Plasticized Polyvinyl Chloride Films Research Articles

A comparative study of comprehensive performances for transparent plasticized polyvinyl chloride films with different plasticizers

AbstractFor flexible polyvinyl chloride (PVC) films with excellent mechanical performances and high transparency, the demand for antistatic properties is becoming increasingly urgent in textile and electronic fields. This study compares the effects of 60 phr bis (2‐(2‐butoxyethoxy) ethyl) adipate (DBEEA) with other five equal amounts of plasticizers on the conductivity, electrical stability, transparency, and mechanical properties of plasticized PVC. The infrared spectra of plasticizers indicate that there are unique ether groups exist in DBEEA. Then the calculated solubility parameters suggest the good compatibility between DBEEA and PVC. For conductivity, the volume resistivity and surface resistivity of the PVC sample with DBEEA (PVC/DBEEA) are 107 Ω· m and 1010 Ω, respectively, which are both lower by 3–4 orders of magnitude than that of other plasticized PVC. For electrical stability, the results indicate that PVC/DBEEA placed in air still maintains lowest resistivities. Under 10, 23, and 30°C, PVC/DBEEA keeps high and stable electrical properties. The similar refractive indices of DBEEA and PVC resin prepared by suspension method indicate good transparency for PVC/DBEEA. Moreover, PVC/DBEEA still has good mechanical property.

Synthesis and evaluation of oleic acid‐derived hyperbranched polyester as an efficient plasticizer for PVC

AbstractIn response to the health and environmental concerns associated with the plasticizer dioctyl phthalate (DOP), this research explores the utilization of methyl oleate (MO) derived from plant oil, 1,2,4‐Benzeneticarboxylic anhydride (TMA) and isobutyric anhydride (IA) as a precursor for synthesizing a hyperbranched polyester named IA‐MO‐TMA. This polyester serves as an alternative plasticizer for Polyvinyl chloride (PVC). The chemical structure of IA‐MO‐TMA was thoroughly characterized using Fourier Transform Infrared Spectrometer (FTIR) and nuclear magnetic resonance hydrogen spectra, and its molecular weight was assessed. The PVC film, plasticized with IA‐MO‐TMA, underwent comprehensive testing using techniques such as differential scanning calorimetry, scanning electron microscopy, and thermogravimetric analysis. Notably, the glass transition temperature (Tg) of the plasticized PVC film exhibited a significant reduction from 75°C to −6.7°C. The plasticized film demonstrated an elongation at break of 318.1%, a tensile strength of 19.2 MPa, and a plasticizing efficiency of 109.9%. Moreover, the use of IA‐MO‐TMA as a plasticizer increased the initial decomposition temperature of PVC film from 235.6 to 264.1°C. Additionally, the extraction rate of IA‐MO‐TMA in petroleum ether was found to be 35.6% lower than that of DOP.

Synthesis and application of environmental plasticizers based on benzene polyacid ester

AbstractUsing benzene‐1,3,5‐tricarboxylic acid, trimellitic anhydride, 2‐propylheptanol and 2‐ethylhexanol as raw materials, four kinds of environmental plasticizers were prepared, which were used as additives for polyvinyl chloride (PVC) products. Compared with commercially available di (2‐ethylhexyl) phthalate (DOP), di (2‐ethylhexyl) terephthalate (DOTP), and tributyl citrate (TBC), the application performance and plasticizing performance were compared. The structure of the target product was analyzed by fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy to verify the fingerprint region of the molecular structure of the product. The properties of plasticized PVC films were tested by thermal weight loss analysis, oven thermal aging test, migration and volatility resistance test, DMA analysis, and scanning electron microscopy. The plasticizing mechanism was confirmed through quantum chemical calculations, and the results of the calculations were in line with the migration outcomes. The results showed that compared with commercially available plasticizers, benzene polyacid ester plasticizers had better thermal stability, and better cold resistance in the polar environments, suitable for high‐temperature and water‐based environments.Highlights The four plasticizers prepared in this study were compared with reference plasticizers, and the plasticizing mechanism was validated through quantum chemical calculations. The PVC film plasticized with benzene polyacid ester prepared in this study demonstrates outstanding thermal stability, surpassing certain plasticizers reported in current literature. Benzene polyacid esters plasticized PVC film has migration stability under various conditions, it has great potential in packaging and other applications.

