Surface treatment of plasticized poly(vinyl chloride) to prevent plasticizer migration

In this investigation, plasticized poly(vinyl chloride) (PVC) was treated with poly(azido acrylate)s to prevent plasticizer migration. This was achieved by modification of PVC sheets with poly(azido acrylate)s in a dichloromethane solution followed by irradiation under UV light. The surface‐modified PVC sheets with poly (azido acrylate)s were characterized with Fourier transform infrared spectroscopy and scanning electron microscopy analyses. The migration of the plasticizer was prevented to a large extent from modified PVC in comparison with unmodified PVC. The amount of plasticizer migration with respect to the irradiation time, incubation time, and number of dipping times was evaluated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Alloying of poly(vinyl chloride) to reduce plasticizer migration

Concern over the migration of low molecular weight plasticizer from flexible poly(vinyl chloride) (PVC) used in toys and medical products has spearheaded the commercialization of a number of plasticizing polymers. In this study the plasticizing behavior of an ethylene/vinyl acetate/carbon monoxide terpolymer (Elvaloy® from DuPont) was investigated. Blends of PVC, Elvaloy 742, and dioctyl phthalate (DOP) were processed on a twin‐roll mill and compression molded into plaques. These materials were characterized in terms of their hardness, glass‐transition temperature (T_g), clarity, mechanical properties, and plasticizer migration behavior. The ratios of PVC/DOP/Elvaloy investigated were determined by experimental design. Using this approach it was possible to model the results and produce contour plots to map out the properties of a wide range of formulations. It was confirmed that Elvaloy 742 is compatible with PVC and has a plasticizing effect: this was demonstrated both in terms of a reduction in Shore A hardness and a reduction in T_g. Plasticizer migration was reduced in proportion to the amount of liquid plasticizer replaced. Plasticizing with Elvaloy gave an improvement in tear strength. However, at constant hardness there was no improvement in tensile strength from replacing DOP with Elvaloy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2022–2031, 2004     

Plasticizer migration from plasticized into unplasticized poly(vinyl chloride)

There exist important industrial applications, such as hoses or plastic windows, dealing with closely combining plasticized and rigid poly(vinyl chloride). Nevertheless, migration of plasticizer causes severe variation of the mechanical performance of the end-products. This work comprises an effort to investigate and understand these phenomena, also as an extension of previous work of ours in migration to liquid environments. The common system plasticized PVC/dioctylphthalate/unplasticized PVC was studied under two-sided diffusion conditions, i.e., from a thin sheet of plasticized sheet. The whole assembly was placed between two glass plates and then was held in an oven at 64°C to simulate accelerated test conditions. Some pressure was also applied to ensure perfect contact between the plastic sheets. Three different levels of initial plasticizer concentration (48, 66, and 100 phr) have been considered for a period of about five months, until equilibrium was reached. During this period the migration process was monitored by weight changes. Plots of M_t/M_∞ vs. t^½, where M_∞ the amount migrated at equilibrium and M_t the amount lost at time t, resulted in evident linear relationship. Therefore, it was proved that the Fick's law approximation for short times can be used to describe the migration kinetics for this solid/solid system. On the other hand, macroscopic observations revealed that no plasticizer was accumulated at the interface, i.e. all plasticizer leaving the plasticized sheet entered the rigid ones. Finally, it seems that the controlling stage is the diffusion inside plasticized PVC while possible annealing of the plasticized polymer structure cannot be excluded.     

Some aspects of plasticizer migration from poly(vinyl chloride) sheets

Long-term migration data, by radioactivity measurements, are presented for the systems poly(vinyl chloride) (PVC)/labelled dioctyl phthalate (DOP)/methanol, n-propanol, or n-butanol. At equilibrium, migration levels determined exceed 85% for methanol and reveal complete removal for the higher alcohols. Migration kinetics failed to be described by the long-term Fickian approximation with a diffusion coefficient independent of concentration. Nevertheless, q_t/q_∫, where q_∫ the amount migrated at infinite time and q_t the amount lost up to time t, increases linearly with (time)^1/2/(thickness) during the initial stages of the process and then a linear also relationship appears, but with severely reduced slope. Similar data concerning the systems PVC/DOP/petroleum oils confirm the behavior observed.     

