Processability,rheology, and thermal,mechanical, and morphological properties of postconsumer poly(vinyl chloride) bottles and cables

The processability, rheology, and thermal, mechanical, and morphological properties of three different commercial poly(vinyl chloride) (PVC) compounds blended with postconsumer PVC bottles and PVC cables were examined with respect to the recycled PVC content. The addition of PVC bottle recyclates [recycled bottles (RBs)] into virgin PVC bottle (VB) and virgin PVC pipe (VP) compounds caused a progressive reduction in the average torque. No thermal degradation or color change in the RB‐blended PVC compounds used was detected through carbonyl and polyene indices from IR analysis. The rheological properties for VP compounds were more sensitive to RB addition than those of VB compounds. The extrudate swell ratio did not change with the RB content. The decomposition temperature for the VB and VP compounds increased at 60–80% RB, whereas the glass‐transition temperature was unaffected by the RB loading. The 20 and 80 wt % RB loadings were recommended for the VB and VP compounds, respectively, for the optimum impact strength, the blends showing ductile fracture with a continuous phase. At the optimum impact and tensile properties, introducing RB recyclates into the VB compounds gave better results than the VP compounds. The hardness and density of the VB and VP compounds did not change with the RB content. The RB property change was comparatively faster than that of recycled PVC pipes. Adding the PVC cable recyclate [recycled cable (RC)] to virgin PVC cable (VC) had no obvious effect on the torque value of the RC/VC blends. The decomposition temperatures of the RC/VC blends stabilized at 20–60% RC and tended to decrease at 80% RC. The ultimate tensile stress was improved by the addition of the RC compounds, whereas the hardness and density of the VC compounds were unaffected by the RC content. It was concluded that the optimum concentrations of PVC recyclates to be added to virgin PVC compounds were different from one property to another and also depended on the type of virgin PVC grade used. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2738–2748, 2003     

Influence of additional thermal stabilizers on the reprocessing of postconsumer poly(vinyl chloride) bottles

The addition of heat stabilizers is essential for preventing the degradation of poly(vinyl chloride) (PVC) during its processing. The heat stabilizers consumed in the first run have to be made up before the reprocessing of recycled PVC. In this study, solvent‐cast films, which were prepared from granulated postconsumer PVC bottles mixed with plasticizers and thermal stabilizers, were used. The films were subjected to various heat treatments. No considerable structural change upon heat treatments at 140–160°C was found in IR and differential scanning calorimetry analyses. Polyene formation observed through ultraviolet analysis was not severe, indicating that the added stabilizers worked well in preventing degradation. The weight loss during the heat treatments was attributed partly to the decomposition of PVC and the evaporation of volatile components and mainly to the removal of the solvent upon heating. Although this study was conducted with water bottles that were to be recycled, it may be equally well applied to other similarly formulated PVC‐based materials, such as packaging films. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3994–3999, 2003     

Compatibility study of recycled poly(vinyl chloride)/styrene‐acrylonitrile blends

The aim of the present study is to analyze the compatibility between recycled Poly(vinyl chloride) (PVC) and styrene‐acrylonitrile copolymer (SAN). With this objective recycled PVC coming from credit cards have been blended with both virgin and recycled SAN with the aim of increase the benefits of recycled PVC. The compatibility of the components will be crucial for the final properties of the material. Furthermore, the recycled nature of some of the components will determine the compatibilization capability of the blend. The degradation level in the recycled materials was determined using Fourier transform infrared spectroscopy (FTIR). The compatibility between the PVC and the SAN was studied using differential scanning calorimetry and dynamic mechanical analysis. A greater compatibility was observed in mixtures of PVC and virgin SAN than in mixtures of PVC and recycled SAN. Finally, a morphological study of the fracture surface under cryogenic conditions was carried out using scanning electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Chemical recycling of poly(vinyl chloride): Application of partially dehydrochlorinated poly(vinyl chloride) for producing a chemically modified polymer