Hyperspectral Imaging Based Detection of PVC During Sellafield Repackaging Procedures

Traditionally, special nuclear material (SNM) at Sellafield has been stored in multilayered packages, consisting of metallic cans and an overlayer of plasticized polyvinyl chloride (PVC) as an intermediate layer when transitioning between areas of different radiological classification. However, it has been found that the plasticized PVC can break down in the presence of both radiation and heat, releasing hydrochloric acid, which can corrode these metallic containers. Therefore, internal repackaging procedures at Sellafield have focused recently on the removal of these PVC films from containers, where as much degraded and often adhered PVC as possible is manually removed based on visual inspection. This manual operation is time-consuming, and it is possible that residual fragments of PVC could remain, leading to corrosion-related issues in future. In this work, hyperspectral imaging (HSI) was evaluated as a new tool for detecting PVC on metallic surfaces. The Samples of stainless steel type 1.4404—also known as 316L, the same as is used to construct SNM cans—and PVC were imaged in our experiments, and support vector machine (SVM) classification models were used to generate detection maps. In these maps, pixels were classified into either PVC or 316L based on their spectral responses in the range 954–1700 nm of the electromagnetic spectrum. Results suggest that the HSI could be used for an effective automated detection and quantification of PVC during repackaging procedures, detection and quantification that could be extended to other similar applications.

Performance assessment of polyvinyl chloride films plasticized with Citrullus lanatus seed oil based novel plasticizer

Biobased plasticizers for polymers is a necessity to replace conventional phthalates based plasticizers. In the present study, Citrullus lanatusseed oil (ECLO) was epoxidized in a magnetically stirred reactor. Polyvinyl chloride (PVC) films were synthesized using different concentrations of ECLO. At 40% of ECLO, films showed better surface morphology and exhibited maximum strength and elongation at break. Plasticized PVC film shown tensile strength of 18.6 MPa and elongation at break of 136.18%. No migration was observed in water, designating hydrophobic characteristics of the films. In gasoline, acid (Acetic acid) and alkali (Sodium hydroxide), plasticized samples exhibited a low resistance for migration. X-ray diffraction analysis confirmed no change in crystallinity of PVC after addition of ECLO. Thermogravimetric analysis presented the plasticized PVC films are thermally stable. Differential scanning calorimetry established the plasticizing effect of ECLO as a glass transition temperature (Tg) of plasticized films was shifted to a lower temperature.Furthermore, Fourier transform infrared spectroscopy revealed interaction of ECLO with PVC as peaks of C–Cl bond (833 cm−1) and CO stretch (1739 cm−1) were detected. Thus, the present study delivered a better substitute for phthalates as it endorses the application of ECLO in the PVC blend as a plasticizer.

Spectrophotometric characterization of plasticizer migration in poly(vinyl chloride)-based artificial leather

Plasticized polyvinyl chloride (PVC) is one of the most commonly used material in the manufacture of artificial leather because of its flexibility, high durability and low cost. While hundreds of plasticizers have been produced to obtain PVC films and artificial leathers, it is important to choose the correct plasticizer to produce the desired products. Therefore, here five non-phthalate type plasticizers with three levels (40 phr, 60 phr and 80 phr); trioctyl trimelliate (TOTM), tributyl trimelliate (TBTM), dioctyl terephthalate (DOTP), dioctyl adipate (DOA) and dioctyl succinate (BIO) were used to prepare plasticized PVC films. They were studied in terms of their compabilities with PVC polymer chains, and their effects on mechanical properties of PVC films. Although, linear plasticizers e.g. BIO and DOA have higher compabilities with PVC, a branched plasticizer e.g. TOTM showed higher mechanical properties. Moreover, a new spectrophotometric method for determination of plasticizer migration from PVC polymer matrix to the surface of artifical leather was developed. According to lightness change on the surface of PVC artifical leather before and after heat treatment at 70 °C, the migration rates of used plasticizers increase in this order: TOTM < TBTM < DOTP < BIO < DOA.