Soiling of plasticized poly(vinyl chloride)

The effects of three plasticizers and two plasticizer concentrations on the topography and soiling of poly (vinyl chloride) (PVC) were studied. Palmitic acid and triolein were chosen to represent solid and liquid soils. The feasibility of using infrared spectroscopy to quantify the amount of soil on PVC was examined. The structure of the solid model soil on plasticized PVC was studied with optical microscopy and atomic force microscopy. Palmitic acid formed two different structures on the PVC surface. Both the type and concentration of the plasticizer influenced the structure of the oily soil on plasticized PVC. The wetting of plasticized PVC with the liquid oily soil was compared to wetting with water through the measurement of the contact angles. Plasticized PVC was hydrophobic and oleophilic. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Weathering of plasticized poly(vinyl chloride)

A series of flexible plasticized poly(vinyl chloride) (PVC) compositions containing different organotin compounds and ultraviolet absorbers has been exposed for 4.5 years at four outdoor sites in Australia with widely differing climatic conditions. Loss of plasticizer by evaporation during the exposure was measured and an empirical correlation was found with the average daily maximum temperature at each site. The relative effectiveness of the organotin compounds and ultraviolet absorbers in preventing deterioration of the PVC was estimated by measuring the viscosity of the polymer after exposure. This method of assessment is compared with the results of mechanical tests on the specimens.     

Smoke suppressants for plasticized poly(vinyl chloride)

Addition of plasticizers to poly(vinyl chloride) generally increases its flammability and frequently increases smoke production during its burning. Flame retardants added to plasticized PVC can reduce flammability, but increase smoke production. This study shows that proper choice of combined use of other polymers, phosphate plasticizers, fillers and other flame retardants, produces measured synergistic improvements in flame retardance and smoke suppression which could benefit applications such as PVC wire and cable insulation.     

Influence of plasticizer configurational changes on the mechanical properties of highly plasticized poly(vinyl chloride)

The effects of configurational changes among nine plasticizers were studied using puncture tests. Ion-selective poly(vinyl chloride) (PVC) membranes were plasticized with three citrate-related compounds (Citroflex A-4 (CFA4), Citroflex A-6 (CFA6), and Citroflex B-6 (CFB6)) and six sebacate-related compounds (dimethyl sebacate (DMS), diethyl sebacate (DES), dibutyl sebacate (DBS), dioctyl sebacate (DOS), dioctyl azelate (DOZ), and dioctyl adipate (DOA)). The strengths, stiffnesses, and toughnesses of the membranes increased at low PHR ratios (which are defined as the actual concentrations of plasticizer to PVC divided by the minimum concentrations of plasticizer required to isolate all of the PVC polar groups) and then monotonically decreased as plasticizer was added above these ratios. The ductilities increased up to PHR ratios of about 2.0 and decreased above PHR ratios of about 4.0. The citrate-related compounds could not be distinguished according to the mechanical properties. The DMS-, DES-, and DOA-plasticized membranes were generally stronger and stiffer than the DBS-, DOS-, and DOZ-plasticized membranes, but the ductilities were reduced using DMS, DES, and DOA. A nomogram was constructed to predict the strength, based on the plasticizer selection and PHR ratio. The strengths, stiffnesses, and toughnesses of the membranes decreased as the log (ionic conductivity, σ) increased, and the ranking of the configurational differences was similar to those of the mechanical properties versus PHR ratio.     

A hysteresis in plasticized poly(vinyl chloride)

Plasticized poly(vinyl chloride) formulations were prepared in solid and foam form, and mechanical hysteresis was measured by low-speed tension and compression on an Instron tester and by high-speed rebound on a resiliometer. Hysteresis was greatest in copolymers with vinyl acetate, at low plasticizer concentration, with inefficient plasticizers, at high concentrations of reinforcing fillers, at high expansion to low density, and at high speed of testing. Conversely, resilience was greatest at high plasticizer concentration, with more efficient plasticizers, with non-reinforcing fillers, and at high density.     

