Study of poly(vinyl chloride) blends with solid‐state chlorinated polyethylene

The influence of solid‐state chlorinated polyethylene of various chlorine content and residual crystallinity on the mechanical properties of rigid poly(vinyl chloride) has been studied. The impact strength of poly(vinyl chloride) was found to increase significantly as 10–20 mass% chlorinated polyethylene, containing from 10.2 to 27.3% chlorine content (preferably 21.8% Cl) were added. This dependence corresponded to the higher elasticity and impact strength of the solid‐state chlorinated polyethylene with chlorine content below 30% as well as the microstructure of its chlorinated block fragments. Multicomponent system of high impact strength and good flowability, consisting of poly(vinyl chloride), chlorinated polyethylene, hydroxyl‐terminated polybutadiene, and ethylene–propylene–ethylidenenorbornene terpolymer was also obtained. Regardless of the incompatibility between the polymer components of this blend, the similarity in the chemical nature of poly(vinyl chloride) and chlorinated polyethylene blocks on one hand, and the methylene sequences in the chlorinated polyethylene and elastomers on the other, resulted in the formation of an efficient interfacial layer. The changes in the structure of the blends were established by both calorimetric and microscopic studies. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2602–2613, 2006     

Translucent blends of chlorinated polyethylene with poly(vinyl chloride)

Some experimental chlorinated polyethylene (CPE) resins that produced translucent blends with PVC were used to study the effects of CPE chlorine content and chlorine distribution on the morphology, optical clarity, and toughness of blends with PVC. The CPE resins were characterized in terms of the glass transition temperature, residual crystallinity, density, and refractive index. Increasing residual crystallinity and increasing chlorine content both increased the refractive index closer to that of PVC. A linear relationship was observed between the fourth power of the refractive index and the CPE glass transition temperature. With a phase-separated blend morphology in all cases, improved transparency was achieved in this system by reducing the refractive index difference between CPE and PVC. Both haze and transparency showed the predicted linear dependence on the square of the refractive index difference. To a first approximation, modifications of the experimental CPE resins that improved optical transparency of the blends also tended to reduce the toughness enhancement.     

A study on poly(vinyl chloride) blends with chlorinated polyethylene and polyethylene

By means of a twin-roll masticator and Brabender rheometer, the effect of chlorinated polyethylene (CPE) and polyethylene (PE) on the impact strength and processability of poly(vinyl chloride) (PVC) was studied. The experimental results show that CPE can promote the plasticity of PVC and the effect increases with the amount of CPE. Addition of a small amount of PE in PVC/CPE (100/12) makes an impressive improvement in the impact strength of the mixture. The impact strength of PVC/CPE/PE (100/ 12/2.5) at 20°C is 30.0 kJ/m² higher than that of PVC/CPE (100/12). The dynamic viscoelastic spectra, tensile strength, and elongation test reveal that CPE is incompatible with PVC but may act as a compatibilizer for PVC/PE. The disperse state of the polyblend was studied by differential scanning calorimetry (DSC); it was found that the mixing sequence has an influence on the impact strength of the blend.     

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.     

A study on poly(vinyl chloride) blends with chlorinated polyethylene and acrylic resin

The compatibility, morphology, fusion behavior, and mechanical properties of blends of poly(vinyl chloride) (PVC), acrylic resin (ACR), and chlorinated polyethylene (CPE) (100/0–30/0–20) were studied. The experimental results show that the compatibility of the polyblend increases with the amount of ACR added. The blends composed of PVC/ACR/CPE (100/3–25/10–15) are fairly compatible. So far as impact strength is concerned, partially compatible blends are preferred.     

