Preparation and application of triglyceride plasticizers for poly(vinyl chloride)

A series of triglyceride plasticizers were prepared from glycerol, acetic acid, and benzoic acid through a two‐step reaction to develop potential uses of glycerol. The optimum reaction conditions were determined by the esterification of glycerol and acetic acid to produce glyceryl triacetate. When the molar ratio of glycerol to benzoic acid to acetic acid was 1:1:3.5, a novel plasticizer triglyceride mixture (GTM) was successfully synthesized; it had a good plasticizing effect on poly(vinyl chloride) (PVC). The elongation at break of PVC composites containing 80 phr GTM increased around 350%; the corresponding hardness (Shore D) and tensile strength decreased to around 35 D and 20 MPa, respectively. Moreover, the glass‐transition temperature (T_g) of PVC composites containing 40 phr GTM decreased to around 50°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influences of individual and composed poly(vinyl alcohol) suspending agents on particle morphology of suspension poly(vinyl chloride) resin

Effects of individual and composed poly(vinyl alcohol) (PVA) suspending agents on the particle morphology of poly(vinyl chloride) (PVC) resins were investigated and discussed in the view of PVA absorption at the oil/water interface and interfacial behavior. It was shown that the percentage and surface coverage of PVA at the oil/water interface decreased with the increase of the degree of hydrolysis (DH) of PVA in the DH range of 70–98 mol %, while the interfacial tension of VC/PVA aqueous solution increased linearly with the increase of DH of PVA. PVC resin with more regular particle shape, increased agglomeration and fusion of primary particles, lower porosity and higher bulk density, was prepared by using PVA with a higher DH as a suspending agent. This was caused by the occurrence of drop coalescence at the very early stage of VC polymerization, the increase of particle shrinkage, and the lower colloidal protection to primary particles. It was also shown that the interfacial tension of VC/water in the presence of composed PVA suspending agents varied linearly with the weight composition of the composed PVA suspending agents. The particle properties of PVC resin prepared by using the composed PVC suspending agents were usually situated in between the properties of PVC resins prepared by using the corresponding individual PVA suspending agent. The particle morphology and properties of PVC resin could be controlled by the suitable choice of the composed PVA suspending agents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3848–3855, 2003     

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     

Studies of electrical and mechanical properties of semiconductive poly(vinyl chloride) compositions

A sample of poly(vinyl chloride) (PVC) and a polar plasticizer consisting of dioctylphthalate (DOP) and triisopropylphenylphosphate (TIPPP) was prepared and found to possess some electrical conductivity. Different samples of PVC compositions were formulated from the PVC-DOP-TIPPP system and also variable proportions of the conductive materials polyaniline or the Ni salt of ethylene glycol bisadipate ester. Dibutyltindilaurate as a heat stabilizer, titanium oxide as a filler, and sandorin red 20 pigment were added. The effect of the structure of polyaniline and Ni adipate ester on the electrical and mechanical properties of the PVC–DOP–TIPPP system was studied to obtain a semiconductive plasticized PVC with good mechanical properties. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 685–693, 1998     

Lanthanum histidine with pentaerythritol and zinc stearate as thermal stabilizers for poly(vinyl chloride)

Lanthanum histidine [La(His)₂·(NO₃)·2H₂O or La(His)₂] was synthesized via the reaction of histidine and lanthanum nitrate, and it was investigated as a stabilizer for poly(vinyl chloride) (PVC). The results show that La(His)₂ exhibited a stabilizing effect on PVC as a long‐term stabilizer because it prolonged the stability time of PVC to 76 min, which was about 24 times longer than the stability time of the pure PVC. The stabilizing effect of La(His)₂ as a costabilizer with pentaerythritol (Pe) and zinc stearate (ZnSt₂) was also studied. The results show that the use of La(His)₂ with Pe or Pe/ZnSt₂ improved the stability time of PVC. La(His)₂/Pe/ZnSt₂ provided PVC with a good initial color and long‐term stability, and when it was prepared at mass ratios of 0.8:2.4:0.8 and 1.6:1.6:0.8, the stability times of PVC were improved to 86 and 88 min, respectively. As a nontoxic stabilizer, La(His)₂/Pe/ZnSt₂ has the potential to replace the toxic stabilizers widely used in PVC manufacturing. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42878.     