Rosin‐derived poly(vinyl chloride) plasticizer: Synthesis, structure, and properties

In this work, rosin‐based plasticizer was synthesized by Diels–Alder (DA) and esterification. First, the maleopimaric acid (RT) was obtained by DA between the double bond of rosin and maleic anhydride. Then, the carboxyl group and anhydride group of RT was esterified with tetrahydro geraniol to obtain the rosin‐based polyacid esters (RTT) under the catalysis of p‐toluene sulfonic acid. The structure of RT and RTT was detected by FTIR and 1H‐NMR. RTT was used as main plasticizer to obtain plasticized polyvinyl chloride (PVC) materials and compared with DOP. The results showed that RTT improved the thermal stability and reduced Tg of PVC film. Plasticized PVC films had excellent mechanical properties with the elastic modulus of −4,793.67 MPa and tensile strength of −111.86 MPa, higher than that of pure PVC and DOP‐6. RTT showed better volatility stability, migration, and solvent extraction in PVC compared to DOP. J. VINYL ADDIT. TECHNOL., 26:180–186, 2020. © 2019 Society of Plastics Engineers

A solid-contact pH-selective electrode based on tridodecylamine as hydrogen neutral ionophore

The solid-state pH electrode has the potential possibility to be used in many extreme situations with satisfactory accuracy and low cost. But its performance is affected by the solid electrolyte, preparation process, and the structure of the sensitive membrane, etc. In this work, the relationships between these factors and the characteristic of the prepared electrode were verified by controlling the preparation conditions with a variety of electrochemical methods. Firstly, the solid electrolyte poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT/PSS) was electrochemically deposited on the screen-printed carbon electrode (SPCE) substrate by a potentiostatic method in an aqueous solution containing 0.01 M 3,4-ethylenedioxythiophene (EDOT) and 0.1 M polystyrene sulfonic (PSS) acid as the supporting electrolyte. The PEDOT films were then characterized by cyclic voltammetry (CV) in the 0.1 M NaNO3 aqueous solution in order to obtain the optimized polymerization potential and charges where the PEDOT film would have a higher redox capacitance. Finally, the pH electrode was prepared by coating the SPCE/PEDOT(PSS) with a plasticized polyvinyl chloride (PVC) membrane containing tridodecylamine as hydrogen ionophore manually, and experiments were carried out to study the effect of the usage of PVC per square millimeter on the response time and stability of the electrode to optimize the PVC film thickness. The potentiometric response of the pH electrode was studied in the buffer solutions with pH ranging from 5.00 to 10.81 by the open-circuit potential (OCP) method. Experimental results show that the sensitivity of the electrode is −55.7 ± 0.5 mV pH−1 (r2 > 0.9980) at room temperature (24 ± 1 °C) with pH ranging from 2.00–10.50, approximating to the theoretical nernstian slope (−59.16 mV pH−1),and the response time was less than 10 s. Moreover, it has low impedance, high accuracy and potential stability as well as some other useful properties such as pressure and heat resistance, hydrofluoric acid resistance, and it is not as fragile as the glass electrode.

Phenyl benzoate derivatives with anisotropic molecular structure as stabilizers for formulations based on plasticized polyvinyl chloride

The photo- and thermostabilizing performance of nine phenyl benzoate derivatives with chemically active terminal substituents in formulations based on plasticized polyvinyl chloride was studied. The substituted phenyl benzoates exhibit thermal activity allowing them to withstand without decomposition the temperatures at which the polymeric formulations are processed. The potential stabilizers studied are capable of shielding the polymeric matrix from the most hazardous UV radiation. The plasticized polyvinyl chloride film samples stabilized with anisotropic phenyl benzoates surpass in the thermal stability the samples containing commercial stabilizers and exhibit good physicomechanical characteristics.

