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     

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     

Mechanical properties of poly(vinyl chloride) blends and corresponding graft copolymers

The mechanical properties of the poly (vinyl chloride) (PVC) and poly (glycidyl methacrylate) [poly (GMA)] blend system and the PVC and poly (hydroxyethyl methacrylate) [poly (HEMA)] blend system and their crosslinked films were investigated. At the same time, the mechanical properties for the corresponding graft copolymers such as PVC-g-GMA, PVC-g-HEMA, and their crosslinked films were also investigated in this study. The results showed that the tensile strengths for PVC–poly (GMA) blend systems were higher than those for PVC-g-GMA graft copolymer, and the tensile strengths for PVC-g-HEMA were higher than those for PVC-poly (HEMA) blend systems. However, the mechanical properties for the PVC–poly (GMA) blend system were not affected by the crosslinking of the blend system, but those for PVC-poly (HEMA) and their graft copolymers decreased with an increase of the equivalent ratio ([NCO]/[OH]) of the crosslinker. Finally, the surface hydrophilicity of the PVC-g-HEMA graft copolymer and PVC-poly (HEMA) blends were also assessed through measuring the contact angle. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 307–319, 1998     

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     

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     

Effects of carbon‐coated titanium dioxide nanoparticles as a photostabilizer on the photodegradation of rigid poly(vinyl chloride)

In this study, nanocomposites of rigid poly(vinyl chloride) (UPVC) using the synthesized carbon‐coated titanium dioxide (TiO₂) nanoparticles and commercial powder of titanium dioxide (with rutile structure) were prepared by melt blending. The presence of carbon‐coated TiO₂ nanoparticles with rutile structure in UPVC matrix led to an improvement in photo stability of UPVC nanocomposites in comparison with commercial UPVC. The photocatalytic degradation behavior of nanocomposites was investigated by measuring their structural changes, surface tension, and mechanical and morphological properties before and after UV exposure for 700 h. It was found that mechanical and physical properties of UPVC nanocomposites are not considerably reduced after UV exposure in the presence of carbon‐coated TiO₂ nanoparticles even in small percentage of nanoparticles in comparison with the presence of commercial TiO₂ particles. Therefore, it can be concluded that UPVC/TiO₂ nanocomposite with low content of carbon‐coated TiO₂ nanoparticles(0.25 wt %) illustrated high stability under light exposure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40228.     

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.     

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     

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     

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     

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 effect of pentaerythritol‐aluminum on the thermal stability of rigid poly(vinyl chloride)

Pentaerythritol‐aluminum (PE‐Al) was synthesized by a solid‐phase reaction in this study. The formation and characteristics of PE‐Al were confirmed by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). SEM images showed that the shapes of PE‐Al particles were spherical and the average size was around 23 nm. The thermal properties of rigid poly(vinyl chloride) (PVC) with PE‐Al were tested by Congo red test, thermal aging test, conductivity test, thermogravimetric analysis (TGA), and UV–visible spectroscopy test. The results showed that combination of PE‐Al, in comparison with commercial thermal stabilizers, presented an obvious improvement in stabilization efficiency of PVC. Moreover, addition of PE‐Al could significantly prolong static stability time of PVC, reduce weight loss, and improve the initial color of PVC films. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3704–3709, 2013     

Stabilization of poly(vinyl chloride) against photo‐degradation using dienophilic compounds

As dienophilic compounds, N‐ aminophenylmaleimides would be expected to act as radical traps and thus, could be investigated as organic photo‐stabilizers for rigid poly(vinyl chloride) (PVC). Their stabilizing efficiencies were evaluated by measuring the extent of discoloration and the change in the mechanical properties of the photo‐irradiated polymer. Their stabilizing efficiencies were compared with phenyl salicylate, which is a commonly used industrial photo stabilizer. The results have proved the higher stabilizing efficiency of all the investigated materials as compared with phenyl salicylate. The stabilizing efficiency of the aminomaleimides is attributed to their radical trapping potency which intervenes with the radical degradation of the photo‐irradiated PVC. Moreover, it was found that these materials lower the extent of discoloration of the polymer during later stages of degradation. This improvement in the color stability is most probably attributable to the ability of the aminomalemides to react by a Diels–Alder reaction with the conjugated double bonds created on the polymeric chains as a result of the degradation of the polymer. Finally, the results illustrate the blending of aminomaleimide derivatives with phenyl salicylate improve the photo stabilization of the polymer as shown from the absorbance coefficient Δa values, and this improvement attains its maximum when both the investigated stabilizers and phenyl salicylate are taken in equivalent ratios. The observed synergism is attributed to the combination of the mechanisms by which both stabilizers function. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Studies of electrical and mechanical properties of poly(vinyl chloride) mixed with electrically conductive additives

