Investigation of multiphase polymeric systems of poly(vinyl chloride)/ethylene-propylene-diene-gp-(styrene-CO-acrylonitrile) blends

The graft copolymer, ethylene-propylene-diene rubber (EPDM)-gp-(styrene-co-acrylonitrile) has been synthesized by solution precipitation polymerization using benzoyl perixide as initiator. The graft copolymer has been characterized after separation through soxhlet extraction by IR, NMR, and elemental analysis techniques. The graft copolymer of EPDM is melt blended with PVC. The nature of compatibility of the graft copolymers with PVC has been studied by means of morphological analysis and by thermal analysis. The mechanical properties, Izod impact strength, tensile strength, and flexural modulus of the blends are extensively studied over the wide range of concentrations. The results of both compatibility and mechanical properties are compared with those of PVC/EPDM blends. The nature of compatibility obtained shows that PVC/EPDM blends are incompatible and the PVC/EPDM-gp-SAN system is semicompatible. Also, these results indicate that the PVC/EPDM-gp-SAN system has its highest impact strength at 14 wt% of EPDM/gp-SAN graft copolymer. The fractured surface analysis of the impact fractured samples is also undertaken by an SEM technique. The results of the mechanical properties are discussed in view of existing theories of impact modification, along with the morphological feature of fractographs.     

Thermal stability of PVC/chlororubber-20-graft polyblend–styrene–acrylonitrile blends. I

Thermal stability of PVC blends with chlororubber-20-graft polyblend-styrene-acrylonitrile [CR-20gp-SAN (2:1)] was studied by HCI evolution techniques and thermogravimetry under isothermal condition. The thermal stability of PVC/CR-20gp-SAN (2:1) blends has been compared with those of PVC/CR-20 and PVC/KM-365B blends. It has been observed that the thermal stability of modified PVC is less than that of unmodified PVC. The CR-20gp-SAN (2:1) modified PVC blends were found to be more stable than PVC/CR-20 blends but less stable than PVC/KM-365B blends. The rate of degradation in PVC blends were observed to be unaffected by the concentration of the modifiers, but the PVC/KM-365B blends were found to be degrading slower in comparison with PVC/CR-20 and PVC/CR-20gp-SAN (2:1) blends. The rate of degradation for PVC/CR-20 blends at lower concentrations (<10%) of modifiers is almost equal to that of PVC/CR-20-gp-SAN (2:1) blends, but more at higher concentrations of modifiers (>10%). The experimental results have been explained on the basis of the chemical nature of the modifiers and their miscibility with PVC.     

Compatibility and thermal stability studies on PVC/chlororubber-20-graft polyblend-styrene–vinyl acetate–acrylonitrile blends. II

Compatibility and Thermal stability studies have been performed on PVC blends with chlororubber-20-graft polyblend-styrene–vinyl acetate–acrylonitrile (1:1:1) [CR-20gp-SVAAN (1:1:1)]. The grafting of styrene, vinyl acetate, and acrylonitrile onto chlororubber-20 backbone chain generates some amount of heterogeneity in the system. The compatibility behavior of PVC/CR-20gp-SVAAN (1:1:1) blends has been reflected in the ultrasonic velocity and absolute viscosity vs. composition plots of the blend. These blends have been found to be thermally miore stable than PVC/chlororubber-20 blends, but less stable than PVC/KM-365B blends. The rate of degradation is equal to that of the PVC/chlororubber-20 blends. The results have been discussed on the basis of compatibility, stabilizing, and destabilizing behavior of various component polymers with PVC matrix.     

Stabilization of poly(vinyl chloride). IV. Color changes on heating poly(vinyl chloride)–dye systems

The stabilization of poly(vinyl chloride) (PVC) involving complementary colors has been previously reported. Obliterating polyene color with various dyes containing complementary colors with the polyene color is studied on the basis of colorimetry. The changes in the color of heated PVC containing Thren Blue IRN, Ceres Blue GN, Oplas Violet 730, Macro-Lex Violet 3R, Macro-Lex Green 5B, or Macro-Lex Red 5B were investigated using a differential colorimeter. When the PVCs containing various dyes were heated, the discoloration from the color of each dye to the color mixture of each dye and polyene color was observed with increased heating times for all systems. In particular, an achromatic color has been observed, during the heat treatments, in PVC containing blue dyes such as Thren Blue IRN or Ceres Blue GN, which set up complementary color relationship with the polyene color. Thus the color of polyenes, which appears with advancing dehydrochlorination of PVC, is masked by the blue dyes. It is also apparent that the obliteration of polyene color does not depend on the chemical influences of the dyes added, but by color mixing of polyenes and the dyes. Cool-color dyes markedly slow down the appearance of polyene colors.     

