A rheological study of the ageing of emulsion and microsuspension-based PVC plastisols

A PVC plastisol is a homogeneous dispersion of PVC resin in a liquid continuous phase consisting basically of a plasticizer and a thermal stabilizer; the PVC resin being usually a fine powder is polymerized by emulsion or microsuspension processes. Plastisol rheology is affected by many aspects of the plastisol formulations, such as type and amount of each ingredient, the mixing procedure, temperature, and the effect of PVC resin properties. In this work, the ageing behavior of PVC plastisols with different resin types was studied, with the results showing an unexpected behavior in the elastic modulus, probably originating from plasticizer adsorption at the surface of the PVC particles. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of zinc stearate and/or epoxidized soybean oil on gelation and thermal stability of PVC‐DOP plastigels

The effects of zinc stearate (ZnSt₂) and/or epoxidized soybean oil (ESO) on mechanical properties and on thermal stability of plastigels obtained from polyvinylchloride (PVC) and dioctylphthalate (DOP) plastisols were studied using calorimetric, spectroscopic, and tensile‐testing techniques. Plastigels having 2.5 or 5.0 part ZnSt₂ and/or 5 part ESO and 60 part DOP per 100 part PVC (phr) were gelled by heating at 140°C. The tensile strength of plastigels with no additive and having 5 phr ZnSt₂, ESO, and both ZnSt₂ and ESO were 0.79, 0.46, 0.98, and 0.58 kN/cm², respectively. The decrease of tensile strength of plastigels with ZnSt₂ could be explained by the existence of ZnSt₂ in the solid phase in plastigels, as shown by differential scanning calorimetry (DSC). ESO helped better fusion of the plastisols without any additive and with ZnSt₂. Higher tensile strengths of ESO containing plates indicated more complete gelation of the plastisols. The thermal stability of plastigels in terms of color and their yellowness index (YI) were higher for ZnSt₂ containing plastigels. Conjugated polyene concentrations were calculated from UV spectra of the films heated at 140°C. The reaction rate constant of the dehydrochlorination of PVC changed with the additives. Faster dehydrochlorination than control gels occurred in gels having ZnSt₂ at long heating times due to the autoaccelerating effect of ZnCl₂ formed by reaction of eliminated hydrogen chloride and ZnSt₂. Organic acid formation reaction between ZnSt₂ and HCl formed by dehydrochlorination is investigated from the IR band at 1540 cm⁻¹ and 3400 cm⁻¹ during heating of the plastigel films. A synergistic effect of ESO and ZnSt₂ was observed when the mechanical strength and heat stability were considered together. Although ESO increased tensile strength, ZnSt₂ increased thermal stability of the plastigels at early times when they were present simultaneously in plastisols. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2488–2498, 1999     

Dynamic TG studies on the thermal decomposition of PVC plastisols

The kinetics involved in the thermal decomposition of PVC plastisols and unmixed PVC-plasticizer systems were compared using dynamic thermogravimetric (TG) analysis. Three kinetic models were tested. In all cases thermograms obtained at different heating rates were simultaneously correlated with the same constants. Significant differences indicative of PVC-plasticizer (DOP) interactions were found between the plastisol systems and the unmixed PVC-plasticizer systems. When the plasticizer is in the paste, its evolution suffers a delay with respect to the case when PVC and plasticizer were separated. The activation energy for DOP evolution takes the value 109.2 in the first case and 81.6 KJ/mol in the second case. PVC decomposition takes place at lower temperatures when it is in the paste, and its activation energy is 177.4 and 206.7 KJ/mol for PVC in plastisol and unmixed PVC, respectively.     