Poly(vinyl chloride) (PVC) pipes were chemically modified to produce a sulfonated polymer with dehydrochlorinated PVC samples as intermediates. Two intermediates were formed: (1) partially dehydrochlorinated PVC with long sequences of conjugated double bonds and (2) the product of the partial dehydrochlorination of PVC and the nucleophilic substitution of chlorine by hydroxyl groups. The IR spectra showed that the dehydrochlorinated samples were heterogeneous materials, showing different proportions of elimination products, hydroxyl substitution, and partial oxidation. Samples dehydrochlorinated with poly(ethylene glycol) with a molecular weight of 400 g/mol for 24 h and 15 min showed the highest sulfonation yield, which was related to the sulfonation mechanism occurring predominantly because of the presence of hydroxyl groups in a mixture of vinyl alcohol and vinyl chloride units. The sulfonation was confirmed by the presence of a medium‐intensity band at 1180 cm^?1, assigned to sulfonic groups. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and application of a natural plasticizer based on cardanol for poly(vinyl chloride)

A natural plasticizer with multifunctional groups, similar in structure to phthalates, cardanol derivatives glycidyl ether (CGE) was synthesized from cardanol by a two‐step modification process and characterized by FT‐IR, ¹HNMR, and ¹³CNMR. The resulting product was incorporated to PVC (CGE/PVC), and plasticizing effect was compared with PVC incorporated with two kinds of commercial phthalate ester plasticizers bis (2‐ethylhexyl) benzene‐1,4‐dicarboxylate (DOTP) and diisononyl phthalate (DINP). Dynamic mechanical analysis and mechanical properties testing of the plasticized PVC samples were performed in order to evaluate their flexibility, compatibility, and plasticizing efficiency. SEM was employed to produce fractured surface morphology. Thermogravimetric analysis and discoloration tests were used to characterize the thermal stabilities. Dynamic stability analysis was used to test the processability of formulations. Compared with DOTP and DINP plasticized samples, CGE/PVC has a maximum decrease of 9.27% in glass transition temperature (T_g), a maximum increase of 17.6% in the elongation at break, and a maximum increase of 31.59°C and 25.31 min in 50% weight loss (T50) and dynamic stability time, respectively. The obtained CGE also has slightly lower volatility resistance and higher exudation resistance than that of DOTP and DINP. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42465.     

Dehydrochlorination of poly(vinyl chloride) modified with titanium dioxide/poly(ethylene oxide) based paint photocatalysts

The dehydrochlorination of poly(vinyl chloride) (PVC) film samples modified with titanium dioxide (TiO₂)/poly(ethylene oxide) (PEO) based paint photocatalysts [the addition of methyl linoleate (ML) or methyl oleate (MO)] was performed. After 24 h of UV photoirradiation, the sample with TiO₂/PEO showed that there existed a structure with the longest polyene length, whereas that with TiO₂/PEO/ML contained the most polyene structures. The chloroform‐soluble fraction of the sample with TiO₂/PEO contained a poly(vinyl alcohol) (PVA) structure instead of a polyene one and showed a novel method of PVA production via PVC photodegradation. The molecular weight curve of the fraction shifted slightly to a lower molecular weight compared to that without the photocatalyst; this showed that slight polymer chain scission occurred. The ¹H‐NMR and ¹³C‐NMR spectra showed that the content of PVA units was about 20%, and the PVA sequence was blocky. The fraction of the sample with TiO₂/PEO/ML contained the highest methyl group content; this showed that the branch degree was highest as was the polyene content. These highest contents were due to the existence of the grafted ML. Pyrolysis gas chromatography/mass spectroscopy measurements suggested that there existed more polyene and graft units in the chloroform‐insoluble fractions of the samples with TiO₂/PEO, TiO₂/PEO/ML, and TiO₂/PEO/MO, respectively. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40760.     

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.     

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     

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.     

