The effect of an epoxidized plasticizer on the thermo-oxidative ageing of poly(vinyl chloride)/epoxidized natural rubber thermoplastic elastomers

The effects of an epoxidized plasticizer on the mechanical properties and thermo-oxidative ageing behaviour of poly(vinyl chloride)/epoxidized natural rubber thermoplastic elastomers (TPEs) were investigated. Aged and unaged blends were characterized by FTIR, tensile properties, tear strength, hardness and dynamic mechanical analysis (DMA). The properties of the epoxidized soya oil (ESO) plasticized TPEs were compared with those of the di-2-ethylhexylphthalate (DOP) plasticized counterparts. The presence of epoxide groups in ESO has been shown to produce two conflicting effects. On the one hand, the presence of excessive epoxide groups has resulted in poor ageing behaviour. On the other hand, it has resulted in a good interaction and compatibility with PVC/ENR. It was found that the tensile strength of the ESO plasticized blends were comparable with the DOP plasticized ones, but the elongation at break (EB) of the ESO blends fell short of that of the DOP blends. Also the retention of both tensile properties for the ESO blends was poorer than for DOP blends. Hardening and embrittlement also occurred in the ESO blends. Despite these weaknesses, ESO could be an ideal plasticizer for the PVC/ENR system as indicated by plasticizer permanence and the greater efficiency of plasticization. © 1998 SCI.     

Mechanical and thermo-oxidative properties of blends of poly(vinyl chloride) with epoxidized natural rubber and acrylonitrile butadiene rubber in the presence of an antioxidant and a base

Being polar and compatible with poly(vinyl chloride), epoxidized natural rubber (ENR) is similar in behaviour to acrylonitrile butadiene rubber (NBR). To assess the extent of this similarity, the mechanical properties of 50/50 blends of PVC with these two rubbers were compared. Their response to thermo-oxidative ageing in the presence of an antioxidant and a base was also investigated by ageing the blends at 100°C for 7 days. Studies involving mechanical properties and FTIR were used to evaluate the extent of thermal degradation. The results revealed that blends of ENR show mechanical properties which are as good as, and in some instances better than, those of the NBR blends. However, the ENR blends with PVC are very prone to oxidative ageing. This might be attributed to the susceptibility of the oxirane group to ring-opening reactions, particularly in the presence of PVC, which yields HCl as it degrades. The amine-type antioxidant 2,24-trimethyl-1,2-dihydroquinoline (TMQ) improved the oxidative stability of both blends. This was more significant in the ENR blend, which in some cases attained stability comparable with that of NBR. The addition of a base, calcium stearate [Ca(St)₂], did not show any influence in the PVC/ENR blend, even though it was expected to curb acid-catalysed degradation. Ca(St)₂, however, improved the oxidative stability of the PVC/NBR blend. The combination of optimum amounts of TMQ and Ca(St)₂ effectively improved the tensile strength of both unaged blends, without appreciable adverse effect on elongation at break. This combination also imparted stability better than that of TMQ alone.     

Radiation crosslinking of poly(vinyl chloride)/epoxidized natural rubber blend: effect of lead stabilization of the poly(vinyl chloride) phase

The irradiation crosslinking of 50/50 poly(vinyl chloride)/epoxidized natural rubber blend was investigated in the presence of 1–5 parts per hundred resin (phr) tribasic lead sulfate (TBLS) with blends prepared at various mixing temperatures. The blends were irradiated using a 3.0 MeV electron accelerator at 0, 100 and 200 kGy irradiation doses. Changes in tensile strength, elongation at break and stress‐strain curves of the blends with the increase TBLS content and blending temperatures were observed before and after irradiation. The results on the tensile properties revealed the inhibition of the irradiation‐induced crosslinking by the TBLS although it stabilizes the blend against thermal and irradiation‐induced degradation. The Fourier transform infrared spectroscopy studies further confirmed these observations. Control on the thermal degradation of the blend during blending found to be crucial in achieving maximum enhancement in blend properties upon irradiation. Evidence from dynamic mechanical analysis was also used to support this contention. Addition of 2 phr TBLS and blending at 150 °C found to be adequate in order to achieve the best enhancement in blend properties through irradiation‐induced crosslinking. © 2001 Society of Chemical Industry     