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     

Mechanical properties of oriented poly(vinyl chloride)–poly(caprolactone) blends

Blends of poly(vinyl chloride) (PVC) with polycaprolactone (PCL) of different compositions were prepared from solutions in tetrahydrofuran (THF). The dried blends were stretched at different temperatures above the glass transition, and the birefringence and mechanical properties were studied. It is shown that the birefringence of PVC and the 75/25 PVC/PCL blend follows an affine deformation scheme with a decreasing number of segments with deformation. The 50/50 PVC/PCL blend shows a complex orientation behavior because of the presence of crystallinity in the PCL phase. The mechanical properties of the blends are shown to increase with orientation, and the aggregate model is acceptably followed by the amorphous oriented blends.     

Morphology and properties of poly(vinyl chloride)–polyurethane blends

The objective of this research was to study the morphology and properties of PVC–polyurethane blends. Studies on blends of a segmented polyether polyurethane with PVC were carried out utilizing differential scanning calorimetry, Rheovibron, stress–strain, infrared peak position studies, and infrared dichroism experiments. This thermodynamically incompatible system was made kinetically compatible by precipitation from tetrahydrofuran (THF) solutions. THF–dioxane solution casting and melt processing produced an incompatible system. The compatible polyurethane–PVC system contains a well-mixed PVC–polyether matrix phase as evidenced by T_g shifts, orientation characteristics, and infrared peak position changes. The aromatic urethane segments which exhibit microphase separation in the pure polyurethane are not solubilized by blending with PVC by any of sample preparation methods used in this study.     

Contributions to characterization of poly(vinyl chloride)–lignin blends

The present study evaluates the impact of blending organosolv and kraft lignins, which are natural polymer by‐products in the pulp and paper industry, with plasticized poly(vinyl chloride) (PVC) in flooring formulations. Also examined is the impact of replacing dioctyl phthalate, a PVC industry general‐purpose plasticizer, with diethylene glycol dibenzoate (Benzoflex 2‐45), tricresyl phosphate (Lindol), or alkyl sulfonic phenyl ester (Mesamoll) in these formulations. The influence of the different types of lignins and plasticizers on the processibility, thermal, and mechanical properties of the blends is discussed. These properties demonstrate that partial replacement of PVC (20 parts) with different lignins is feasible for some formulations that can be successfully used as matrices for a high level of calcium carbonate filler in flooring products. In addition, the data demonstrate that the presence of certain plasticizers, which interfere with the intramolecular interactions existing in lignins, may allow the lignin molecules to have more molecular mobility. The morphology and the properties of PVC plasticized lignin blends are strongly influenced by the degree and mode of the lignin plasticization and its dispersion within the PVC matrix. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2732–2748, 2006     

The supermolecular structure of poly(vinyl chloride)–poly(methyl methacrylate) blends

Investigations of the supermolecular structure of PVC/PMMA blends, covering a wide range of composition, are presented. It was found that a transition layer exists between PVC and PMMA phases. The thickness of the transition layer is independent of blend composition. The scattering intensity distribution function for blends is characteristic of isotropic, amorphous systems with a completely random distribution of phases. It was shown that scattering intensity distribution function may be used for calculation of a distribution, which corresponds a two-phase system with sharp phase boundaries. Values of correlation lengths, inhomogeneity lengths, and specific surfaces were then calculated. A model of the supermolecular structure of PVC/PMMA blend was finally proposed.     

Miscibility and rheological properties of poly(vinyl chloride)/styrene–acrylonitrile blends prepared by melt extrusion