Evaluation of the effects of biobased plasticizers on the thermal and mechanical properties of poly(vinyl chloride)

Blends were prepared of poly(vinyl chloride) (PVC) with four different plasticizers; esters of aconitic, citric, and phthalic acids; and other ingredients used in commercial flexible PVC products. The thermal and mechanical properties of the fresh products and of the products after 6 months of aging were measured. Young's modulus of the PVC blends was reduced about 10‐fold by an increase in the plasticizer level from 15 to 30 phr from the semirigid to the flexible range according to the ASTM classification, but a 40‐phr level was required for PVC to retain its flexibility beyond 6 months. At the 40‐phr level, tributyl aconitate performed better than diisononyl phthalate (DINP) or tributyl citrate, in terms of lowering Young's modulus, both in the fresh materials and those aged for 6 months. The effects of the four plasticizers on the glass‐transition temperature (T_g) were similar, with T_g close to ambient temperature at the 30‐ and 40‐phr levels in freshly prepared samples and at 40–60°C in those aged for 6 months. The thermal stability of the PVC plasticized with DINP was superior among the group. Overall, tributyl aconitate appeared to be a good candidate for use in consumer products where the alleged toxicity of DINP may be an issue. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1366–1373, 2006     

Diester based on castor oil fatty acid as plasticizer for poly(vinyl chloride)

Castor oil is a renewable resource that has potential uses as an environmental friendly material for a range of applications. In recent years, much efforts have been driven to develop alternate plasticizer for medical and commodity plastics due to growing concerns about dioctyl phthalate (DOP) for flexible poly(vinyl chloride) (PVC). In this study, a bio‐based plasticizer was synthesized by a two‐step esterification reaction of castor oil fatty acid (COFA) with benzyl alcohol and octanoic acid in the presence of catalyst (dibutyl tin dilaurate). The structure of the octanoic ester (OE) was confirmed by proton nuclear magnetic resonance, Fourier transform infrared spectroscopy, acid value, and hydroxyl value. OE was used as a coplasticizer in PVC for partial replacement of DOP. The addition of OE exhibited good incorporation and plasticizing performance in the PVC sheets. Incorporation of OE resulted in good plasticizing, tensile strength, percentage elongation, exudation, thermal stability, and chemical resistance because of the presence of long carbon chains of COFA. Differential scanning calorimetry (DSC), thermogravimetric analysis, and color measurements were also performed to evaluate the effect of OE. With the increase in OE, DSC and hardness results showed marginal deviation from those obtained for DOP‐plasticized sheets. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40354.     

Epoxylsilane crosslinking of rigid poly(vinyl chloride)

Crosslinking is an effective way to improve the qualities of poly(vinyl chloride). A crosslinking system consisting of R‐glycidoxypropyltrimethoxysilane (KH560) has been first used to introduce crosslinking into rigid poly(vinyl chloride). Different thermal stabilizers (organotin, Ca/Zn stearate, and Ba/Zn stearate) as well as sodium bisulfite additive were tried to promote the grafting of epoxyl group and enhance the degree of crosslinking. FTIR spectra showed that grafting and crosslinking of KH560 with poly(vinyl chloride) could take place, and a gel content of 40% could be obtained when more than 10 phr epoxylsilanes were used in the condition of 2 : 1 (parts by weight) ratio of BaSt₂/ZnSt₂ and 1 : 1M ratio of NaHSO₃/KH560, while the premature crosslinking was avoided. Thermal properties had been studied. The results showed that the Vicat softening temperature of crosslinked PVC could be improved about 10°C when 5 phr epoxylsilane was added, and thermal degradation could be delayed with increase in gel content. Therefore, epoxylsilane‐crosslinked PVC will have the potential for extensive applications © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Effect of lignin esters on improving the thermal properties of poly(vinyl chloride)

To improve the thermal stability of poly(vinyl chloride) (PVC) and the utilization of lignin (L), different L esters were added to PVC to produce the plates with enhanced thermal stabilities. The properties and structures of the L ester–PVC plates and the properties of the L esters and their mixtures with PVC were analyzed by universal mechanical testing, static thermal stability testing, thermogravimetry–Fourier transform infrared (FTIR) spectroscopy, UV–visible spectroscopy, FTIR spectroscopy, scanning electron microscopy, and differential scanning calorimetry. The results show that L improved the thermal stability of PVC, but the mechanical properties were substantially deteriorated. Proper esterification of L improved the thermal stabilities and mechanical properties of the plates. Noncyclic anhydride acetylated L–PVC plates possessed good static and dynamic thermal stabilities and mechanical properties. The PVC plates incorporated with the L esters with a degree of esterification of around 40% exhibited the best combination properties. Maleated L–PVC plates had good dynamic thermal stability and mechanical properties but poor static thermal stability. The opposite properties were found for succinylated L–PVC plates. The differences in the properties of different L ester–PVC plates were attributed to the different abilities of L esters to capture free radicals, the crosslinking reaction between L esters and PVC, and their compatibility. Different properties of the L esters indicated their different applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47176.     