Impact modification of poly(vinyl chloride) with chlorinated polyethylene I. Blend morphology

The solid state morphology of chlorinated polyethylene (CPE)-modified poly(vinyl chloride) (PVC) and the relationship of blend structure to impact strength and mode of fracture have been investigated. Selective staining of the CPE phase showed that the morphology of the two phase system changes with increasing CPE content from a dispersion of discrete CPE particles to a network structure enveloping the primary PVC particles. The network formation coincides with a transition from brittle to ductile impact fracture. When the blend was mixed for too long a time or above the fusion temperature of the primary PVC particles, the CPE network was destroyed. The resulting indistinct domain structure is associated with a reduction in the impact properties.     

The toughness and morphology of (chlorinated poly[vinyl chloride])/(methyl methacrylate‐butadiene‐styrene) blends

A series of methyl methacrylate‐butadiene‐styrene (MBS) graft copolymers were synthesized via seeded emulsion polymerization techniques by grafting styrene and methyl methacrylate on poly(butadiene‐co‐styrene) (SBR) particles. The chlorinated poly(vinyl chloride) (CPVC)/MBS blends were obtained by melting MBS graft copolymers with CPVC resin, and the effect of the core/shell ratio of MBS graft copolymer and SBR content of CPVC/MBS blends on the mechanical properties and morphology of CPVC/MBS blends was studied. The results showed that, with the increase in the core/shell ratio, the impact strength of the blend increased and then decreased. It was found that, when the core/shell ratio was 50/50, the impact strength was about 155 J/m, and the tensile strength evidently increased. The toughness of the CPVC/MBS blend was closely related to the SBR content of the blend, and with the increasing of SBR content of blend, the impact strength of the blend increased. The morphology of CPVC/MBS blends was observed via scanning electron microscopy. Scanning electron microscopy indicated that the toughness of CPVC/MBS blend was consistence with the dispersion of MBS graft copolymers in the CPVC matrix. J. VINYL ADDIT. TECHNOL., 22:501–505, 2016. © 2015 Society of Plastics Engineers     

Rheological and mechanical properties of poly(vinyl chloride)/chlorinated poly(vinyl chloride) miscible blends

The properties of poly(vinyl chlorlde)/ehlorinated poly(vinyl chloride) (61.6 percent C1) blends, prepared by melt and solution blending, were measured by various tests. Based on the chlorinated poly(vinyl chloride) (CPVC) composition, percent chlorine, and mole percent CC1₂ groups, these blends were expected to show intermediate properties between miscible and immiscible systems. Indicative of miscible behavior were the single glass transition temperatures over the entire composition range for both melt and solution blended mixtures. A single phase was also indicated by transmission electron microscopy. However, the yield stress showed a minimum value less than either of the pure components in the 50 to 75 percent CPVC range, which is characteristic of two-phased systems. Specific volume, glass transition temperature, and heat distortion temperature were linear with binary composition. The storage modulus showed a small maximum, suggesting a weak interaction between the two miscible polymers. Heats of melting for the residual PVC crystallinity were also less than expected from linear additivity. At 160°C and 210°C, the logarithm of the complex viscosity was essentially linear with volume fraction of CPVC, except for a very slight decrease in the 50 to 75 percent CPVC range, which may have been a result of lower crystallinity. At 140°C, the complex viscosity of the CPVC was less than that of PVC owing to the higher crystallinity of the latter. The viscosities were similar at 160°C, but at 210°C, where most of the crystallites had melted, the complex viscosity of the CPVC was higher because of its higher glass transition temperature.     

Studies of polyester/chlorinated poly(vinyl chloride) blends

Chlorinated poly(vinyl chloride) (CPVC) was solution blended with poly(caprolactone) (PCL), poly(hexamethylene sebacate) (PHMS), poly(α-methyl-α-n-propyl-β-propiolactone) (PMPPL), poly(valerolactone) (PVL), poly(ethylene adipate), poly(ethylene succinate) and poly(β-propiolactone). From calorimetric glass transition temperature (T_g) measurements, it is concluded that CPVC is miscible with polyesters having a CH₂/COO ratio larger than three (PCL, PHMS, PMPPL and PVL). The Gordon-Taylor k parameter was also calculated and found equal to 1.0 and 0.56 for PCL/CPVC and PHMS/CPVC blends, respectively. From these values, it is concluded that CPVC gives a stronger interaction with polyesters than poly(vinyl chloride) due to its larger chlorine content.     