Contact angle behaviour of poly(vinyl chloride)/ epoxidized natural rubber miscible blends

—Contact angle studies of miscible poly(vinyl chloride)/epoxidized natural rubber (PVC/ ENR) blends were carried out in air using water and methylene iodide. The solid surface free energy was calculated from harmonic mean equations. Blending of PVC and ENR decreased their contact angle or increased their solid surface free energy due to the improved chain mobility, and the accumulation of excess polar sites at the surface through conformational alterations resulting from the specific interaction of PVC and ENR. The work of adhesion, interfacial free energy, spreading coefficient, and Girifalco-Good's interaction parameter changed markedly with the blend composition. In blends, PVC and ENR improved hydrophilicity, and wettability with polar and non-polar liquids. The presence of a plasticizer in PVC, in general, further improved the wettability and hydrophilicity in blends.     

The effect of epoxide content on compatibility of poly(lactic acid)/epoxidized natural rubber blends

The objective of this work was to determine the effect of the epoxide content in epoxidized natural rubber (ENR) on the miscibility and compatibility with poly(lactic acid) (PLA) in prepared PLA/ENR blends. PLA was blended with 10 wt% of ENRs (epoxidized at 10, 15, 20, and 25 mol%). The presented study showed that the in situ graft copolymer, PLA-g-ENR, was formed during melt blending in the blends containing 10 and 15 mol% ENR. This work is the initial study showing the presence of PLA-g-ENR in the blends by ¹H-NMR and ¹³C-NMR. PLA-g-ENR acted as a compatibilizer, producing a partially miscible blend, indicated by an inward shift of the α-transition temperatures of PLA and ENR in the blends. PLA-g-ENR also greatly reduced the particle size of ENR and increased the impact strength, tensile strength, and elongation at break of the blends. The epoxide content of ENR changed deformation mechanisms of the blends.     

Assessment of di-(2-ethylhexyl)phthalate (DEHP) Removal in a Rotating Biological Contactor and Activated Sludge Process Treating Domestic Wastewater

Di-(2-ethylhexyl)phthalate (DEHP) is one of the most representative persistent micro-pollutants detected in the sewage sludge. In the present study, the presence of DEHP and its removal in various treatment units of a sewage treatment plant (STP) including an attached growth biological system i.e., a rotating biological contactor (RBC) and a suspended growth biological system i.e., activated sludge process (ASP) were investigated. Representative samples of sewage and sludge were collected at each stage of the STP for 2 years to explore the DEHP flow in the dissolved (DEHP_d) and adsorbed (DEHP_a) phases. The combination of RBC with a final clarifier was responsible for 50.4 and 58.2% of DEHP_d and DEHP_a removals, respectively. Both DEHP_d and DEHP_a removals were greater in RBC compared to ASP, demonstrating that an attached growth biological system is more efficient in the removal of DEHP compared to the suspended growth biological system. A good correlation between DEHP and organic matter removal was observed by using Pearson-correlation matrix approach.     

Tensile,stress-strain and creep rupture properties of poly (vinyl chloride)/poly(neopentyl glycol adipate)/poly(vinylidene fluoride) blends

Poly (vinyl chloride), PVC, and poly(vinylidene fluoride), PVDF, are incompatible polymers. Poly(neopentyl glycol adipate), PDPA, is miscible with both PVC and PVDF. With PDPA acting as a compatibilizer between PVC and PVDF. compatible PVC/PDPA/PVDF blends can be formed at PVDF content of about less than 50wt%. Above 50wt% PVDF the ternary blends exist in two phases exhibiting two glass transition temperatures, T_g, PVC is the main contributor to the mechanical strength while PDPA and PVDF contribute to the elastic properties of these blends. A compatible blend of 55/22.5/22.5 wt% PVC/PDPA/PVDF exhibiting one single T_g appears to show an interesting balance of the properties of the blend components.     