Changes in rheological properties of polyvinyl chloride plastisols with storage time

In this study, the changes in the rheological curves of polyvinyl chloride (PVC) plastisols with increasing storage time and the factors affecting these changes were studied. The results show that with increasing storage time, all the “viscosity–temperature” and “viscosity–time” rheological curves of PVC plastisols exhibit nonnormal distribution change trends, that is, the viscosity first decreases, and then changes from slow increasing to rapid increasing, forming a shoulder peak, reaches to the maximum value and gradually decreases. With increasing storage time, the complex viscosities of PVC plastisols increased generally in the first, the second, and the fourth stages, and the gelation process shortened in the third stage. The first and second stages of the viscosity changes reflect the “time–temperature” equivalence principle of PVC plastisol in suspension stage. However, the maximum viscosity of PVC plastisol corresponding to temperature Tη_max does not change with increasing storage time.     

Photolysis of dialkyl phthalates and poly(vinyl chloride) plasticized with dialkyl phthalates at wavelengths exceeding 290 nm

When dialkyl phthalate plasticizers, neat poly(vinyl chloride), PVC, and PVC plasticized with dialkyl phthalate are subjected to near UV radiation at λ_inc > 290 nm, chemical alterations are induced by traces of impurities capable of absorbing light in this wavelength range. The main photoproducts formed in the case of neat phthalates are olefins, alcohols, and phthalic acid anhydride. Neat PVC undergoes C? Cl bond cleavage and, in addition, carbonyl and polyene groups are formed. The formation of carbonyl groups is a nonlinear (auto-accelerated) process whereas polyene generation occurs linearly with increasing irradiation time. The photolysis of phthalate-plasticized PVC is characterized by the decomposition of the plasticizer, evidenced by the decrease in the absorption band at 278 nm, and by the formation of carbonyl groups attached to PVC and the cleavage of C? Cl bonds as evidenced by the increase or decrease in the IR absorption bands at about 1710 and 617/639 cm^?1, respectively. Phthalates hardly influence the incorporation of carbonyl groups into PVC (an auto-accelerated process) and retard only slightly the cleavage of C? Cl bonds. By contrast, phthalates sensitize the incorporation of carbonyl groups upon irradiation at λ_inc = 254 nm. Within the error limit no effect of the chemical nature of the phthalate on the formation of photoproducts was detectable upon performing irradiations at λ_inc > 290 nm.     

Meaningful evaluation of plastisol gelation and fusion temperatures by dynamic mechanical analysis

In most PVC plastisol processing operations, gelation and fusion characteristics of the plastisol are critically important. For example, in chemically foamed plastisols, plastisol fusion temperature and blowing agent decomposition temperature must be carefully coordinated. In rotomolded parts, rates of gelation may determine the quality of the finished parts. For plastisol products made by any process, the final fusion temperature determines the processing temperatures required to give the finished product acceptable mechanical properties. For a variety of reasons, the methods commonly used to characterize plastisol gelation and fusion (hot bar test, resin in plasticizer clear point, torque rheometer measurements, etc.) provide comparisons between plastisols but do not provide temperatures that are easily related to actual industrial processes. With dynamic mechanical analysis (DMA), one can characterize, under low shear conditions, the temperatures at which gelation begins, gelation ends, and complete fusion occurs. Additionally, it is possible to record plastisol viscosities (and other dynamic mechanical properties) over the processing temperature range. We used a multiple linear regression program to analyze the DMA data for plastisols heated from 30 to 210°C and containing either 70, 80 or 90 phr of Jayflex dihexyl phthalate (DHP) or Jaylflex di-isodecyl phthalate (DIDP). Further, we determined the plasticizer phr dependence and the reproducibility of gel and fusion temperatures given by data analyzed in this manner. Finally, for comparison, we analyzed the reproducibility of initial and final plastisol gel temperatures and fusion temperatures, which were determined by visually analyzing the DMA data for plastisols containing 70, 80, and 90 phr of Jyflex plasticizers DHP, Jayflex 77, diisononyl phthalate (DINP), and DIDP. Precise characterization of plastisol gelation and fusion behavior will, undoubtedly, facilitate substitution of plastisol ingredients as is often required by those who manufacture and process plastisols.     