Degradation kinetics ofPVCplasticized with different plasticizers under isothermal conditions

ABSTRACTThe aim of the present work is to elucidate the degradation kinetics of polyvinyl chloride (PVC) plasticized with some phthalate and nonphthalate plasticizers. A PVC thermomat instrument was utilized to maintain the isothermal degradation conditions at 140 and 160°C, and to suppress the oxidative degradation by means of nitrogen flow. The conductivity measurements were performed to follow hydrogen chloride (HCl) gas which is released upon PVC degradation and trapped in water. Dehydrochlorination of plasticized PVC films occurred with activation energies of about 23–160 and 26–117 kJ mol−1and the isokinetic temperatures, at which the dehydrochlorination rate constants of all p‐PVC films would have the same value, were found to be 171 and 128°C for initial and linear regions of dehydrochlorination curve, respectively. Plasticizer incorporation contributes to the stability of the films particularly after the consumption of stabilizer due to the dehydrochlorination. Influence of temperature rise by 20°C on the degradation rate constant is the lowest for DINCH having p‐PVC films as 0.36 and 0.42% increment at the initial region and linear region, respectively. On the other hand, DOTP reveals greater stability than the others do since the compensation ratio of the PVC film having DOTP is greater than the other films. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2015,132, 41579.

Migration of phthalate and non‐phthalate plasticizers out of plasticized PVC films into air

AbstractThe aim of the present work is to provide information about the migration of phthalate and non‐phthalate plasticizers generally used in flexible polyvinyl chloride (PVC) applications. Plastisols (pastes) were prepared by mixing PVC, plasticizer, and thermal stabilizer. The plasticized PVC (p‐PVC) films are obtained by gelation at 160°C for 15 min. The p‐PVC films were heat treated at 50, 85, 100, 130, and 160°C up to 420 min to follow the mass loss to find out diffusivity of plasticizer out of films into air and to determine related activation energies. The films having di‐octyl terephthalate (DOTP) and di‐isononyl 1,2‐cyclohexanedicarboxylic acid (DINCH) exhibited the lowest mass loss in general, among the phthalate and non‐phthalate plasticizer having p‐PVC films, respectively, as confirmed by FTIR investigation. The same tendency was observed for diffusion coefficients and for the activation energies of migration. The diffusion coefficients were found to be around 3.5 × 10−18–2.1 × 10−17 m2/sec for the studied plasticizers in PVC at 50°C and around 4.0 × 10−15–9.9 × 10−14 m2/sec at 160°C. The activation energies for 85–160°C interval were determined to be between 70 and 153 kJ/mol (0.72–1.58 eV) for the plasticizers used herein those could be treated as a homologous series as deduced from the related compensation factors. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Sum Frequency Generation and Coherent Anti-Stokes Raman Spectroscopic Studies on Plasma-Treated Plasticized Polyvinyl Chloride Films

Polyvinyl chloride (PVC) is a widely used polymer to which various phthalates are extensively applied as plasticizers. PVC materials are often treated with plasma to vary the hydrophobicity or for cleaning purposes, but little is known of the nature of the surface molecular structures after treatment. This research characterizes molecular surface structures of PVC and bis-2-ethylhexyl phthalate (DEHP)-plasticized PVC films in air before annealing, after annealing, and after exposure to air-generated glow discharge plasma using sum frequency generation (SFG) vibrational spectroscopy. In addition, we compare the vibrational molecular signatures on the surfaces of PVC with DEHP (at a variety of percent loadings) to those of the bulk detected using coherent anti-Stokes Raman scattering (CARS). X-ray photoelectron spectroscopy (XPS) and contact angle measurements have been used to analyze PVC surfaces to supplement SFG data. Our results indicate that DEHP was found on the surfaces of PVC films even at low weight percentages (5 wt %) and that DEHP segregates on surfaces after annealing. The treatment of these films with glow discharge plasma resulted in surface-sensitive reactions involving the removal of chlorine atoms, the addition of oxygen atoms, and C-H bond rearrangement. CARS data demonstrate that the bulk of our films remained undisturbed during the plasma treatment. For the first time, we probed the molecular structure of the surface and the bulk of a PVC material using combined SFG and CARS studies on the same sample in exactly the same environment. In addition, the methodology used in this research can be applied to characterize various plasticizers in a wide variety of polymer systems to understand their surface and bulk structures before and after systematic applications of heat, plasma, or other treatments.