Styrene–acrylonitrile (SAN) with acrylonitrile (AN) concentrations of 11.6–26 wt % and α‐methylstyrene acrylonitrile (αMSAN) with a wide range of AN concentrations are miscible with poly(vinyl chloride) (PVC) through solution blending. Here we examine the rheological properties and miscibility of PVC/SAN and PVC/αMSAN blends prepared by melt extrusion for commercial applications. We have investigated the rheological properties of the blends with a rheometer and a melt indexer. The PVC/SAN and PVC/αMSAN blends have a low melting torque, a long degradation time, and a high melt index, and this means that they have better processability than pure PVC. The miscibility of the blends has been characterized with differential scanning calorimetry, dynamic mechanical thermal analysis, and advanced rheometrics expansion system analysis. The miscibility of the blends has also been characterized with scanning electron microscopy. The SAN series with AN concentrations of 24–31 wt % is immiscible with PVC by melt extrusion, whereas αMSAN with 31 wt % AN is miscible with PVC, even when they are blended by melt extrusion, because of the strong interaction between PVC and αMSAN. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Modification of poly(vinyl chloride). XIX. Electroplating of poly(vinyl chloride)

As a preliminary treatment in the PVC-electroplating procedure, treatment with dimethylformamide followed by sensitization leads to a finely roughened and a highly hydrophilic surface with reducing power. This is caused by the formation of an ionic complex compound between dimethylformamide and tin(II) chloride absorbed in the PVC surface. A much more finely and deeply etched surface which exhibits higher adhesion through the mechanical interlocking effect is obtained with the PVC blends containing the plasticizer with a low value of interaction parameter and with a solubility parameter approximate to that of PVC. Adhesion of the metal layer to the PVC surface thus obtained is improved about 1.5 times by thermal aging at 120°C for 20 min.     

Miscibility in poly(vinyl chloride)/chlorinated poly(vinyl chloride) blends,and blends of different chlorinated poly(vinyl chlorides)

Blends of poly(vinyl chloride) with chlorinated poly(vinyl chloride) (PVC), and blends of different chlorinated poly(vinyl chlorides) (CPVC) provide an opportunity to examine systematically the effect that small changes in chemical structure have on polymer-polymer miscibility. Phase diagrams of PVC/CPVC blends have been determined for CPVC's containing 62 to 38 percent chlorine. The characteristics of binary blends of CPVC's of different chlorine contents have also been examined using differential calorimetry (DSC) and transmission electron microscopy. Their mutual solubility has been found to be very sensitive to their differences in mole percent CCl₂ groups and degree of chlorination. In metastable binary blends of CPVC's possessing single glass transition temperatures (T_g) the rate of phase separation, as followed by DSC, was found to be relatively slow at temperatures 45 to 65° above the T_g of the blend.     

Rheology of poly(vinyl chloride) blends

PVC/EVA blends were studied with an extrusion plastometer in order to examine the effect of EVA on the processability of PVC. The melt flow of PVC/EVA blends containing from 4 to 30 weight percent EVA follows a simple power law between 160 and 180°C. EVA reduced the melt viscosity and enhanced processability. Blends of PVC and EVA were morphologically incompatible. The molecular weight of extruded PVC in the blends was unchanged.     

Polymeric systems for acoustic damping. I. Poly(vinyl chloride)–segmented polyether ester blends

A series of six Hytrel/PVC blends were prepared by solution blending Hytrel in methylene chloride and PVC in tetrahydrofuran. The samples were subsequently prepared in sheet form by hot pressing at 170°C. Physical and mechanical properties of the homopolymers and the blends were investigated. The copolyester homopolymer is a partly crystalline elastomeric material. The level of crystallinity was measured by x-ray diffraction and the sensitivity of this level to heat treatments and quenching determined by DSC. A Morgan pulse propagation meter was used to measure sonic velocity and, indirectly, acoustic impedance of the blends. Dynamic mechanical studies indicated that blends containing 25%–50% by weight of Hytrel were completely compatible in the sense that a single glass transition was observed; but as the Hytrel level was increased to 60% and 65%, a shoulder became apparent on the low-temperature side of the glass transition peak. At 80% Hytrel, two peaks were observed, indicating incompatibility. The glass transition temperatures of these blends were found to decrease linearly with added Hytrel.     

Modification of poly(vinyl chloride). XXXIV. Crosslinked poly(vinyl chloride) via paste-processing

A novel PVC-crosslinking technique using 6-dibutylamino-1,3,5-triazine-2,4-dithiol (DB) was applied for a paste processing to produce a crosslinked PVC product. The paste formulation recommended in the present study consisted of 100 parts of PVC (Zeon 121), 60 parts of dioctyl phthalate, 0.2 parts of MgO, and 6 parts of a 50% solution of DB-Na in butylcarbitol, which gave a highly crosslinked and transparent sheet with an excellent stability for thermal discolouring. The increasing viscosity behaviour of the paste during storage is explained by the effect of interparticle attracting forces of DB-Na which coordinates to the ether oxygen atoms in the glycol derivatives adsorbed on the surface of PVC particles. The increased viscosity can be reduced by addition of 3 parts of N-butyl-benzene-sulfonamide. The tension-distortion properties at elevated temperatures were remarkably improved at the crosslinked product compared with the uncrosslinked. The mechanical properties of the two crosslinked products produced via paste processing and roll-blending are compared in regard to the differences of the uniformity of crosslinking units.     