Preparation and characterization of flexible poly(vinyl chloride) foam films

In this study, the effect of activator ZnO and heating time at 190°C on foaming, gelation, and dehydrochlorination of poly(vinyl chloride) (PVC) plastisol was investigated. For this purpose, a PVC plastisol was prepared by mixing PVC, dioctyl phthalate (DOP), azodicarbonamide (ADC), ZnO, and the heat stabilizers calcium stearate (CaSt₂) and zinc stearate(ZnSt₂). PVC plastisol films were heated for 3, 6, 12, and 24 min periods at 190°C to see the effect of heating time on the gelation and foaming processes of the PVC foam. The time of 12 min was determined to be optimum for the completion of gelation and foaming processes without thermal degradation of PVC. No foaming was observed under the same conditions for the samples without ZnO. ZnO had a significant catalytic effect on ADC decomposition, accelerating the foaming of the films. Average porosity measurement showed a consistent increase in porosity with heating time up to 76% and the average density decreased from 1.17 to 0.29 g/cm³ on foaming. Tensile tests showed that the tensile strength and tensile strain both increased considerably up to 0.98 MPa and 207%, respectively, with heating time and the elastic modulus was seen to gradually decrease from 4.7 to 0.7 MPa with heating time. Films without ZnO had higher tensile strength since there were no pores. PVC thermomat tests showed that ZnO lowered the stability time of plastigel film with azodicarbonamide. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

DSC study of foamable poly (vinyl chloride‐co‐vinyl acetate) plastisols of different commercial plasticizers

In this article the characterization of the thermal behavior of foamable PVC (Poly (vinyl chloride)) plastisols from 20 different plasticizers has been studied by differential scanning calorimetry (DSC). The interactions between the resin and the plasticizer as well as the decomposition of the azodicarbonamide (ADC)—the chemical blowing agent (CBA) used—have been analyzed. The latter process is of crucial importance for the knowledge of plasticized PVC flexible foam formation. Clear effects of the chemical nature of the plasticizers and their molecular weight (M_w) have been observed, both in the interactions (swelling and early stages of gelation) between the resin and the plasticizer, as well as in the temperature of the ADC decomposition and the shape of the DSC peak. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Unique benzoate plasticizer for reducing viscosity and fusion temperature

Plastisol viscosity reduction and control is an important property specification in many vinyl plastisol formulations. A unique benzoate plasticizer is under development that functions as a viscosity reducer. It also is a highly solvating plasticizer in standard plastisol systems. Data are presented on the effects of the new benzoate plasticizer on the properties of phthalate‐ and benzoate‐containing plastisols and vinyl sheet.     

Kinetic analysis of the thermal degradation of PVC plastisols

The thermal degradation of plasticized polyvinyl chloride (plastisol) is reported here. Plastisols used in the present work were prepared with the plasticizer diethylhexyl phthalate in different proportions. Thermogravimetric analysis has been applied to study the behavior of plastisols at high temperatures and to evaluate their degradation kinetics. Several tests were carried out at different heating rates and the variation of the degree of reaction with time and temperature was calculated. The influence of the heating rate in dynamic measurements (5–40°C/min) on kinetic parameters, such as activation energies and reaction orders, has also been studied. These parameters were calculated from dynamic thermogravimetric analysis tests using Friedman analysis and a kinetic model for the degradation of poly(vinyl chloride) and plastisols has been then developed. The obtained model was able to simulate the thermal degradation process of plastisols in dynamic conditions and was used to evaluate the effects of additives in the degradation. The results of this study can be used to optimize the concentration of plasticizers and stabilizers in poly(vinyl chloride) formulations. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1069–1079, 1999     

Study on hot air aging and thermooxidative degradation of peroxide prevulcanized natural rubber latex film

