Preparation and structural characterization of nanocrystalline poly(vinyl chloride)

This article describes the development of novel nanocrystalline poly(vinyl chloride) (PVC) for potential applications in PVC processes and reports improvements in the mechanical properties and thermal resistance. Before the preparation of nanocrystalline PVC via jet milling, PVC was spray‐treated and heat‐treated to improve its crystallinity. The pulverization and degradation, morphology, crystalline structure, and melting‐point changes of postmodified PVC during jet milling and the relationship between the distributions of the particle size and processing temperature were investigated. X‐ray analysis and density testing indicated increased density and improved crystallinity. The crystalline region of nanocrystalline PVC was less than 80 nm, with a particle size distribution of 5–20 μm and a melting point of less than 128°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 563–569, 2004     

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     

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     

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     

Behavior of flexible poly(vinyl chloride)/poly(hydroxybutyrate valerate) blends

Blends of flexible poly(vinyl chloride) (PVC) and a poly(hydroxybutyrate valerate) (PHBV) copolymer were prepared and characterized with different techniques. The tensile strength of PVC did not show a marked reduction at PHBV concentrations up to 50 phr, despite a lack of miscibility between the two polymers. The crystallization of the PHBV copolymer was markedly hindered by the presence of PVC, as calorimetric results revealed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

Mechanochemical preparation of a novel polymeric photostabilizer for poly(vinyl chloride)

The preparation of a novel polymeric photostabilizer was carried out via the vibromilling of poly(vinyl chloride) (PVC) powder, a reactive light stabilizer (r‐LS), and a peroxide initiator in ball‐containing jars with a planetary ball mill for a certain time. The effects of the initiator content, milling time, and temperature on the grafting ratio were studied with gravimetric analysis and intrinsic viscosity measurements. Fourier transform infrared and ultraviolet–visible spectra were used to investigate the structural development of the mixture of the r‐LS and PVC during vibromilling. The results showed that the r‐LS was grafted onto PVC chains successfully, and the aforementioned factors had a significant effect on the grafting ratio. The optimum preparation conditions were 0.5 wt % initiator, 8 h, and 20°C. A grafting mechanism is proposed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Formation of conjugated carbon bonds on poly(vinyl chloride) films by microwave‐discharge oxygen‐plasma treatments

Conjugated polyene bonds on poly(vinyl chloride) (PVC) films were rapidly formed by the treatment of oxygen plasma produced by microwave discharge. Changes affecting the formation of conjugated carbon bonds on PVC were studied with respect to plasma emission diagnostic and surface properties of the film with fluorescence, refractant absorption spectroscopy, X‐ray photoelectron spectroscopy analysis, and Raman spectroscopy. The formation of polyene bonds on the film surface was responsible for both the dechlorination and dehydrogenation of PVC in the plasma atmosphere. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 589–594, 2005     

Preparation of chlorinated poly(vinyl chloride)‐g‐poly(N‐vinyl‐2‐pyrrolidinone) membranes and their water permeation properties

Chlorinated poly(vinyl chloride) (CPVC) membranes for microfiltration processes were prepared with the combined process of a solvent evaporation technique and the water‐vapor induced‐phase‐inversion method. CPVC membranes with a mean pore size of 0.7 μm were very hydrophobic. These membranes were subjected to surface modification by ultraviolet (UV)‐assisted graft polymerization with N‐vinyl‐2‐pyrrolidinone (NVP) to increase their surface wettability and decrease their adsorptive fouling. The grafting yields of the modified membranes were controlled by alteration of UV irradiation time and NVP monomer concentration. The changes in chemical structure between the CPVC membrane and the CPVC‐g‐poly(N‐vinyl‐2‐pyrrolidinone) membrane and the variation of the topologies of the modified PVC membranes were characterized by Fourier transform infrared spectroscopy, gel permeation chromatography, and field emission scanning electron microscopy. According to the results, the graft yield of the modified CPVC membrane reached a maximum at 5 min of UV exposure time and 20 vol % NVP concentration. The filtration behavior of these membranes was investigated with deionized water by a crossflow filtration measurement. The surface hydrophilicity and roughness were easily changed by the grafting of NVP on the surface of the CPVC membrane through a simultaneous irradiation grafting method by UV irradiation. To confirm the effect of grafting for filtration, we compared the unmodified and modified CPVC membranes with respect to their deionized water permeation by using crossflow filtration methods. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3188–3195, 2003     