Effect of acrylic acid on the properties of recycled poly(vinyl chloride)/acrylonitrile–butadiene rubber blends

The effect of acrylic acid (AAc) on the torque, stabilization torque, mechanical energy, swelling behavior, mechanical properties, thermal stability, and morphological characteristics of recycled poly(vinyl chloride)/acrylonitrile–butadiene rubber (PVCr/NBR) blends was studied. The blends were melt mixed at a temperature of 150°C and rotor speed of 50 rpm. AAc was used to improve the compatibility of PVCr/NBR blends. Virgin PVCv/NBR blends were prepared to provide a comparison. It was found that PVCr/NBR + AAc blends exhibit higher stabilization torque, mechanical energy, stress at peak, and stress at 100% elongation, but lower elongation at break and swelling index than those of PVCr/NBR and PVCv/NBR blends. SEM study of the tensile fracture surfaces of the blends indicated that the presence of AAc increased the interfacial interaction between PVCr and NBR phases, thus improving the compatibility between PVCr and NBR phases. However, thermal gravimetry analysis of the blends showed that the presence of AAc decreased the thermal stability of PVCr/NBR blends. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2181–2191, 2005     

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     

Study on nitrile-butadiene rubber/poly(propylene carbonate) elastomer as coupling agent of poly (vinyl chloride)/poly (propylene carbonate) blends. I. Effect on mechanical properties of blends

Nitrile-butadiene rubber/poly(propylene carbonate) (NBR-PPC) elastomer was studied as a coupling agent of the blends of poly(vinyl chloride) (PVC) with poly(propylene carbonate) (PPC). It greatly improved the PVC/PPC system mechanical properties that were dependent on the amount and composition of the coupling agent. When the coupling agent consisted of a 70/30 ratio of NBR/PPC (in which NBR had 34% nitrile content) and 2.5 phr of benzoyl peroxide (BPO) initiator and underwent a prevulcanization, the blends of PVC/PPC displayed excellent mechanical properties by adding 8 phr of the coupling agent. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1107–1111, 1997     

High‐performance bio‐based poly(lactic acid)/natural rubber/epoxidized natural rubber blends: effect of epoxidized natural rubber on microstructure,toughness and static and dynamic mechanical properties

Attempts have been made to prepare high‐performance bio‐based blends through blending of poly(lactic acid) (PLA) with natural rubber (NR) in the presence of epoxidized natural rubber (ENR) as a compatibilizer. The prepared samples were characterized using differential scanning calorimetry, measuring the tensile properties and impact resistance, scanning electron microscopy, Fourier transform infrared (FTIR) spectroscopy and dynamic mechanical analysis (DMTA). Morphological studies revealed a matrix‐dispersed morphology for all blends, in which the average droplet size significantly decreased with the use of ENR. The elongation at break and impact strength of the blend containing 3 wt% ENR were 45 and 16 times those of neat PLA, respectively. These values are significantly higher than those previously reported for various simple and dynamically vulcanized rubber‐toughened PLAs. The influence of ENR on compatibility was confirmed by rheological tests, FTIR spectra and DMTA. DMTA also showed a marked increase in elastic modulus for the blend in the presence of 3 wt% ENR. The tensile properties and impact resistance were directly dependent on the ENR content and rubber droplet size. © 2018 Society of Chemical Industry     

丁腈橡胶/聚氯乙烯/受阻酚AO-60共混物的结构与性能

用差示扫描量热法、X射线衍射法、扫描电子显微镜及元素分析法分析了丁腈橡胶(NBR)/聚氯乙烯(PVC)/四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(AO-60)共混物的结构,并研究了共混物的阻尼性能及力学性能。结果表明,当AO-60用量小于50份时,其分子在基体中以非晶态形式存在;当AO-60用量超过50份时,过量的AO-60形成聚集体并在基体中形成少量的晶体;NBR/PVC/AO-60共混物内部呈现“海相-岛相”结构,连续相主要是NBR,而分散相主要是PVC与AO-60分子。NBR/PVC/AO-60共混物的损耗因子-温度曲线呈双峰特征,且随着AO-60用量的增加,峰值明显增大。当AO-60用量为50份时,NBR/PVC/AO-60共混物的综合力学性能较佳。     

Effect of electron‐beam irradiation on poly(vinyl chloride)/epoxidized natural rubber blend: dynamic mechanical analysis