Blends of plasticized poly(vinyl chloride) and waste flexible poly(vinyl chloride) with waste nitrile rubber powder

Blends of poly(vinyl chloride) (PVC) with varying contents of plasticizer and finely ground powder of waste nitrile rubber rollers were prepared over a wide range of rubber contents through high‐temperature blending. The effects of rubber and plasticizer (dioctyl phthalate) content on the tensile strength, percentage elongation, impact properties, hardness, abrasion resistance, flexural crack resistance, limiting oxygen index (LOI), electrical properties, and breakdown voltage were studied. The percentage elongation, flexural crack resistance, and impact strength of blends increased considerably over those of PVC. The waste rubber had a plasticizing effect. Blends of waste plasticized PVC and waste nitrile rubber showed promising properties. The electrical properties and LOI decreased with increasing rubber and plasticizer content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1552–1558, 2004     

Multiscale morphology and thermo‐mechanical history of poly(vinyl chloride) (PVC)

The multiscale morphology of rigid poly(vinyl chloride) (PVC) formulations (in the nanometre to the micrometre range) was investigated by high resolution scanning electron microscopy, ultra‐small‐, small‐ and wide‐angle X‐ray scattering, as a function of thermo‐mechanical history. It has been shown that the hierarchical structure of PVC grains, when in the dry blend, disappeared during gelation that combines mechanical stress (ie shear stress and hydrostatic pressure) and heating. Nevertheless, the memory of the presence of the smallest particles (domains with diameters of about 80 nm) containing dense amorphous PVC and nanoscaled crystallites, has been highlighted by the study of the change of the microstructure when PVC was reprocessed with high mechanical deformation at a lower temperature than the previous gelation temperature. As a result, the main phenomena occurring during gelation were, in a first step, the disappearance of the hierarchical structure of the grains and, in a second step, the inter‐diffusion of the chains across the frontiers of the primary particles (mechanically reversible), but maintaining the domain structure. The crystalline microstructure was affected by thermo‐mechanical history, but the gelation level should not be estimated strictly in relation to the crystalline morphology. Copyright © 2004 Society of Chemical Industry     

Study on thermal,mechanical and morphological properties of recycled poly(vinyl chloride)/fly ash composites

The present study deals with the development of composite materials utilizing recycled poly(vinyl chloride) (r‐PVC) recovered from waste electrical and electronic materials and waste fly ash obtained from thermal power plants. The effect of the incorporation of fly ash on the mechanical, thermal and morphological properties of the r‐PVC matrix was studied. The primary characterization of r‐PVC and fly ash was done employing FTIR, EDX, particle size analysis and XRD analysis. Subsequently, fly ash with a particle size of approximately 9.29 μm was incorporated within the r‐PVC matrix. Composite sheets were prepared using a melt blending process followed by compression moulding. The mechanical test revealed an increase in the tensile strength and elongation at break of the r‐PVC/fly ash composite up to 30 wt% loading of fly ash beyond which there was a decrease in the tensile strength. The impact strength, however, decreased with increasing fly ash content in the r‐PVC matrix. The morphological properties of the composites showed a good distribution of the filler within the recycled matrix. The thermal properties of r‐PVC also improved with the incorporation of fly ash which was revealed from DSC and TGA studies. The water absorption test showed an increase in water uptake with the addition of fly ash in the r‐PVC matrix. © 2020 Society of Chemical Industry     

Succinate-based plasticizers: Effect of plasticizer structure on the mechanical and thermal performance of poly(vinyl chloride) plastic formulations

A new family of succinate-based plasticizers, consisting of molecules with a linear alkyl chain capped with n-alkyl succinates on both ends, was evaluated as potential bio-based plasticizers for stiff polymers. The influence of the central and side alkyl chain lengths on the mechanical and thermal properties as well as the migration behavior of poly(vinyl chloride) (PVC)/plasticizer blends was evaluated. The central chain length had the greatest influence on plasticizer performance, with shorter chains leading to blends with higher stress at break and surface hardness, whereas long chains produced softer blends. An optimum chain central length of five carbon atoms was observed, with longer chains leading to reduced compatibility and exudation of the plasticizer at higher plasticizer concentrations. The entire family of plasticizers performed comparably or better than the commercial plasticizer di(2-ethylhexyl) phthalate (DEHP) when incorporated into the blend at concentrations of 20–60 parts per hundred resin (phr). Overall, the succinate-based plasticizers/PVC blends all exhibited equal or improved tensile properties (by up to 77%), surface hardness (reduced by up to 43%), glass transition temperature (reduced by up to 11°C), and migration into organic media (reduced by up to 38%) when compared with blends with DEHP at 40 phr.     