Networks of photocrosslinked poly(meth)acrylates in linear poly(vinyl chloride)

Five different multifunctional acrylic monomers (trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol pentaacrylate) were photopolymerized alone or in a matrix of linear poly(vinyl chloride) (PVC) with 2,2‐dimethyl‐2‐hydroxyacetophenone as a photoinitiator. The course of photopolymerization was estimated with Fourier transform infrared spectroscopy. The amount of insoluble gel formed during photopolymerization was determined gravimetrically. The crosslinked polymerization of pure monomers was much faster than that in the presence of PVC. However, the efficiency of the reaction was higher when it was carried out in a PVC blend because of the higher mobility of the propagating macroradicals. The influence of the monomer structure and functionality on the polymerization course was examined. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3725–3734, 2002     

Rheology of poly(vinyl chloride) plastisol for superhigh shear‐rate processing. I

In coating operations with poly(vinyl chloride) plastisol, there is a high shear limit because the flow becomes unstable. However, there is an indication that the flow becomes stable at superhigh shear rates well past the unstable region. This article explores the effect of the particle size (with a similar size distribution spread) and the effect of the amount of the emulsifier on the flow at superhigh shear rates. It has been known that below the flow instability, larger particles lead to a lower viscosity, and an increased amount of the emulsifier leads to a higher viscosity. The question is whether or not the same trends persist at superhigh shear rates. Observations in this study confirm these trends. In addition, the emulsifier has been found to enhance the interparticle attraction. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Miscibility of segmented polyurethane/poly(vinyl chloride) blends

Miscibilities of segmented polyurethanes (SPUs) and poly(vinyl chloride) (PVC) or functionalized poly(vinyl chloride) (FPVC) were studied with dynamic mechanical analysis, differential scanning calorimetry, and X‐ray diffraction. Mechanical properties of the blends were also studied with tensile measurements. The miscibility of the blends depended greatly on the hard‐segment content of SPU and the existence of the functional groups. The combination of SPU with a low hard‐segment content and PVC with functional groups made the blend system miscible. Moreover, controlling the blend composition of SPU/FPVC allowed us to modify the mechanical properties of SPU, where the elongation at break was multiplied without a significant change in its tensile strength. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3022–3029, 2001     

Effect of poly(vinyl chloride) resin type in the preparation process of slush powder

During the preparation of the poly(vinyl chloride) (PVC) slush powder, we found that PVC resins obtained by different polymerization methods affected many properties of slush powder and its products. Two types of commercial PVC resins were used for slush powder preparation: mass poly(vinyl chloride) (M‐PVC) and suspension poly(vinyl chloride) (S‐PVC). We used the Haake rheomix test to characterize the absorption of plasticizers into PVC resins, and the results showed that M‐PVC absorbed the plasticizers more quickly than S‐PVC. The fusion behavior of the two slush powders was studied by the thermal plate test and Haake rheomix test, and the results showed that the slush powder of M‐PVC was easier to fuse than that of S‐PVC. The different properties of the two resins and slush powder could be explained by the morphology, average size, and size distribution. Due to the “skin” of the particles' surfaces, the wider size distribution, and the large size of particles, S‐PVC absorbed the plasticizers more slowly and was more difficult to fuse. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3331–3335, 2002     

Experimental investigations of polypropylene and poly(vinyl chloride) composites filled with plerospheres

