymer-polymer miscibility of PVC/PMMA/cyclohexanone blend. Δb values indicated that the highest molecular weight of PMMA is immiscible with PVC resin. The molecular weight of PMMA decrease with the increase of the contention of TDDM, and the contribution of miscibility PVC/PMMA blend in CH is better.     

Effect of the molecular weight on the plasticization properties of poly(hexane succinate) in poly(vinyl chloride) blends

Blends of poly(vinyl chloride) (PVC) and poly(hexane succinate) (PHS) with various molecular weights were analyzed with respect to their mechanical properties, durability, and thermal stability. We found that the molecular weight of PHS played an important role in the plasticizing process, and the single glass-transition temperature (T _g) of the PVC blends measured by dynamic mechanical analysis supported the complete miscibility between PHS and PVC. The plasticizing efficiency of PHS increased as the molecular weight increased; this reflected the gradually increasing elongation at break and the decreased T _g of the PVC blend. Meanwhile, the higher molecular weight of PHS also improved the resistance of migration and thermal stability but decreased the biodegradability of the PVC blends; this was due to the strong intermolecular interactions between PHS and PVC. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47081.     

Preparation and application of low molecular weight poly(vinyl chloride). IV. Preparation and characteristics of poly(vinyl chloride) with broad molecular weight distribution

Poly(vinyl chloride) (PVC) with a broad molecular weight distribution (BMD-PVC) was prepared by suspension polymerization in the presence of PVC with relatively lower molecular weight (LMW-PVC), which was prepared by suspension polymerization in the presence of 2-mercaptoethanol as a chain-transfer agent. It is elucidated using porosity measurement, scanning electron microscopy (SEM), and energy dispersion X-ray microscopy (EDXM) that the resultant BMD-PVC grains have an interesting internal structure at the level of primary particles. Discoloration time and fusion time of the BMD-PVC was studied. Discoloration time and fusion time of BMD-PVC is particularly dependent on the polymerization degree (Pw) of LMW-PVC and LMW-PVC content in the BMD-PVC samples. © 1994 John Wiley & Sons, Inc.     

Preparation and properties of some filled poly(vinyl chloride) compositions

Different samples of filled poly(vinyl chloride) (PVC) compositions were formulated from PVC, a polar plasticizer mixture consisting of dioctylphthalate (DOP) and a chlorinated paraffin, and variable proportions of a white filler such as barite, calcium carbonate, kaoline, quartz, or talc; a conductive filler such as High Abrasion Furnace (HAF) carbon black; or a hydrated mineral filler such as aluminium hydroxide, magnesium hydroxide, or calcium hydroxide. Epoxidized soybean oil as a heat stabilizer and sandorin red (BRN) pigment were added. Electrical and mechanical studies show that the incorporation of white fillers produces a plasticized PVC of good electrical insulation character whereas the addition of HAF carbon black produces a sample with some electrical conductivity; both of them have good mechanical properties. Of the hydrated fillers studied aluminium hydroxide has been found to impart the best fire retardancy and good electrical properties for electric wires and cables. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2657–2670, 1999     

Preparation and application of low molecular weight poly(vinyl chloride). II. Thermal stability of blended poly(vinyl chloride)

The blending effect of poly(vinyl chloride) (PVC) with relatively higher molecular weight (HMW-PVC) and relatively lower molecular weight (LMW-PVC) has been investigated by measuring various thermal stability and fusion times. The thermal stability of the blended PVC is improved when the small amount of LMW-PVC obtained using mercapto compounds as a chain-transfer agent is blended into PVC with HMW-PVC. At the LMW-PVC content from about 5–30 wt %, the thermal stability of the blended PVC is much more improved. Furthermore, the blended PVC with LMW-PVC, obtained using mercapto compounds, exhibits significant improvement in the discoloration time. The fusion time of the blended PVC is related to the weight-average polymerization degree of LMW-PVC and the LMW-PVC content. © 1994 John Wiley & Sons, Inc.     

Flow properties of poly (vinyl chloride)

A detailed review of the material published to date on the flow properties of poly(vinyl chloride) is given. The dependence of viscosity on concentration molecular weight, molecular weight distribution, shear and temperature for concentrated and molten poly (vinyl chloride) is considered. Polymer blends and plastisols are also included.     