The adhesion to hydrophilic surfaces of plasticized poly(vinyl chloride) containing novolac - hexamethylenetetramine

The addition of relatively small amounts of novolachexamethylenetetramine phenolic to poly(vinyl chloride) plastisols has been used to increase the adhesion of the fused plastisol to hydrophilic surfaces like those of glass and steel. The principal mechanism by which this occurs has been studied and found to be, first, the dissolution of the novolachexamethylenetetramine complex in the plasticizer; second, the interaction of the nearby phenolic groups with the hydrophilic surface; and, third, the chain extension and crosslinking of the phenolic to form perhaps a very open cell foam structure through the plasticized vinyl that is attached to the substrate. Additional adhesion may arise from the adsorption of particles of the undissolved novolac complex on the surface and from viscoelastic effects from the cured vinyl composition. The problem with the decreased adhesion of thin plastisol coatings was also studied. It was found to be unrelated to the thickness per se. Rather, it seems to arise from the loss of hexamethylenetetramine at the air interface. Though hexamethylenetetramine is lost also from thicker coatings, the concentration near the adherend interface is less affected.     

Blends of poly(vinyl chloride) with plasticized polyaniline

A series of poly(vinyl chloride) (PVC)/polyaniline (PANI) blends plasticized and protonated simulataneously by bis(2-ethylhexyl) hydrogen phosphate, bis(4-nitrophenyl) phosphate, diphenyl phosphate, or dibenzyl phosphate was prepared by a mass homogenization technique. Thermal analysis studies by means of thermo-gravimetric analysis (TGA) and differential scanning calorimetry (DSC) revealed that PVC/PANI blends with bis(2-ethylhexyl) hydrogen phosphate were characterized by the highest thermal stability values. Kinetic analysis of the decomposition process by the isoconversional Friedman method showed that the activation energy did not change substantially over the broad conversion range; further advanced kinetic analysis by a nonlinear regression method revealed that the kinetic function that was the best approximation for the experimental data was based on a reaction of nth order.     

Nonlinear viscoelastic behavior of plasticized poly(vinyl chloride)

This paper shows how an empirical nonlinear creep relation suggested by Leaderman might be justified on the basis of an approximate nonlinear viscoelastic constitutive equation. In addition, experimental evidence is presented which tends to support the proposed theory.     

Epoxidized rice bran oil (ERBO) as a plasticizer for poly(vinyl chloride) (PVC)

With environmental and toxicity concerns becoming more critical, there are increasing efforts to remove phthalates from polymer compounds around the globe more rapidly. Phthalates can be replaced by natural products; in particular, those obtained from vegetable oils and fats. In the present study, a natural-based plasticizer, synthesized by epoxidation of non-toxic rice bran oil (RBO) with peroxy acid generated in situ has been added to poly(vinyl chloride). The influence of various reaction parameters on epoxidation was studied by investigating the reaction ratio, temperature, reaction time and stirring speed. Epoxidized rice bran oil (ERBO) obtained from an optimized reaction condition was analyzed by iodine number and oxirane content. FTIR was used to analyze epoxy group formation. Product ERBO was obtained with 82 % oxirane conversion within 3 h of reaction period. PVC sheets were formulated using a conventional plasticizer di-(octyl) phthalate and was partially replaced by synthesized ERBO. The effect of ERBO addition was tested by mechanical properties (tensile strength, modulus, elongation-at-break, shore D hardness) and compared with commercially available ESBO (epoxidized soybean oil). ERBO presented fairly good incorporation and plasticizing performance, as demonstrated by the results of mechanical properties, exudation, migration tests, thermal stability by thermogravimetric analysis, T _g values as shown by differential scanning calorimetry, replacing about 60 % of the total plasticizer.     