Environmental degradation of some polymer blends. Blends of polystyrene with acrylonitrile butadiene styrene,poly(vinyl chloride), and polybutadiene and blends of polybutadiene with poly(vinyl chloride)

One class of polymer/additive which has become increasingly important is polymer blends. In this study the ultimate tensile strength, elongation at break, and the modulus of acrylonitrile–butadiene–styrene, poly(vinyl chloride), polybutadiene and polystyrene and their blends have been studied over an entire binary composition range. We have correlated these mechanical properties to their degradation behavior under natural and accelerated weathering by measurement of various indices during thermal and natural weathering. It was found that during natural weathering the presence of polystyrene in acrylonitrile–butadiene–styrene (ABS) improved the weatherability of ABS; the converse was true when the blends were heated in an air oven at 100°C. It was also found that the weatherability of PB was improved in the presence of polystyrene and large improvement in the rigidity was observed. Similarly, from a measurement of carbonyl index, it was found that PVC has a stabilizing effect on PB. In many cases, the 50:50 composition of the polymers gave the best compromise of good mechanical properties, heat stability, and outdoor weathering. The mechanisms of possible interactions between the degrading polymers are discussed.     

Thermooxidative degradation of poly(vinyl chloride)/acrylonitrile–butadiene–styrene blends

The thermal degradation process of poly(vinyl chloride)/acrylonitrile–butadiene–styrene (PVC/ABS) blends was investigated by dynamic thermogravimetric analysis in the temperature range 50–650°C in air. The thermooxidative degradation of PVC/ABS blends of different composition takes place in three steps. In this multistep process of degradation the first step, dehydrochlorination, is the most rapid. The maximal rate of dehydrochlorination for the PVC blends containing up to 20% ABS-modifier is achieved at average conversions of 23.5–20.0%, i.e., at 13.5% for the 50/50 blend. The apparent activation energies (E = 103–116 kJ mol⁻¹) and preexponential factors (Z = 2.11 × 10⁹−3.45 × 10¹⁰min⁻¹) for the first step of the degradation process were calculated after the Kissinger method. © 1996 John Wiley © Sons, Inc.     

Thermal degradation of poly(vinyl chloride) blends

Poly(vinyl chloride) was mixed with various poly(methacrylate)s and polycarbonates by combined precipitation from common solutions. The thermal stability of the samples was measured at 180°C under nitrogen, the HCl evolved was detected by conductometry. UV-Vis-spectra of degraded samples were measured to investigate the influence of the poly(methacrylate)s on the lengths of polyenes formed during the degradation of poly(vinyl chloride). The experiments show that the nature of the ester group is the dominating factor for the thermal stability of poly(vinyl chloride) in these blends. Poly(n-butylmethacrylate) exhibits the best stabilization for poly(vinyl chloride) in this series. Polycarbonates with a higher glass transition temperature than the temperature of degradation destabilize poly(vinyl chloride). Stabilization experiments with dibutyltin-bis(isooctylthioglycolate) show a costabilizing effect of the poly(methacrylate)s and polycarbonates.     

Stabilization of poly(vinyl chloride). I. Change in color of poly(vinyl chloride) compounded with some metal soaps

Poly(vinyl chloride) (PVC) with one or more metal salts added was colored by the action of heat to investigate the stabilization mechanism. The coloration and the color difference of heated PVC compound films varied according to the metal salt added. The decoloration of the colored compound films was advanced markedly in THF, DMF, acetone, and ammonia. On the other hand, the heated achromatic PVC film containing Cd/Ba soaps underwent an opposite change, from colorless to yellow orange, in the above materials. This means that the coloration of heated compound films may result from the formation of some complex (for example, π complex of the polyene with the metal chloride). Furthermore, the colored film with cadmium stearate was decolored by roll mixing with the colored film containing barium stearate. These results indicate that the stabilization with metal soaps may be founded on a physical phenomenon such aa an effect of complementary color.