Plerospheres, defined here as superfine spherical particles (0.5–5 μm) separated from fly ash (rather than as other solid spherical particles, as some have used the term), are separated from coal fly ash but are dramatically different from it. Plerospheres can be used as polymer fillers to improve the properties of composites. With plerospheres used as fillers for polypropylene (PP) and unplasticized poly(vinyl chloride) (UPVC), the effects of the filler content, the particle sizes of the plerospheres, and the coupling agent on the composite properties were studied. The particle sizes of the plerospheres were 2 and 5 μm. The results suggested that the notched impact properties both at a normal temperature and a low temperature and the tensile and flexural properties of plerosphere/PP increased significantly when the content was increased from 0 to 30 wt % and further increased with the addition of a coupling agent. Differential scanning calorimetry indicated that the thermal properties of the plerosphere/PP composite improved. The surface characteristics and morphology of the impact fracture surface were examined in detail with scanning electron microscopy. The rheological performance of plerosphere/UPVC pipe composites obviously improved; the plasticizing time was shortened, and the maximum torque was reduced. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 126–131, 2004     

Synthesis of glycidylethylhexylphthalate and its effects on poly(vinyl chloride) films as a novel plasticizer

To improve the processability and prevent the thermal degradation of poly(vinyl chloride) (PVC), various plasticizers and heat stabilizers have to be compounded. Phthalic plasticizers and metal soap stabilizers are usually used with epoxides as costabilizers. Epoxidized soybean oil (ESO), is one of the most commonly used epoxides because of its typical combined roles as a plasticizer and heat stabilizer in PVC compounds. ESO, however, sometimes causes surface contamination of PVC compounds because saturated fatty acids such as stearic and palmitic acids in soybean oil easily bleed onto the surface. In addition, some ingredients in ESO with hydroxide groups and unreacted double bonds during epoxidization also tend to increase the bleeding of ESO. This is due to their low compatibility with PVC resins. In this study, a novel plasticizer of PVC resins, glycidylethylhexylphthalate (GEHP), was synthesized, and its performance was evaluated. GEHP was designed to act as a plasticizer like normal phthalic plasticizers and to act as a heat stabilizer like ESO. Through the addition of epoxy groups in phthalic compounds, the resistance to bleeding was improved, and the plasticizing and heat‐stabilizing effects on the PVC compounds were preserved. Soft PVC films were prepared with GEHP. The mechanical properties, thermal stability, and bleeding properties of the films were investigated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1347–1356, 2005     

Thermal stability of poly(vinyl chloride)/layered double hydroxide nanocomposites

Effects of nanoscale dispersed layered double hydroxides (LDHs) on thermal stability of poly(vinyl chloride) (PVC) in thermal and thermooxidative degradation processes are investigated by dynamic and isothermal thermogravimetric analysis (TGA), discoloration test, fourier transform infrared (FTIR), and ultraviolet‐visible (UV‐vis) spectroscopic techniques. During both stages of thermal degradation, the degradation temperatures, including onset degradation temperature and temperature of the maximum degradation rate, increase, and the final residue yield of the PVC/LDH nanocomposites reaches 14.7 wt %, more than double that for neat PVC. The thermooxidative degradation process is more complex. During the first two stages, the presence of nanoscale dispersed LDH particles enhances the thermal stability, whereas in the last stage accelerates the thermal degradation possibly due to the accumulation of heat released. Additionally, the studies of the isothermal thermooxidative degradation process by FTIR and UV‐vis spectra indicate that both polyene backbone formation and some carbonyl groups are simultaneously developed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Study of poly(vinyl chloride) interfaces using slow positron beams

