Melt flow behavior of blends from poly(vinyl chloride) and epoxidized natural rubber

Blends from poly(vinyl chloride) (PVC) and epoxidized natural rubber (ENR) were prepared in a Brabender plasticorder by the melt blending technique. The melt flow behavior of these blends with respect to blend ratio and temperature has been examined using a melt flow indexer and capillary rheometer. ENR decreases the Brabender torque, increases the melt flow index (MFI), and decreases the melt viscosity of PVC in the blends. Arrhenius plots were used to study the effect of temperature on melt flow index (MFI) and viscosity. Moreover, the flow behavior index (n′) obtained from capillary rheometer data was found to be dependent on temperature and blend ratio.     

Internal mixer studies of poly(vinyl chloride)/epoxidized natural rubber blends

Blends of polyvinyl chloride/epoxidized natural rubber (PVC/ENR) blends were studied. Their rheological properties were studied with a Brabrender Plasticorder. It was found that the rheological properties of any PVC/ENR blends are governed by their blending conditions. To ensure homogenous PVC/ENR blends, adequate and suitable blending conditions must be utilized. PVC thermoplastics phases enhances rigidity while ENR rubbery phases imparts flexibility and processability to the blends. With premixing, Ba/Cd/Zn-based PVC stabilizer is effective in stabilizing the PVC/ENR blends. Their properties are further enhanced by the addition of curatives.     

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.     

Determination of optimum blending conditions for poly(vinyl chloride)/epoxidized natural rubber blends

An attempt to resolve the difficulties normally faced in preparing PVC-dominant PVC/ENR blends with the Brabender plasticorder is discussed. As expected, it was found that the mechanical properties of PVC/ENR blends are greatly influenced by the mixing parameters, which are further reinforced with evidence from both dynamic mechanical analysis (DMA) and morphological studies. Both techniques showed the attainment of compatible 50/50/PVC/ENR blends, the former a single glass transition temperature (T_g) and the latter a single-phase system, albeit their inherent properties are dependent on the blending parameters. By utilizing the correlation between mixing temperature and rotor speed derived, good PVC/ENR blends can be easily procured. © 1993 John Wiley & Sons, Inc.     

Miscible polymer blends containing poly(vinyl chloride)

Polymer blends have received particular interest in the past several decades in both industrial and academic research. An initial survey of miscible polymer pairs (1) (1968) revealed 12 combinations. A later survey (2) (1979) noted approximately 180 miscible pairs. Today possibly over 500 miscible combinations have been noted in the open and patent literature (3). However, the vast majority of possible polymer blend combinations are not miscible (thus phase separated). A significant number of diverse polymer structures have been shown to exhibit miscibility with PVC. Several of these blends have been studied in detail and have shown specific interactions primarily involving the α-hydrogen and PVC (considered the proton donor in proton donor-proton acceptor hydrogen bonding type interactions). The blend of poly(?-caprolactone) with PVC illustrates this interaction and has been reported in many published papers. While polymer miscibility in PVC blends offers significant academic interest, industrial utility is also of considerable importance. The addition of low T_g, miscible polymers to PVC offers permanent plasticization. The addition of high T_g, miscible polymers to PVC yields the desired heat distortion temperature enhancement of rigid PVC. A specific example of permanent plasticization involves nitrile rubber blends which have been commercial since the early 1940's. This presentation will review the growing number of polymers noted to be miscible with PVC. The importance of specific interactions will be discussed.     

Melt elasticity behavior and extrudate characteristics of rigid poly(vinyl chloride)/epoxidized natural rubber miscible blends

A study on the melt elasticity behavior and extrudate characteristics of melts of rigid poly(vinyl chloride), PVC, and rigid poly(vinyl chloride)/epoxidized natural rubber (ENR) miscible blends were conducted. Extrusion studies were carried out in a capillary rheometer and examinations of the surface characteristics of the extrudate were made by taking photomicrographs in a scanning electron microscope. The anomalous behavior in the die swell ratio of rigid PVC arising from the particle agglomerates continued in its blends up to 50 wt% composition of ENR. Temperature independence for high ENR blends was noted for the principal normal stress difference and elastic shear modulus, when shear stress was held constant. Recoverable shear strain and die swell ratio behaved identically in terms of blend composition and processing temperature. Factors which control the extrudate distortion and melt fracture of the melts of rigid PVC/ENR systems were fusion of particle agglomerates and strength of melts. Diamond cavitations were typical of the extrudate surface of PVC melts as those of the fracture surface of the tensile failure of PVC. Conditions to obtain a smooth extrudate surface of rigid PVC melts in blends with ENR have been found to be the low ENR content, low shear rate, or stress and high processing temperature.     