Effect of zinc maleate/zinc oxide complex on thermal stability of poly(vinyl chloride)

In this study, zinc maleate (ZnMA) and zinc oxide (ZnO) complex (ZnMA/ZnO) was prepared by two methods, namely, by the reaction of maleic acid (MAH) with excess ZnO in aqueous solution and by direct mixing of ZnMA and ZnO at 180°C. The chemical structure of the complex was analyzed by X‐ray diffraction, thermogravimetric analysis (TGA), and Fourier transform infrared (FTIR) spectroscopy. The thermal stabilizing effect of the complex on poly(vinyl chloride) (PVC) was evaluated through static and dynamic stability methods. Compared to calcium and zinc soaps and ZnMA alone, the complex exhibited better thermal stabilizing effect on PVC. The stabilization mechanism was also investigated by ultraviolet–visible spectrometer, FTIR, TGA, and gel content analysis. The results indicated that the complex which involved the replacement of labile chlorine atoms hindered the formation of conjugated double bonds in PVC chains via Diels–Alder reaction, and ZnMA/ZnO complex also exhibited the ability to absorb hydrogen chloride. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41464.     

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     

Insights into the use of zinc–mannitol alkoxide as a novel thermal stabilizer for rigid poly(vinyl chloride)

Zinc–mannitol alkoxide (Zn–Man) was synthesized through alcohol exchange reaction, and investigated by means of Fourier transform infrared spectroscopy and elemental analysis. The thermal stability of Zn–Man for rigid poly(vinyl chloride) (PVC) was evaluated by Congo red testing, conductivity measurements, thermal aging testing, thermogravimetric analysis (TGA), and ultraviolet–visible (UV–vis) spectroscopy test. The experimental results demonstrate that the addition of Zn–Man not only apparently prolonged the static thermal stability time to approximately 96.5 min but also evidently improved the initial color of PVC. More importantly, the color of the PVC sheets stabilized with Zn–Man did not change to black within 180 min; this showed that no zinc‐burning phenomenon occurred. In addition, the results of TGA reveal that Zn–Man raised the initial degradation temperature of PVC to about 273.4°C. UV–vis testing indicated that the presence of Zn–Man decreased the content and shortened the length of the conjugated double bonds of PVC. The possible thermal stability mechanism is discussed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42038.     

Effect of hydrotalcite on the thermal stability,mechanical properties,rheology and flame retardance of poly(vinyl chloride)

Compounds of poly(vinyl chloride) (PVC) and hydrotalcite were prepared via melt blending, and the thermal stability, mechanical properties, rheology and flame retardance were studied. Transmission electron microscopy showed that the hydrotalcite achieved an optimal dispersion in PVC compounds when surface‐treated with titanate coupling agent. The Congo Red test and thermogravimetric analysis demonstrated that the thermal stability of PVC was improved significantly only in the presence of a complex of the hydrotalcite and the organotin stabilizer. Such a significantly positive thermal stabilizing effect was attributable to the stabilizing mechanisms that the electrostatic interaction generated between the electron cloud of chlorine atoms in PVC chain and the positive lay charge of hydrotalcite, which resulted in a decrease in electronic cloud density of chlorine atoms. This weakened the activity of chloride atoms, and restricted the initiation of the dehydrochlorination. A surface treatment for the hydrotalcite with the titanate coupling agent could reduce deterioration of the mechanical and rheological properties of the PVC at low concentration of hydrotalcite. The hydrotalcite also enabled useful application of PVC as a flame retardant as well as a smoke retarder in the light of a LOI value of more than 28.7 and UL 94 V‐0 grade at a PVC/hydrotalcite weight ratio of 70/30. Copyright © 2004 Society of Chemical Industry     

The effect of sodium stearate‐modified hydrocalumite on the thermal stability of poly(vinyl chloride)