The irradiation‐induced crosslinking in 50/50 poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blend was investigated by means of dynamic mechanical analysis. The influence of trimethylolpropane triacrylate on the irradiation‐induced crosslinking of PVC/ENR blends was also studied. The enhancement in storage modulus and T_g with irradiation dose indicated the formation of irradiation‐induced crosslinks. This is further supported by the decrease in tan δ_max and loss modulus peak. The compatibility of the blend was found to be improved upon irradiation. The Fox model was used to provide a further insight into the irradiation‐induced compatibility in the blend. Scanning electron microscopy studies on the cryofracture surface morphology of the blends as well as the homopolymer have been undertaken in order to gain more evidence on the irradiation‐induced crosslinking. © 2001 Society of Chemical Industry     

Miscibility,phase behavior,and mechanical properties of ternary blends of poly(vinyl chloride)/polystyrene/chlorinated polyethylene-graft-polystyrene

The effectiveness of chlorinated polyethylene-graft-polystyrene (CPE-g-PS) as a polymeric compatibilizer for immiscible poly(vinyl chloride)/polystyrene (PVC/PS) blends was investigated. The miscibility, phase behavior, and mechanical properties were studied using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), Izod impact tests, tensile tests, and scanning electron microscopy (SEM). DSC and DMA studies showed that PVC is immiscible with chlorinated polyethylene (CPE) in CPE-g-PS, whereas the PS homopolymer is miscible with PS in CPE-g-PS. The PVC/PS/CPE-g-PS ternary blends exhibit a three-phase structure: PVC phase, CPE phase, and PS phase that consisted of a PS homopolymer and PS in CPE-g-PS. The mechanical properties showed that CPE-g-PS interacts well with both PVC and PS and can be used as a polymeric compatibilizer for PVC/PS blends. CPE-g-PS can also be used as an impact modifier for both PVC and PS. SEM observations confirmed, after the addition of CPE-g-PS, improvement of the interfacial adhesion between the phases of the PVC/PS blends. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 995–1003, 1998     

Electron‐beam irradiation of poly(vinyl chloride)/epoxidized natural rubber blends in presence of trimethylolpropane triacrylate

Electron‐beam initiated crosslinking of poly(vinyl chloride)/epoxidized natural rubber blends, 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 gel content increased with the irradiation dose and the TMPTA level, although the increase was marginal at higher doses and higher TMPTA levels. Blends containing 3–4 phr TMPTA achieved optimum crosslinking, which in effect caused the maximum tensile strength (TS) at a dose of 70 kGy. A further addition of TMPTA caused a decline in the TS above 40 kGy that was due to embrittlement, which is a consequence of excessive crosslinking and the breakdown of the network structure. The possible formation of a more open network as a result of the breakdown of the network structure was further confirmed by the modulus results. Dynamic mechanical analysis (tan δ curve) and scanning electron microscopy studies on samples irradiated at 0 and 200 kGy were undertaken in order to gain further evidence on the irradiation‐induced crosslinking. The plasticizing effect of TMPTA prior to irradiation and the formation of microgels upon irradiation were also discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1926–1935, 2001     

Rheological properties of poly(vinyl chloride)/epoxidized natural rubber blends. Part I: Composition dependence and the effect of compounding conditions

Epoxidized natural rubber is a recently commercialized modified form of natural rubber. This paper is part of our continuing effort to study the responses of this new material to melt mixing and other shaping processes. The Shimadzu capillary rheometer was used to evaluate the composition dependence of miscibility of polyvinyl chloride/epoxidized natural rubber blends (PVC/ENR blends). The rheometer was also used to evaluate the effect of compounding parameters on the rheological properties of the blends. The results confirmed PVC/ENR blends as miscible systems that show a synergism in apparent shear viscosity highlighted by the positive deviation from the logarithmic additivity rule. These results based on capillary rheometry are also in very good agreement with our earlier attempt to predict optimum mixing from torque rheometry by using the Brabender Plastogram as an indicator.     

Rheological properties of poly(vinyl chloride) / epoxidized natural rubber blends. Part II: The effect of processing variables

The effect of processing variables on the rheological properties of PVC/ENR blends was investigated. The role of crosslinking in determining the flow behavior of blends was also examined by means of dynamically cured blends. It was found that PVC/ENR blends yield melts that are power law fluids. The flow of the melts improves with an increase in temperature and shear rate. However, the introduction of crosslinks reverses this trend, although under more rigorous conditions, the influence of crosslinks is superseded, and subsequently, flow becomes shear rate and temperature dependent. PVC/ENR systems also manifested elastic phenomena. The dependence of the elastic phenomena such as die swell and melt fracture on L/D ratio of the die was demonstrated.     