Aspects of miscibility in poly(vinyl chloride)/epoxidized natural rubber blends. Part II: Dynamic mechanical properties

Miscibility in poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blends was further investigated by means of dynamic mechanical analysis. The single glass transition temperature shown by the blends supported earlier observations of miscibility Furthermore, observed synergism in storage modulus has again reaffirmed the miscibility of these blends. A critical examination of the damping peaks at various compositions again revealed the microheterogeneous nature of the blends. Some theories relating glass transition temperature and modulus with miscibility were also used to examine miscibility. Agreement of the results with theories proposed by Gordon—Taylor and Kleiner has provided a further insight into the miscible nature of PVC/ENR blends.     

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.     

Miscibility of blends of epoxidized natural rubber and poly(ethylene-co-acrylic acid)

The blends of epoxidized natural rubber (50 mol %) (ENR) and poly(ethylene-co-acrylic acid) (PEA) (6 wt %) are demonstrated to be partially miscible up to 50% by weight of PEA and completely miscible beyond this proportion. The miscibility has been confirmed by a DSC study which exhibits a single second-order transition (T_g) for the 30 : 70 and 50 : 50 (ENR : PEA) blends. For the 70 : 30 (ENR : PEA) blend, the T_g's shift toward an intermediate value but do not merge to form a single T_g, making the blend partially miscible. The miscibility has been assigned to the esterification reaction between – OH groups formed in situ during melt blending of ENR and – COOH groups of PEA. The occurrence of such reactions have been confirmed by UV and IR spectroscopic studies. The existence of a single phase of the blends beyond 50 wt % of PEA has been shown by SEM studies. © 1995 John Wiley & Sons, Inc.     

Aspects of miscibility in poly(vinyl chloride)/epoxidized natural rubber blends. Part I: Mechanical and morphological properties

Miscibility in poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) blends was studied by examining evidence from tensile, impact, and physical properties. The observation of synergism in tensile strength, percent elongation at break, hardness, and relative density has reaffirmed PVC/ENR blends as miscible systems. Studies of impact properties, however, revealed that the blends are microheterogeneous in nature. This could be attributed to the large sizes of polymer molecules involved and the microgel content of ENR-50. Results from Fourier transform infrared spectroscopy (FTIR) revealed that hydrogen bonding is extensively involved in PVC/ENR systems. This evidence unveiled the exact nature of the specific interactions responsible for miscibility and hence the enhanced mechanical properties of PVC/ENR blends.     

Oil-resistance studies of dynamically vulcanized poly(vinyl chloride)/epoxidized natural rubber thermoplastic elastomer

Dynamically vulcanized poly(vinyl chloride)/epoxidized natural rubber (PVC/ENR) thermoplastic elastomers (TPEs) were prepared with a Brabender plasticorder coupled with a mixing attachment by melt mixing. The blends were prepared at 150°C at a rotor speed of 50 rpm. Curatives concentration was steadily increased from 0 to 1 phr in order to study the vulcanization effect on the plasticized blend. The effectiveness of the dynamic vulcanization was indicated by the Brabender plastograms. The properties investigated include mass swell, tensile strength, elongation at break, modulus at 100% elongation (M100), tear strength, and hardness. The PVC/ENR samples were exposed to two types of environments, namely, air and oil under otherwise identical conditions. The effect of oil and thermooxidative aging on the mechanical properties were characterized at room temperature and 100°C. It was found that at ambient temperature the samples immersed in oil possessed similar properties to those that were exposed to air. Significant enhancement in mechanical properties were observed for both environments at 100°C. This has been attributed to the increase in crosslink density which was manifested by a steady reduction in percent mass swell with increased sulfur loading. The excellent mechanical behavior of the PVC/ENR TPEs even after immersing the samples in oil at 100°C has provided a good indication of the oil resistance of the materials. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1357–1366, 1998     

Weathering of plasticized poly(vinyl chloride)

A series of flexible plasticized poly(vinyl chloride) (PVC) compositions containing different organotin compounds and ultraviolet absorbers has been exposed for 4.5 years at four outdoor sites in Australia with widely differing climatic conditions. Loss of plasticizer by evaporation during the exposure was measured and an empirical correlation was found with the average daily maximum temperature at each site. The relative effectiveness of the organotin compounds and ultraviolet absorbers in preventing deterioration of the PVC was estimated by measuring the viscosity of the polymer after exposure. This method of assessment is compared with the results of mechanical tests on the specimens.     