The air‐aging process at 120°C and the thermooxidative degradation of peroxide prevulcanized natural rubber latex (PPVL) film were studied with FTIR and thermal gravity (TG) and differential thermal gravity (DTG) analysis, respectively. The result of FTIR shows that the ? OH and ? COOH absorption of the rubber molecules at IR spectrum 3600–3200 cm^?1, the ? C?O absorption at 1708 cm^?1, and the ? C? OH absorption of alcohol at 1105 and 1060 cm^?1 increased continuously with extension of the aging time, but the ? CH₃ absorption of saturated hydrocarbon at 2966 and 2868 cm^?1, the ? CH₃ absorption at 1447 and 1378 cm^?1, and the C?C absorption at 835 cm^?1 decreased gradually. The result of TG‐DTG shows that the thermal degradation reaction of PPVL film in air atmosphere is a two‐stage reaction. The reaction order (n) of the first stage of thermooxidation reaction is 1.5; the activation energy of reaction (E) increases linearly with the increment of the heating rate, and the apparent activation energy (E₀) is 191.6 kJ mol^?1. The temperature at 5% weight loss (T_0.05), the temperature at maximum rate of weight loss (T_p), and the temperature at final weight loss (T_f) in the first stage of degradation reaction move toward the high temperature side as the heating rate quickened. The weight loss rate increases significantly with increment of heating rate; the correlation between the weight loss rate (α_p) of DTG peak and the heating rate is not obvious. The weight loss rate in the first stage (α_f1) rises as the heating rate increases. The final weight loss rate in second stage (α_f2) has no reference to heating rate; the weight loss rate of the rubber film is 99.9% at that time. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3196–3200, 2004     

The interaction of hydrogen sulfide with lead- and barium–cadmium–zinc-stabilized poly(vinyl chloride)

Poly(vinyl chloride) polymers stabilized with tribasic lead sulfate discolor upon exposure to hydrogen sulfide gas as a result of lead sulfide formation. The discoloration occurs for samples in both cord and sheet forms and is shown to be a function of total H₂S exposure, reaching a limiting value that is determined by the amount of lead stabilizer used in the polymer formulation. The permeation and diffusion constants for H₂S through PVC stabilized with tribasic lead sulfate and with a liquid Ba–Cd–Zn formulation are found to be P_Pb = (6.0 ± 0.2) × 10^?9, P_BaCdZn = (5.2 ± 0.2) × 10^?9 (both in cm³ gas?cm film/cm² area?sec?cm Hg), D_Pb = (1.3 ± 0.2) × 10^?7 cm²/sec, and D_BaCdZn = (6.4 ± 0.6) × 10^?8 cm²/sec, all measured at 21°C. The stabilizing efficiencies of the formulations were assessed by HCl evolution measurements, which show that exposure to H₂S decreases the initial polymer stability for both Pb-stabilized and Ba–Ca–Zn-stabilized formulations. Protection of stabilized PVC formulations from diffusing hydrogen sulfide is thus advisable for long-term stability as well as for color integrity.     

Extensional viscosity measurements and characterization of poly (vinyl chloride‐co‐vinyl acetate) plastisols and foams

The foaming of PVC‐VA [Poly (vinyl chloride‐co‐vinyl acetate)] plastisols is a complex combination of processes involving the simultaneous curing of the paste with the evolution of gases caused by the decomposition of the chemical blowing agent. The extensional viscosity is a fundamental characteristic of the material, responsible for the behavior of the system when undergoing the extensional stress produced by the released gases. Nevertheless, such changes have not been considered to the same extent as the complex viscosity evolution or the thermal processes suffered by PVC‐VA plastisols. The objective of the present work is to study the extensional viscosity of the PVC‐VA plastisols prepared with three plasticizers of similar structure, but with different curing and rheological behavior in order to investigate its influence on the quality of the foams obtained. Extensional viscosity measurements under forced prestretch conditions revealed that depending on the structure and consequently on the compatibility of the plasticizer used, each plastisol develops its properties and structure accordingly. DINCH plasticizer (Diisononyl cyclohexane‐1,2‐dicarboxylate presenting alicyclic ring) seems to be the less compatible compared with the other two studied (both presenting aromatic rings) according to its behavior during the curing and foaming processes and may not be able to withstand the pressure evolved by the released gases during the foaming process yielding foams of poorer quality. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Infrared study of combined effect of γ-radiation and elevated temperature on poly(vinyl chloride)