Effects of hydrothermal ageing on the thermal behaviour of poly(vinyl chloride) filled with wood flour

The hydrothermal ageing of wood‐flour‐filled PVC produced by dry‐blending in a high‐speed mixer in the presence of a plasticizer and other processing additives was carried out to investigate its thermal behaviour, and the results obtained were compared with those for the unfilled material. The dry‐blended compounds were prepared as films by a calendering process. The accelerated hydrothermal ageing was carried out by immersing the samples in boiling water at 100 °C for 110 h. The thermal behaviour of the reference and the aged samples in water was characterized by differential scanning calorimetry (DSC) and determination of the weight changes. The study has shown that during hydrothermal ageing, the samples from the whole formulations absorbed water, for instance, for 30 wt% filled PVC (F30), 16 wt% of water absorption was obtained, while this was only 2.2 wt% for unfilled PVC (F0). It was also noticed that the formulations filled with wood flour up to 10 wt% exhibited similar water absorption kinetics, i.e. the water was mostly absorbed during the first 50 h and the amount absorbed was less than 5 wt%. On the other hand, the 30 wt% filled samples regularly absorbed water up to almost 16 wt% after 100 h of immersion. The DSC data showed that hydrothermal ageing significantly affected the onset temperature of decomposition (T_d) of the unfilled samples by decreasing this temperature from 228 to 215 °C. For the 30 wt% filled samples, only additive migration was observed, while the T_d remained almost unchanged. Furthermore, from the DSC data, processability of the 30 wt% filled PVC samples at elevated temperatures, i.e. 180 to 200 °C was shown. Copyright © 2004 Society of Chemical Industry     

Effects of epoxidized sunflower oil on the mechanical and dynamical analysis of the plasticized poly(vinyl chloride)

Epoxidized soybean oil (ESBO), is one of the most commonly used epoxides because of its typical combined roles as a plasticizer and heat stabilizer. In this study, a novel plasticizer of poly(vinyl chloride) (PVC) resins, epoxidized sunflower oil (ESO), was synthesized, and its performance was evaluated. ESO was designed to act as a coplasticizer and a heat stabilizer like ESBO. ESO is used as organic coplasticizer for plasticized PVC containing Ca and Zn stearates as primary stabilizers and stearic acid as lubricant. Di‐(2‐ethylhexyl) phthalate (DEHP), a conventional plasticizer for PVC, was partially replaced by ESO. Mechanical properties (tensile and shore D hardness) were investigated. The performance of ESO to ESB0 (20 g) for comparison, indicated that ESO could be used as secondary plasticizer for PVC in combination with DEHP. All mechanical and dynamical properties of plasticized PVC sheets varied with the oxirane oxygen of the ESO. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of olive residue benzylation on the thermal and mechanical properties of poly(vinyl chloride)/olive residue composites

The changes in mechanical properties, the thermal stability, and the water absorption capacity of poly (vinyl chloride)/olive residue flour composites were studied as a function of various residue olive flour ratios, i.e., 0, 5, 15, and 25% by weight taking into account the effect of benzylation chemical treatment of the filler. The study showed that composite samples prepared with the untreated filler exhibited higher tensile modulus and hardness compared with the neat resin, whereas elongation and tensile strength were observed to decline. On the other hand, the PVC hardness was found to increase with addition of the untreated olive residue flour (ORF), however the composite samples prepared with the benzylated flour exhibited lower hardness than those prepared with untreated olive residue. Moreover, the amount of absorbed water depends on the amount of filler in the composite. The comparison of the results obtained from the samples of F5, F20, and F30 formulations between the untreated and treated ORF indicated a reduction in absorbed water for the composite samples containing treated ORF with benzyl chloride. As a result, the mechanical properties of the treated composites were improved. Furthermore, the thermal characterization of the different samples carried out by color change test and thermogravimetric analysis revealed an increase in the onset temperatures of decomposition for the treated composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008