Miscible blends of poly(butyl methacrylate) densely grafted on fumed silica with poly(vinyl chloride)

Poly(butyl methacrylate) (PBMA) densely grafted on a fumed silica particle consisting of primary particles with an average diameter of 14 nm, has been synthesized by surface-initiated atom transfer radical polymerization (SI-ATRP). In these syntheses, a newly designed initiator, p-(bromomethyl)benzyl 2-bromoisobutylate was used for the immobilization of the initiator moiety on the silica particle to give the densely grafted PBMA. Thus synthesized nanocomposites have exhibited unusual miscibility with poly(vinyl chloride) (PVC) through differential scanning calorimetry (DSC). The derivative DSC peaks for the composite/PVC blends were significantly different from those for the conventional PBMA/PVC blends. This interesting finding is due to a wide gradient of the PVC concentration on a microscopic scale, resulting from the densely grafted PBMA chains; the PBMA component is enriched near the surface of the fumed silica, while the PVC component is enriched far from the surface. This gradient miscible state is strongly supported by dynamic mechanical analysis. Furthermore, a synergistic effect on storage modulus was seen in the nanocomposite/PVC blends.     

Plasticizer migration from plasticized into unplasticized poly(vinyl chloride)

There exist important industrial applications, such as hoses or plastic windows, dealing with closely combining plasticized and rigid poly(vinyl chloride). Nevertheless, migration of plasticizer causes severe variation of the mechanical performance of the end-products. This work comprises an effort to investigate and understand these phenomena, also as an extension of previous work of ours in migration to liquid environments. The common system plasticized PVC/dioctylphthalate/unplasticized PVC was studied under two-sided diffusion conditions, i.e., from a thin sheet of plasticized sheet. The whole assembly was placed between two glass plates and then was held in an oven at 64°C to simulate accelerated test conditions. Some pressure was also applied to ensure perfect contact between the plastic sheets. Three different levels of initial plasticizer concentration (48, 66, and 100 phr) have been considered for a period of about five months, until equilibrium was reached. During this period the migration process was monitored by weight changes. Plots of M_t/M_∞ vs. t^½, where M_∞ the amount migrated at equilibrium and M_t the amount lost at time t, resulted in evident linear relationship. Therefore, it was proved that the Fick's law approximation for short times can be used to describe the migration kinetics for this solid/solid system. On the other hand, macroscopic observations revealed that no plasticizer was accumulated at the interface, i.e. all plasticizer leaving the plasticized sheet entered the rigid ones. Finally, it seems that the controlling stage is the diffusion inside plasticized PVC while possible annealing of the plasticized polymer structure cannot be excluded.     

Thermovulcanization of polychloroprene rubber and its blends with poly(vinyl chloride)

Heat and mechanical stressing at higher temperatures effect changes in polychloroprene rubber leading to network formation. During thermovulcanization of polychloroprene rubber in the temperature range of 150–200°C, two reactions have been observed and their kinetic parameters determined. When the rubber is stressed by shearing forces, the rate of degradation crosslinking is fairly high even at relatively low temperatures (90–150°C). Thermovulcanization of polychloroprene rubber/poly(vinyl chloride) blends has been investigated in the entire concentration range at 180°C. Maxima have been observed on the dependences of some kinetic parameters of the thermovulcanization reaction on polymer blend composition.     

Smoke suppressants for plasticized poly(vinyl chloride)

Addition of plasticizers to poly(vinyl chloride) generally increases its flammability and frequently increases smoke production during its burning. Flame retardants added to plasticized PVC can reduce flammability, but increase smoke production. This study shows that proper choice of combined use of other polymers, phosphate plasticizers, fillers and other flame retardants, produces measured synergistic improvements in flame retardance and smoke suppression which could benefit applications such as PVC wire and cable insulation.     

Developments of high performance vibration absorber from poly(vinyl chloride)/chlorinated polyethylene/epoxidized natural rubber blend

A high performance vibration absorber requires a high loss factor behavior over a wide temperature and frequency range. An investigation was carried out to prepare such materials based on poly(vinyl chloride), chlorinated polyethylene, and epoxidized natural rubber ternary blends. The loss factor and damping behavior of several compositions were measured using a viscoelastic spectrometer and a polymer‐laminated steel cantilever‐beam damping device. Suitable compositions were found to give good mechanical properties and high loss factor over a wide temperature and frequency range. It was also observed that flake‐type fillers improve the damping behavior. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 855–863, 1999     

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.     

A hysteresis in plasticized poly(vinyl chloride)

Plasticized poly(vinyl chloride) formulations were prepared in solid and foam form, and mechanical hysteresis was measured by low-speed tension and compression on an Instron tester and by high-speed rebound on a resiliometer. Hysteresis was greatest in copolymers with vinyl acetate, at low plasticizer concentration, with inefficient plasticizers, at high concentrations of reinforcing fillers, at high expansion to low density, and at high speed of testing. Conversely, resilience was greatest at high plasticizer concentration, with more efficient plasticizers, with non-reinforcing fillers, and at high density.