Migration resistant polymeric plasticizer for poly(vinyl chloride)

Flexible films of poly(vinyl chloride) (PVC) and linear or branched poly(butylene adipate) (PBA), synthesized from 1,4‐butanediol and adipic acid or dimethyl ester of adipic acid, were aged in an aqueous environment for 10 weeks to study how branching, molar mass, and end‐group functionality affect the leaching of polyester plasticizer from thin films. Principal component analysis was applied to reveal patterns and correlations between mechanical properties, material characteristics, and aging behavior. Introduction of branches in the polyester structure increased the miscibility between PVC and the polyester, resulting in improved mechanical properties and lower water absorption. Methyl ester end‐group in PBA polyester stabilized the polymeric plasticizer toward hydrolysis, and reduced the formation and migration of monomeric degradation products from the blends during aging in water. The combination of branched structure with methyl ester end‐groups resulted in a migration resistant polymeric plasticizer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2458–2467, 2007     

Chlorinated poly(vinyl chloride) and plasticized chlorinated poly(vinyl chloride)—thermal decomposition studies

The thermal decomposition of chlorinated poly(vinyl chloride) and three plasticized chlorinated poly(vinyl chloride) systems has been investigated. The routes of decomposition of these systems have been elucidated by investigating char formation and by using a combination of thermogravimetric analysis (TGA) and prolysis/gas chromatography/mass spectroscopy methods (Py/GC/MS). The effects of the charforming/smoke‐suppressing iron(III) compound FeOOH in these polymer systems has also been investigated. The structure of both CPVC polymer and plasticzer determine the path of thermal decomposition and also the quantity and nature of the decomposition compunds formed. Changes in oxygen index and the formation of smoke during burning in these systems have been related to the char that is formed and also to the chemical nature of the decomposition products.     

On the dynamic state of plasticized poly(vinyl chloride)

The spin probe technique is suggested to be suitable for the study of polymer-plasticizer interactions. In this work it was found that the rotational relaxation time (τ) of probe radicals in plasticized poly(vinyl chloride) (PVC) diminishes strongly when the amount of plasticizer is increased. A linear correlation between τ and Young's modulus (G) was observed. This indicated that the microstate considerably influences the mechanical behaviour of the gel. The translational diffusion constant of plasticizer molecules at 25°C was calculated to change from 0.2 times; 10^-8 cm²/s (PVC weight fraction 0.83) to 4.6 times; 10^-8 cm²/s, (PVC weight fraction 0.20). These values indicate a high degree of freedom for lateral motion of plasticizer molecules in gels.     

Simultaneous diffusion of benzyl alcohol into plasticized poly(vinyl chloride) and of plasticizer from polymer into liquid

The diffusion of benzyl alcohol and plasticizer in compression-molded sheets of plasticized poly(vinyl chloride) was studied over the temperature range 30–55°C. A simultaneous diffusion occurred for benzyl alcohol into polymer and for dioctyl phthalate as plasticizer from polymer into liquid when the polymer was soaked in benzyl alcohol. The concentration of benzyl alcohol in polymer increased, rose to a maximum, and then decreased. Diffusion coefficients were measured by considering a nonsteady-state phenomenon for plasticizer concentration of 25, 38, and 50 wt %, both for dioctyl phthalate and benzyl alcohol. Plasticizer concentration and temperature were found to play an important role.     

Rheological and mechanical properties of plasticized poly(vinyl chloride)

The dependence of rheological properties of a plasticized, filled poly(vinyl chloride) compound on three different methods of thermomechanical treatments has been studied. These three different states of the compound are the dry blend mixed at a maximum temperature of 93°C, the two-roll milled sample prepared at 150°C from the dry blend and the molded sample pressed at 170°C from the previously milled material. At 150°C the viscosity and elasticity of the molded sample are considerably higher than those of the dry blend and the milled sample. At higher temperatures, although their flow curves more or less merge, extrudate swell, extrudate appearance and extrudate tensile properties of the three samples vary. The mechanical and Theological properties of the quenched and annealed molded samples and those of the same compound without filler have also been investigated.     

Irreversible deformation of plasticized and impact-modified poly(vinyl chloride)

Tensile mechanical properties of DOP-plasticized poly(vinyl chloride) (PVC) and methyl methacrylate-butyl acrylate copolymer (MMA-BA) or ethylene vinyl acetate-vinyl chloride copolymer (EVA-VC) modified PVC have been studied. The irreversible deformation processes have been investigated using optical microscopy. Thermal analysis and x-ray diffraction were used to investigate the structure of the PVC blends. The differences in behavior observed for the modified and plasticized PVC are discussed on the basis of their morphology.