Studies of electrical properties of some fire-retarding poly(vinyl chloride) compositions

Several fire-resistant formulations were prepared from a sample of poly(vinyl chloride) (PVC), small variable proportions of chloroorganic adducts [1,2,3,4,7,7-hexachloro-5-carboxy,bicyclo(2,2,1)heptene-2] or [1,2,3,4,7,7-hexachloro-5-carboxy,5-methyl-bicyclo(2,2,1)heptene-2] as fire-retarding modifiers, plasticizers (dibutylphthalate and a chlorinated paraffin), and a heat stabilizer (dibutyltindilaurate). The fire-resistance and electrical properties of the obtained formulations were studied to obtain a fire-retarding plasticized PVC of good electrical insulation character. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 27–35, 1997     

Influences of diallyl phthalate as chain extender on the properties of high molecular weight poly(vinyl chloride) resin

A higher porosity with better thermostability is desirable for poly(vinyl chloride) (PVC) resin. In this study, high molecular weight PVC resins are prepared by vinyl chloride monomer (VCM)‐diallyl phthalate (DAP) suspension copolymerization in a 20‐L reactor at 50 °C using DAP as chain extender. SEM, BET, and analyses of plasticizer absorption results show the high molecular weight poly(vinyl chloride) (HPVC) by DAP‐VCM copolymerization is loose and porous. With increasing DAP content when the mass ratio of DAP/VCM (ω) is below the gel point, the porosity and the degree of polymerization increase. Nevertheless, the bulk density and particle size decrease. When more than the gel point, these relationships are reversed. Thermogravimetric analysis revealed that the HPVC had better thermostability than that of commercial PVC, and its thermostability increases with increasing ω before it reaches the gel point. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45093.     

Influence of the thermal history on dielectric properties of poly(vinyl chloride)

In this paper, we report dielectric permittivity and loss of poly (vinyl chloride) samples that have received three different thermal treatments: (a) as received, (b) quenched from 110°C to 20°C and (c) slow cooled at 5°C/h. There are several observations: first, the secondary (β) loss peak-is not representative of a simple mechanism of transition, in agreement with results of other authors (10), second, in the glass transition zone, there are clearly two peaks (α₁ and α₂)—α₁, is a typical peak of an amorphous glass transition; the second, α₂, has possibly a crystalline origin—and, third (and the most interesting fact), there is an increase of the loss tangent in the intermediate zone between α and β peaks showing a new relaxational peak with high activation energy (70 Kcal/mole), in agreement with dynamic mechanical results (6).     

Influence of thermal aging on the electrical properties of poly(vinyl chloride)

This article reports on the study of the thermal aging of poly(vinyl chloride) (PVC) used in medium‐ and high‐voltage cables. It is shown that the thermal aging leads to the degradation of the material and to the modification of its electrical properties. The degradation is all the more important and faster as the temperature is high. This degradation is attributed to a progressive evaporation of the plasticizer at the beginning of aging and to a weight loss of stabilizer followed by a change in the color of polymer and a release of hydrochloric acid at more advanced stages of aging. It also results in a crosslinking of the material and a shrinking of samples. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4728–4733, 2006     

Electrical properties of poly(vinyl chloride) compositions

A sample of poly(vinyl chloride) (PVC) and a polar plasticizer consisting of dioctyl phthalate (DOP) and dibutyl phthalate (DBP) was prepared and found to possess inconvenient electrical properties (permittivity, dielectric loss, and conductivity). Different samples of PVC compositions were formulated from the PVC–DOP–DBP system and also variable proportions of a copolymer of 1-octadecene-maleic anhydride or its hexadecylester. Lead stearate as a heat stabilizer and kaolin as a filler were added. The effect of copolymer structure on the electrical properties of the PVC–DOP–DBP system was studied to obtain a plasticized PVC of good electrical insulation character. © 1993 John Wiley & Sons, Inc.     

Rheological and mechanical properties of poly(vinyl chloride)/chlorinated poly(vinyl chloride) miscible blends

The properties of poly(vinyl chlorlde)/ehlorinated poly(vinyl chloride) (61.6 percent C1) blends, prepared by melt and solution blending, were measured by various tests. Based on the chlorinated poly(vinyl chloride) (CPVC) composition, percent chlorine, and mole percent CC1₂ groups, these blends were expected to show intermediate properties between miscible and immiscible systems. Indicative of miscible behavior were the single glass transition temperatures over the entire composition range for both melt and solution blended mixtures. A single phase was also indicated by transmission electron microscopy. However, the yield stress showed a minimum value less than either of the pure components in the 50 to 75 percent CPVC range, which is characteristic of two-phased systems. Specific volume, glass transition temperature, and heat distortion temperature were linear with binary composition. The storage modulus showed a small maximum, suggesting a weak interaction between the two miscible polymers. Heats of melting for the residual PVC crystallinity were also less than expected from linear additivity. At 160°C and 210°C, the logarithm of the complex viscosity was essentially linear with volume fraction of CPVC, except for a very slight decrease in the 50 to 75 percent CPVC range, which may have been a result of lower crystallinity. At 140°C, the complex viscosity of the CPVC was less than that of PVC owing to the higher crystallinity of the latter. The viscosities were similar at 160°C, but at 210°C, where most of the crystallites had melted, the complex viscosity of the CPVC was higher because of its higher glass transition temperature.     