Infrared absorption spectroscopy has been used to investigate the combined effect of γ-radiation and heat on poly(vinyl chloride) (PVC). The recorded spectra showed that exposure of PVC samples to gamma doses from 0.5 to 15 Mrad results in remarkable changes in the absorbances of their absorption bands. Also, the exposure to doses from 3 to 15 Mrad results in an appearance of a C?O band at 1720 cm^?1 and O? H band at 3450 cm^?1. The nature of the formation of these bands was discussed in terms of peroxide-mediated oxidative degradation mechanism. Moreover, it was found that heat treatment of PVC samples over the temperature range 25–180°C causes no noticeable changes in their spectra apart from slight changes in the absorbances of the bands. On other hand, it was found that heat treatment of the irradiated samples causes considerable increase in the intensity of the C?O band. In addition to the well-defined and sharp band appearing at 1720 cm^?1, the spectra of the samples irradiated with 10 and 15 Mrad exhibited two bands at 1070 and 1120 cm^?1. The obtained data led also to the conclusion that the C? Cl bands cannot be used as a measure of crystallinity of PVC.     

Processing and properties of high-temperature creep-resistant PVC plastisols

The effect of the use of an unsaturated reactive plasticizer trimethylopropane trimethacrylate, TMPTMA, on the structure and the creep behavior of poly(vinyl chloride), PVC, plastisols has been investigated as part of a program to develop a high-temperature creep-resistant liner material. The crosslinking reaction was initiated with a peroxide. The effect on the network structure of using a free radical scavenger in the formulation has also been studied. Gel yield and grafted PVC content in the gel increase with increased TMPTMA content in the plastisol. However, the residual unsaturation of TMPTMA decreases with increase of TMPTMA content. Introduction of TMPTMA into the plastisol promotes the creep resistance at high temperatures, and the effectiveness increases when there are PVC molecules grafted onto TMPTMA networks.     

Formulation and properties' evaluation of PVC/(dioctyl phthalate)/(epoxidized rubber seed oil) plastigels

Epoxidized rubber seed oil (4.5% oxirane content, ERSO) was prepared by treating the oil with peracetic acid generated in situ by reacting glacial acetic acid with hydrogen peroxide. The thermal behavior of the ERSO was determined by differential scanning calorimetry. The effect of the epoxidized oil on the thermal stability of poly (vinyl chloride) (PVC) plastigels, formulated to contain dioctyl phthalate (DOP) plasticizer and various amounts of the epoxidized oil, was evaluated by using discoloration indices of the polymer samples degraded at 160°C for 30 min and thermogravimetry at a constant heating rate of 10°C/min up to 600°C. The thermal behavior of the ERSO was characterized by endothermic peaks at about 150°C, which were attributed to the formation of network structures via epoxide groups, and at temperatures above 300°C, which were due to the decomposition of the material. Up to 50% of the DOP plasticizer in the PVC plastisol formulation could be substituted by ERSO without a marked deleterious effect on the consistency of the plastigel formed. In the presence of the epoxidized oil, PVC plastigel samples showed a marked reduction in discoloration and the number of conjugated double bonds, as well as high temperatures for the attainment of specific extents of degradation. These results showed that the ERSO retarded/inhibited thermal dehydrochlorination and the formation of long (n > 6) polyene sequences in PVC plastigels. The plasticizer efficiency/permanence of ERSO in PVC/DOP plastigels was evaluated from mechanical properties' measurements, leaching/migration tests, and water vapor permeability studies. The results showed that a large proportion of DOP could be substituted by ERSO in a PVC plastisol formulation without deleterious effects on the properties of the plastigels. J. VINYL ADDIT. TECHNOL., 2008. © 2008 Society of Plastics Engineers.     