Hydrocalumite as a new‐type of thermal stabilizer used in poly(vinyl chloride) resin had been well prepared by using precipitation transformation method. The as‐prepared hydrocalumite was then modified by sodium stearate in different condition including temperature, stirring time, and the amount of sodium stearate. Scanning electron microscopy tests demonstrate that hydrocalumite had been well modified. Illustrated by activation grade, the static oven heat aging experiments and the rate of thermal weight loss, it turns out that the best modification condition is when the addition of sodium stearate is 6% of hydrocalumite (wt), the reacting temperature is 90 °C, and the stirring time is 100 min. Static thermal aging test shows that the aging time got improved at least 30 min under the high temperature of 190 °C, and the time when Congo red test paper began to turn blue for modified hydrocalumite is 20 min longer than that of unmodified hydrocalumite. All results turn out to be that the hydrocalumite modified by sodium stearate in such condition had good compatibility with poly(vinyl chloride) and presented better thermal stability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45758.     

The molecular, physical and mechanical properties of highly plasticized poly(vinyl chloride) membranes

Highly plasticized poly(vinyl chloride) membranes (200 parts per hundred resin, phr) form the basis of ion-selective electrodes. The effects that five different plasticizers with different chemical structures, polarities and molecular weights have on modified mechanical properties such as strength, secant stiffness, toughness and ductility were examined by puncture testing. As a function of membrane thickness, strength, toughness, and secant stiffness increase, while ductility remains constant. For maximal membrane strength and toughness, plasticizer should be roughly 1000. The optimal ratio of experimental plasticization level (phr_exp = 200) to the minimal level required for complete plasticization (phr_min) was found to be 2. A ‘tube’-like model for plasticizer interaction with polymer chains is proposed to explain the vast differences in the mechanical properties of membranes.     

Modification of poly(vinyl chloride) by IPN formation with poly(ethyl acrylate)

Semi‐1 and semi‐2 interpenetrating polymer networks (IPNs) of poly(vinyl chloride) (PVC) and in situ formed poly(ethyl acrylate) (PEA) have been synthesized using diallyl phthalate and ethylene glycol dimethacrylate as the crosslinkers of PVC and PEA, respectively. These two types of IPNs have been compared with respect to their physical, mechanical, and thermal properties and an endeavor has been made to find a correlation of these properties with the morphology generated in these systems. The semi‐1 IPNs displayed a decrease in their tensile strength and modulus while in contrast; the semi‐2 IPNs exhibited a marginal increase with increasing crosslinked PEA incorporation. The semi‐1 and semi‐2 IPNs containing 10 and 30 wt % of PEA displayed a two‐stage degradation typical of PVC in their thermogravimetric and DSC studies while confirming the increased stability of the samples with higher percentages of PEA. The softening characteristics as detected by the extent of penetration of the thermomechanical probe as has been detected by thermomechanical analysis are in conformity with their mechanicals. The biphasic cocontinuous systems as explicit from the morphological studies reveal fibrillar characteristics in both the systems. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

The influence of poly(vinyl alcohol) suspending agents on suspension poly(vinyl chloride) morphology

The requirements for PVC suspension resin have changed considerably in the last few years, so much so that few companies have products on their ranges that are more than 4 or 5 years old. The suspending agent has a crucial influence on the morphology of the resin, so the changes in resin characteristics have largely been achieved by changes in the suspending agent systems. After a brief review of the mechanism of PVC suspension polymerisation, the properties of polymers made using PVOH suspending agents are related to changes in the latter. The effect of variations in PVAc degree of hydrolysis and viscosity are related to changes in surface tension. Methods of achieving higher porosity by using low hydrolysis co-suspending agents are described. It is shown that higher bulk densities can be achieved by delayed addition of the PVOH. Levels of conjugated unsaturation and copolymer distributions are also shown to have important influences.     

Optical properties of poly(vinyl chloride)-gel-based microlens arrays

We use a poly(vinyl chloride) (PVC) gel and an electrode to fabricate adaptive microlens arrays (MLAs). The electrode has a zoned-array pattern. By applying a direct current voltage to the electrode, the PVC gel on each zoned electrode exhibited the character of a lens. The imaging of the MLA can be analyzed using either an optical microscope or a beam profiler or both. The topography of the PVC gel can be measured using an optical surface profiler. Compared to the imaging and focusing, the topographic map can discover additional information about the performances of the MLA. For example, the focal length of each lens in the MLA can be calculated precisely, and the aberration of the MLA can also be evaluated. Results show that the surface profile is an important factor for characterizing the performance of PVC-gel-based MLA. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47407.