Stabilization of poly(vinyl chloride) by elemental sulfur

The process of stabilization of a poly(vinylchloride) elemental sulfur in thermal and thermooxidative destruction conditions is investigated. The high stabilizing efficiency of elemental sulfur is revealed at the destruction of plasticized poly(vinylchloride) compared with the efficiency of phenolic antioxidants. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Peroxide crosslinking of unplasticized poly(vinyl chloride)

A crosslinking system consisting of 1,1‐di‐t‐butylperoxy‐3,3,5‐trimethyl cyclohexane peroxide and trimethylolpropane trimethacrylate (TMPTMA) has been used to introduce crosslinks into unplasticized poly(vinyl chloride) (PVC). The influence of the concentration of both reagents has been investigated, and crosslinking monitored by determination of the remaining sample weight after Soxhlet extraction with tetrahydrofuran. The system used (i.e., 0.5–2.0 phr peroxide with 5 to 15 phr TMPTMA) has been shown to be effective for crosslinking PVC. Gel contents of 30–40% have been obtained, premature crosslinking during processing is largely avoided, but thermal stability still needs to be improved. Considerable improvements in elevated temperature mechanical properties can be attained using an appropriate TMPTMA/peroxide concentration. The best tensile properties were obtained with 0.5 phr peroxide and 15 phr TMPTMA. Observed increases in T_g, also achievable with only 0.5 phr peroxide, but only slightly dependent on TMPTMA concentration, represent a useful increase in service temperature for the resulting compound. Lower peroxide levels may be adequate to achieve property improvements. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2657–2666, 2000     

Thermodestruction in the surface layer of poly(vinyl chloride) during extrusion

Polymeric raw material passing through the extrusion machine and other forming devices undergoes the processes of destruction, which result in the formation of potentially harmful substances and their accumulation in the surface layers of the product directly contacting with heated parts of forming machines. The research of the top layer of a poly(vinyl chloride) profile has shown that the surface layer of polymer contains a number of chlorinated hydrocarbons. The following substances have been identified during the research of the hydrocarbons composition contained of the surface layer: hexachlorobenzene, hexachlorobutene, chloroform, acetyl chloride, biphenyl, anthracene, naphthalene, and other hydrocarbons. The difference of calculated activation energy of thermooxidizing destruction of surface and internal layers of a polymeric product reveals the process of partial destruction of a surface layer. Data about semivolatile substances, concentrating in polymer surface during processing will be used for development of stabilizers, ecology, and polymer‐manufacturing techniques. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008.     

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     

In-situ polymerization of n-butyl acrylate in poly(vinyl chloride)

The in situ polymerization of n-butyl acrylate with poly(vinyl chloride) has been studied. Butyl acrylate was polymerized using a peroxydicarbonate initiator and a thiol chain transfer agent in the presence of poly (vinyl chloride) beads suspended in water. The products were examined, after pressing into sheets, for optical clarity and by dynamic mechanical analysis. It was found that if 10% butyl acrylate was peesent in the mixture homogeneous blends were formed but if 15% or more butyl acrylate was present two phase mixtures were formed. If homogeneous blends prepared as above were reswollen in butyl acrylate, and the latter then polymerized, homogeneous blends containing more poly(butyl acrylate) could be prepared. The interaction parameters between both poly(vinyl chloride' and poly(butyl acrylate) and butyl acrylate were estimated by inverse gas chromatography. Using these and an estimate of the polymer/polymer interaction parameter the three component phase diagram could be qualitatively explained.     

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