Elemental and X‐ray fluorescence analyses were performed to determine the chemical compositions of insulator and jacket poly(vinyl chloride) (PVC) samples. In addition, differential scanning calorimetry (DSC) measurement was performed to determine their glass‐transition temperatures (T_g) and melting points. The effect of additives on the two investigated samples, as well as on a pure PVC sample, was studied using Doppler‐broadening energy spectra coupled with the slow positron beam technique. Significant variation in the S parameter as a function of positron implantation energy and depth from the surface to the bulk was observed in all samples. The S parameter increased at a very low positron energy (< 1 keV), saturated to about 6 keV, and then decreased up to 27 keV. The S parameter (ΔS) changed to the extent of the change in the breadth of the distribution of free‐volume defects, which was larger in the jacket PVC sample, which had more additives, than in the insulator PVC sample. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3789–3793, 2006     

Flame retardant flexible poly(vinyl chloride) compound for cable application

ZnO/MgO, ZnO/CaO, and ZnO/CaO/MgO can form solid solutions. The solid solution for we as flame retardant (SSFR) was obtained by annealing at 1023 K for 4.5 h in a muffle furnace. Flexible poly (vinyl chloride) (PVC) filled with SSFR and Sb₂O₃ was investigated by differential thermal analysis thermogravimetry. Limiting oxygen index (LOI), mechanical properties, and electrical properties were studied. The surface of the char formed after combusting of the PVC compounds was observed through scanning electron microscopy and the effect of the surface area to the LOI was also studied. The data suggested that a small amount of SSFR and Sb₂O₃ have good synergy and can greatly increase the LOI and the char yield, and that the thermal degradation temperature and the activation energy decreased. It can be concluded that the mechanism of SSFR is a condensed‐phase mechanism. Moreover, one can conclude that the surface area can enhance the LOI. All the results showed that SSFR is effective and safe as a flame retardant in flexible PVC. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3137–3142, 2003     

Comparison of the toughening mechanisms of poly(vinyl chloride)/chlorinated polyethylene and poly(vinyl chloride)/acrylonitrile–butadiene–styrene copolymer blends

In this study, the influence of chlorinated polyethylene (CPE) and acrylonitrile–butadiene–styrene copolymer (ABS) on the mechanical properties of poly(vinyl chloride) (PVC)/CPE and PVC/ABS hybrids were examined. The experimental results show that the toughness of the hybrids could be modified greatly by the introduction of CPE or ABS. The microstructure and impact surfaces of the blends were investigated by scanning electron microscopy and transmission electron microscopy. ABS dispersed in the form of particles or agglomerates in the PVC matrix, and CPE tended to disperse as a net structure. In the tensile test, ABS initiated crazes as stress concentrators to toughen the PVC matrix, whereas CPE, with the PVC matrix together, caused a yield deformation by shear stress to form a shear band. The formation of crazes and shear bands benefited the toughening of PVC, but to the different extent. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 916–924, 2003     

Preparation and characterization of poly(vinyl chloride)–continuous carbon fiber composites

In this article, we report on the preparation and characterization of novel poly(vinyl chloride) (PVC)–carbon fiber (CF) composites. We achieved the reinforcement of PVC matrices with different plasticizer contents using unidirectional continuous CFs by applying a warm press and a cylinder press for the preparation of the PVC–CF composites. We achieved considerable reinforcement of PVC even at a relatively low CF content; for example, the maximum stress (σ_max) of the PVC–CF composite at a 3% CF content was found to be 1.5–2 times higher than that of the PVC matrix. There were great differences among the Young's modulus values of the pure PVC and PVC–CF composites matrices. The absolute Young's modulus values were in the range 1100–1300 MPa at a 3% CF content; these values were almost independent of the plasticizer content. In addition, we found a linear relationship between σ_max and the CF content and also recognized a linear variation of the Young's modulus with the CF content. The adhesion of CF to the PVC matrix was strong in each case, as concluded from the strain–stress curves and the light microscopy and scanning electron microscopy investigations. The mechanical properties of the PVC–CF composites with randomly oriented short (10 mm) fibers were also investigated. At low deformations, the stiffness of the composites improved with increasing CF content. Dynamic mechanical analysis (DMA) was used to determine the glass‐transition temperature (T_g) of the PVC–CF composites. The high increase in the Young's modulus entailed only a mild T_g increase. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012