Kinetics of thermal degradation of poly(vinyl chloride)

Extensively studied thermal degradation of polyvinyl chloride (PVC) occurs with formation of free hydrogen chloride and conjugated double bonds absorbing light in visible region. Thermogravimetric monitoring of PVC blends degradation kinetics by the loss of HCl is often complicated by evaporation and degradation of plasticizers and additives. Spectroscopic PVC degradation kinetics monitoring by absorbance of forming conjugated polyenes is specific and should not be affected by plasticizers loss. The kinetics of isothermal degradation monitored by thermal gravimetric analysis in real time was compared with batch data obtained by UV/Visible absorption spectroscopy. Effects of plasticizer on kinetics of polyene formation were examined. Thermal degradation of PVC films plasticized with di-(2-ethylhexyl) phthalate (DEHP) and 1,2,4-benzenedicarboxylic acid, tri-(3-ethylhexyl) ester (TOTM) was monitored by conjugated double bonds light absorption at 350 nm at 160, 180, and 200 °C. Plasticizer-free PVC powder degradation kinetics and that of plasticized films were also obtained thermogravimetrically at temperatures ranging from 160 to 220 °C. Plasticizer-free PVC powder degradation and spectroscopically monitored degradation of plasticized PVC films occurred with the same apparent activation energy of ≈150 kJ mol−1. No difference in degradation kinetics of films plasticized with DEHP and TOTM was detected.

A study on the blending effect of polyvinyledene fluoride in the ionic transport mechanism of plasticized polyvinyl chloride + lithium perchlorate gel polymer electrolytes

The gel polymer electrolytes composed of the blend of polyvinylchloride (PVC) and polyvinylidene fluoride (PVdF) as host polymers, the mixture of ethylene carbonate (EC) and propylene carbonate (PC) as a plasticizer, and LiClO4 as a salt was studied. An attempt was made to investigate the effect of PVdF in the plasticized PVC + LiClO4 system in three blend ratios. The differential scanning calorimetry study confirms the formation of polymer–salt complex and miscibility of the PVC and PVdF. The X-ray diffraction results of plasticized PVC (S1, S2, S3) and PVdF-blended films (S4, S5, S6) were compared, in that an increase in PVC concentration decreases the degree of crystallinity for S1 and S3, respectively, but drastically increases for PVC (S2). The increase in PVC content has not accounted in the conductivity studies also noted. However, the blending effect of PVdF showed decreases in crystallinity homogeneously for (S6 > S5 > S4), which were reflected in ionic conductivity measurements. The surface morphology of the films were also studied by scanning electron microscope, and it corroborates the same.

Migration of plasticizers from plasticized polyvinyl chloride films

The migration of plasticizers [EDOS, di(2-ethyl hexyl) o-phthalate, di-n-butyl o-phthalate] from unfilled and chalk-filled polyvinyl chloride films plasticized with individual and binary plasticizers was studied by gravimetric analysis and IR spectroscopy. The intermolecular interaction of components in model systems was studied by IR spectroscopy and isothermal calorimetry.

Di(2-ethylhexyl) adipate (DEHA) induced developmental toxicity but not antiandrogenic effects in pre- and postnatally exposed Wistar rats

Di(2-ethylhexyl) adipate (DEHA) has replaced the phthalates in thin plasticized polyvinyl chloride films used for food packaging, mainly because some phthalates induce testis toxicity and antiandrogenic effects. A dose-range finding study followed by a dose–response/effect study in Wistar rats investigated whether pre- and postnatal DEHA doses of 0, 800, or 1200 mg/kg/day body weight and doses of 0, 200, 400, or 800 mg/kg/day (main study) elicited developmental toxicity including antiandrogenic effects. In the main study, DEHA induced a prolonged gestation period (800 mg/kg/day) and a dose-related increase in postnatal death (400 and 800 mg/kg/day). DEHA also induced a permanent decrease in offspring body weight (800 mg/kg/day). No antiandrogenic endpoints were affected. We conclude that DEHA induced developmental toxicity and the NOAEL is 200 mg/kg. DEHA did not induce antiandrogenic effects similar to those of di(2-ethylhexyl) phthalate even though the chemical structures have similarities and the two chemicals have a common metabolite.