Different samples of poly(vinyl chloride) (PVC) compositions were formulated from PVC, a polar plasticizer such as dioctylphthalate (DOP), and variable proportions of electrically conductive additives such as fast extrusion furnace (FEF) carbon black (CB), poly(vinylpyridine) (PVP), or polyacrylonitrile (PAN). Epoxidized soybean oil was added as a heat stabilizer. Samples of the PVC–CB system were also prepared by dispersing different concentrations of CB into the PVC matrix. The electrical studies showed that the addition of CB to the PVC–DOP system produces a plasticized PVC with high electrical conductivity whereas the compounding of PVC with CB produces a sample with much higher electrical conductivity. The effect of the structure of PVP and PAN on the electrical and mechanical properties of the PVC–DOP system was also studied to obtain a semiconductive plasticized PVC with good mechanical properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1590–1598, 2004     

Evidence of irradiation‐induced crosslinking in miscible blends of poly(vinyl chloride)/epoxidized natural rubber in presence of trimethylolpropane triacrylate

Electron‐beam initiated crosslinking of a poly(vinyl chloride)/epoxidized natural rubber blend (PVC/ENR), which contained trimethylolpropane triacrylate (TMPTA), was carried out over a range of irradiation doses (20–200 kGy) and concentrations of TMPTA (1–5 phr). The gelation dose was determined by a method proposed by Charlesby. It was evident from the gelation dose, resilience, hysteresis, glass‐transition temperature (T_g), IR spectroscopy, and scanning electron microscopy studies that the miscible PVC/ENR blend underwent crosslinking by electron‐beam irradiation. The acceleration of crosslinking by the TMPTA was further confirmed in this study. Agreement of the results with a theory relating the T_g with the distance between crosslinks provided further evidence of irradiation‐induced crosslinking. The possible mechanism of crosslinking induced by the irradiation between PVC and ENR is also proposed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1914–1925, 2001     

A new biobased plasticizer for poly(vinyl chloride) based on epoxidized cottonseed oil

The use of epoxidized cottonseed oil as plasticizer for poly(vinyl chloride) was studied. The plasticizer content was set to 70 phr and the optimum isothermal curing conditions were studied in the temperature range comprised between 160 and 220 °C with varying curing times in the 7.5–17.5 min range. The influence of the curing conditions on overall performance of cured plastisols was followed by the evolution of mechanical properties (tensile tests with measurements of tensile strength, elongation at break, and modulus), change in color, surface changes of fractured samples by scanning electron microscopy (SEM), thermal transitions by differential scanning calorimetry, and migration in n‐hexane. The optimum mechanical features of cured plastisols are obtained for curing temperatures in the 190–220 °C range. For these curing conditions, fractography analysis by SEM gives evidences of full curing process as no PVC particles and free plasticizer can be found. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43642.     

Blends of poly(vinyl chloride) with acrylonitrile-chlorinated polyethylene-styrene copolymer. II. Mechanical properties

Blends of poly(vinyl chloride) (PVC) and acrylonitrile-chlorinated polyethylene-styrene (ACS) graft copolymer were prepared by melt blending. Mechanical properties were studied by the use of dynamic mechanical analysis (DMA), impact tests, tensile tests, and scanning electron microscopy (SEM). The DMA study showed that PVC is immiscible with chlorinated polyethylene in ACS but partially miscible with poly(styrene-co-acrylonitrile) (25% acrylonitrile content) in ACS. Mechanical property tests showed that there is a significant increase in the impact strength while other good mechanical properties of PVC such as high modulus and high strength remain. SEM observations supported the results of the mechanical properties studies. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 399–405, 1997     

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     

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     

Determination of gelation temperature of poly(vinyl chloride) by thermomechanical and thermogravimetric parameters

Preheating between the temperatures of 200 and 280°C is done to a film‐structured poly(vinyl chloride) (PVC) sample, which has a gelation temperature ∼ 250°C. After this preheat, the PVC's thermomechanical and thermal differences, at temperatures before and after thermal gelation, are observed. Consequently, when some thermomechanical and thermal parameters, obtained at temperatures before and after gelation, are compared, it can be said that this is an easier method to determine the gelation temperature of a polymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1635–1640, 2005