Influences of some polymerization conditions on particle properties of suspension poly(vinyl chloride) resin

Effects of polymerization temperature, conversions, and nonionic surfactant on the particle properties of suspension poly(vinyl chloride) (PVC) resins were investigated. It was shown that polymerization temperature has no significant influences on the mean particle size of PVC resin, and that the cold plasticiser absorption (CPA) of resin decreases linearly with the increase of polymerization temperature. Agglomeration of VCM droplets finishes before 20% conversion, and the mean particle size keeps almost constant at later stages of the polymerization process, but the CPA continues decreasing with the increase of conversion. Scanning Electron Microscopy (SEM) micrographs show that the degree of agglomeration of primary particles increases with polymerization temperature and conversion. Addition of nonionic surfactant to the VCM suspension system, as a secondary suspending agent, has a great influence on the particle properties of PVC resin. The particle size and CPA increase as the concentration of nonionic surfactant increases. The nonionic surfactant with a greater HLB value is more effective in raising the mean particle size, but is less effective in raising the CPA. It is considered that the added nonionic surfactant would be absorbed faster on the VCM/water interface than the poly(vinyl alcohol) (PVA), which was used as the primary suspending agent. Because the colloid protection ability of the nonionic surfactant is less than that of PVA, droplets become less resistant to coalescence, and the mean particle size of the final PVC resin increases consequently. The increase of porosity is caused by the combined effects of increased coalescence of VCM droplets and the nonionic surfactant's steric effect inside the droplets. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1544–1552, 2002     

Influence of temperature on the ultrasonic degradation of poly(vinyl acetate) and poly(vinyl chloride)

This study investigates the effect of temperature on the ultrasonic degradation of polyvinyl acetate and polyvinyl chloride in chlorobenzene. The time evolution of molecular weight distribution was determined using gel permeation chromatography. Continuous distribution kinetics was used to obtain the degradation rate coefficients. The rate coefficients decrease with increasing temperature, and this is attributed to the increase of vapor pressure and the decrease of kinematic viscosity. The degradation rate coefficient also changes sharply near the glass transition temperature, indicating that this factor may play a role in the degradation process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 12: 2818–2822, 2003     

Rheological properties of syndiotacticity-rich ultrahigh molecular weight poly(vinyl alcohol) dilute solution

Viscoelastic behavior of the dilute solution of ultrahigh molecular weight syndiotactic poly(vinyl alcohol) (UHMW s-PVA)/dimethyl sulfoxide (DMSO)/water was investigated through rheological response. Below a critical temperature, the dynamic storage modulus (G′) of the solution became greater than the dynamic loss modulus (G″) and the viscoelastic exponent for G′ became smaller than that for G″ before macroscopic gelation, which indicates the evolution of viscoelastic solid properties at the sol state. Also, the loss tangent (tan δ) of the solution below the critical temperature increased with increasing frequency. Consequently, the dilute solution of UHMW s-PVA/DMSO/water showed the rheological behaviors as can be observed in general chemical or physical gel systems below the critical temperature. These results suggest that solid-like heterogeneity prevailed in the solution before macroscopic gelation with decreasing temperature. Such heterogeneity was considered as phase-separated domains attributed to spinodal decomposition. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 569–576, 2001     

The powder properties of poly(vinyl chloride) resins

The properties of powders depend mainly upon the characteristics of the individual particles and their interactions. In the case of PVC resins, particle characteristics vary broadly depending upon the manufacturing process used or variables within a given process. In this paper, the effects of grain size, size distribution, grain shape, degree of compaction and static on the bulk density and flow properties of PVC resins are studied. Results indicate that grain shape mainly affects bulk density while grain size and distribution mainly affect powder flow. The degree of compaction and the amount of static on the resin grains are variables which can overwhelm other powder properties.     

Surface properties of carbons from poly(vinyl chloride)

Non-activated carbons were prepared by the thermal degradation of poly(vinyl chloride) (PVC) in air or nitrogen atmosphere in the temperature range 600-1000°C. Carbon dioxide-activated carbons from PVC were also obtained by gasification of non-activated carbon from PVC at 900°C burn-off (4-50%). Thermal degradation in air atmosphere gave high carbon yield because the oxygen of air increased crosslinking at lower temperature and chemisorbed on the carbon surface at high temperatures. Thermal degradation in air and gasification with carbon dioxide created carbon-oxygen surface groups which increased the hydrophilicity of the carbon surface and consequently increased water adsorption capacity. Gasification with carbon dioxide to high burn-off created new pores and widened already existing pores.