Membrane electrodes selective for hydrogen phosphate ions

The possibility of using plasticized polyvinyl chloride film membranes with dispersed electroactive substances (MgNH4PO4, BiPO4, and CrPO4) for developing electrodes selective for hydrogen phosphate ions has been investigated. It is shown that a chromium(III) phosphate-based electrode is characterized by the linearity range KT-1-KT-6 M of the hydrogen phosphate function with a slope of 26.5 mV/pc and a satisfactory selectivity in the presence of chloride, nitrate, sulfate, and hydrogen carbonate ions.

Polyethylene oxide additive-entrapped polyvinyl chloride as a new blood bag material

Until now, most widely used blood bag material has been a plasticized polyvinyl chloride (PVC) because it has many desirable properties as a blood bag material. One of main concerns of using plasticized PVC as a blood bag material is the toxicity of the plasticizers that are leached out of the material. We tried to solve this problem by the addition of polyethylene oxide (PEO)-containing amphiphilic block copolymers as additives in the PVC. The PEO additives may play two roles: they can act as nontoxic plasticizers to PVC, and they can also act as blood-compatible surface modifiers. In this study, PEO additive-entrapped PVC films were prepared by the addition (up to 30 wt%) of PEO-alkyl carbon block copolymers or PEO-polypropylene oxide (PPO)-PEO triblock copolymers with different PEO chain lengths in the PVC. The prepared PEO additive-containing PVC films were characterized by the measurements of water contact angle, Fourier transform IR spectroscopy in the attenuated total reflectance mode, mechanical properties (tensile strength and elongation at break), water absorption, and stability of the PEO additives entrapped in the films. It was observed that the PEO additive-entrapped PVC films were flexible and transparent. It seems that the PEO additives are surface active, resulting in the considerable change of surface characteristics without a significant change of the mechanical properties of the films compared to the control PVC without any additives or a commercial blood bag. The adhesion of platelets on the film surfaces was significantly reduced by the addition of PEO additives. It seems that 10% addition of PEO additives is enough for the suppression of platelet adhesion on the surfaces. This study demonstrated that the use of PEO-containing block copolymers as additives to the PVC can be a feasible approach to prepare a new type of blood bag.

Planar waveguide ion-selective sensors

A potassium ion-selective planar waveguide total internal reflection (TIR) mode optical sensor was prepared for flow injection application by casting thin film optode membranes onto a glass substrate. For this sensor, a potassium selective ionophore is incorporated in plasticized polyvinyl chloride film sensitized with a hydrogen selective ionophore. The sensor response to potassium ion is determined by measuring the attenuation of a HeNe laser propagated in this thin film device. The laser was coupled into and out of the sensor using grating couplers providing an inexpensive, environmentally stable sensor. The sensitivity of the waveguide based flow injection device is approximately 0.05 mM K +, while the rate of analysis is about 180 samples per hour.

Methods for Assessment of Biodegradability of Plastic Films in Soil

Traditional and novel techniques were tested and compared for their usefulness in evaluating biodegrad-ability claims made for newly formulated "degradable" plastic film products. Photosensitized polyethylene (PE), starch-PE, extensively plasticized polyvinyl chloride (PVC), and polypropylene (PP) films were incorporated into aerobic soil. Biodegradation was measured for 3 months under generally favorable conditions. Carbon dioxide evolution, residual weight recovery, and loss of tensile strength measurements were supplemented, for some films, by gas chromatographic measurements of plasticizer loss and gel permeation chromatographic (GPC) measurement of polymer molecular size distribution. Six- and 12-week sunlight exposures of photosensitized PE films resulted in extensive photochemical damage that failed to promote subsequent mineralization in soil. An 8% starch-PE film and the plasticized PVC film evolved significant amounts of CO(2) in biodegradation tests and lost residual weight and tensile strength, but GPC measurements demonstrated that all these changes were confined to the additives and the PE and PVC polymers were not degraded. Carbon dioxide evolution was found to be a useful screening tool for plastic film biodegradation, but for films with additives, polymer biodegradation needs to be confirmed by GPC. Photochemical cross-linking of polymer strands reduces solubility and may interfere with GPC measurements of polymer degradation.