Soft PVC foams: Study of the gelation,fusion, and foaming processes. I. Phthalate ester plasticizers

The use of foamed plastics gains more and more interest every day. Flexible poly(vinyl chloride) (PVC) foams have excellent mechanical properties and low price, thus their application is extensive. Foams are produced from plastisols, which are based on the suspension of the PVC resin in a plasticizer. Phthalates are the most used plasticizers in flexible PVC foam formation. In this study, we have studied the influence of the phthalate ester‐type plasticizers on the foaming process and the quality of the foams obtained from the corresponding plastisols. For the plastisols prepared with the nine phthalate plasticizers considered, we have studied and discussed the complex and extensional viscosities; the thermal behavior (DSC) including the decomposition of the chemical blowing agent, and the foam production by rotational molding. In addition, we have characterized the foams obtained by thermomechanical analysis, density, and bubble size distribution. As expected, clear correlations have been obtained between the molecular weight and structure of the plasticizer with the rheological behavior of the plastisols. The knowledge of the gelation and fusion processes and evolution of the extensional viscosity of the plastisols combined with the study of the thermal decomposition of the blowing agent in each plastisol allows for better understanding of the complex dynamic behavior of these foaming systems. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Plasticizer factors influencing take-up by PVC resins

The ease with which plasticizer is combined with poly(vinyl chloride) resin is a measure of processing characteristics critical in the dry blending of suspension PVC and the gelation of plastisols. By using commercial grade plasticizers, this study developed predictive equations for the following processing parameters of dialkyl phthalates in PVC:

• Relative dry-blend rates in suspension PVC as a function of plasticizer viscosity.
• Relative initial gelation temperatures in plastisols as a function of plasticizer molecular weight and solvating strength.
• Relative final gelation temperatures in plastisols as a function of plasticizer solvating strength.

This information allows one to predict the relative processing characteristics of any dialkyl phthalate plasticizer for PVC on the basis of its chemical and physical properties.     

Structure and properties of poly(vinyl chloride)‐triallyl cyanurate plastisols

Triallyl cyanurate (TAC) has been used as a reactive plasticizer to promote the high‐temperature creep resistance of poly(vinyl chloride) (PVC) plastisols. The resultant crosslinked structure is characterized using gel content and swell ratio measurements as well as Fourier transform infrared spectroscopy. The crosslinking reaction was initiated using peroxide. The effect on the network structure of using a free radical scavenger in the formulation has also been studied. The gel yield and crosslink density in the gel increase with increasing TAC concentration in the plastisol, while the grafted PVC fraction and the residual unsaturation of TAC behave in the opposite way. Introduction of TAC into the plastisol promotes creep resistance at high temperatures, and the logarithmic creep rate was found to decrease linearly with increasing crosslink density.     

Effect of PBMA on PVC‐based polymer blend electrolytes

Poly(vinyl chloride) (PVC)—poly(butyl methacrylate) (PBMA) blended polymer electrolytes with lithium perchlorate (LiClO₄) as the complexing salts are prepared by solution casting technique. The addition of PBMA into PVC matrix is found to induce considerable changes in physical and electrical properties of the polymer electrolytes. Addition of PBMA into PVC matrix is found to increase the conductivity by two orders of magnitude (1.108 × 10^?5 S cm^?1) when compared with that of the pristine PVC polymer electrolyte (10^?7 S cm^?1). Structural, thermal, mechanical, morphological, and polymer–salt interactions are ascertained from X‐ray diffraction (XRD), thermogravimetry/differential thermal analysis (TG/DTA), mechanical analysis, scanning electron microscope (SEM), and Fourier transform infrared spectroscopy (FTIR) respectively. A thermal stability upto 250 °C is asserted from the TG/DTA analysis. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44939.