Phase diagram of poly(vinyl chloride) and solution chlorinated polyethylene

The behaviour of mixtures of poly(vinyl chloride) (PVC) and solution chlorinated polyethylene (SCPE) has been investigated as a function of temperature. These polymers have been found to be compatible over some ranges of composition and exhibit the phenomenon of a lower critical solution temperature (LCST). The thermally-induced phase separation has been investigated by optical, dynamic mechanical, and electron microscope techniques. The single phase mixture has been investigated by scanning analytical electron microscopy. Some investigation of the thermodynamics of the mixture has been made and the heat of mixing term has been found to be negative and small, i.e. favouring mixing. It has been shown that the technique of in situ polymerization overcomes many of the problems of preparing these polymer mixtures in the solid state.     

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     

Analysis of low‐density polyethylene‐g‐poly(vinyl chloride) copolymers formed in poly(vinyl chloride)/low‐density polyethylene melt blends with gel permeation chromatography and solid‐state 13C‐NMR

Gel permeation chromatography (GPC) and solid‐state ¹³C‐NMR techniques were used to analyze the structural changes of poly(vinyl chloride) (PVC) in blends of a low‐density polyethylene (LDPE) and PVC during melt blending. The GPC results showed that the weight‐average molecular weight (M_w) of PVC increased with LDPE content up to 13.0 wt % and then decreased at a LDPE content of 16.7 wt %, whereas the number‐average molecular weight remained unchanged for all of LDPE contents used. The ¹³C‐NMR results suggest that the increase in M_w was associated with the formation of a LDPE‐g‐PVC structure, resulting from a PVC and LDPE macroradical cross‐recombination reaction during melt blending. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3167–3172, 2004     

Studies of rigid poly(vinyl chloride) (PVC) compounds. I. Morphological characteristics of poly(vinyl chloride)/chlorinated polyethylene (PVC/CPE) blends

Chlorinated polyethylene (CPE) is a commonly used impact modifier of poly(vinyl chloride) (PVC). The major goal of this research was to understand the fundamental morphological aspects of PVC/CPE blends. Scanning electron microscopy (SEM) was used to image the surface structure of these blends, and both transmission electron microscopy (TEM) and scanning-transmission electron microscopy (S-TEM) were used to image the morphological boundaries of the blends. TEM imaging distinguishes the boundaries between PVC and CPE more clearly or better than does S-TEM, but it is time-consuming. However, some CPE particles are not observed in TEM because of inefficient staining. S-TEM imaging is much faster and does not depend on staining for the imaging of the CPE phase. © 1995 John Wiley & Sons, Inc.     

Impact modification of poly(vinyl chloride) with chlorinated polyethylene II. Irreversible deformation

The mechanical behavior of chlorinated polyethylene (CPE)-modified poly(vinyl chloride) (PVC) has been determined. The nature of the irreversible deformation processes which are responsible for mechanical energy absorption has been investigated by optical and electron microscopic techniques. Addition of CPE results in a decrease in the shear band initiation stress and an increase in void density and stability. The crazing to shear banding transition is observed at a blend composition between 2 and 7 percent CPE at the strain rate employed. It has been established that voiding occurs in the CPE rubber phase. Voiding accounts for at least part of the increased energy absorption of the blend. The stability of the voids to coalescence and fracture is attributed to strong adherence of the CPE to the primary PVC particles.     

Viscoelastic behavior of chlorinated polyethylene/poly(ethylene‐co‐vinyl acetate) blends in the melt state

Blends of chlorinated polyethylene and an ethylene vinyl acetate copolymer of various compositions were prepared by mixing in the melt state. Dynamic rheological properties of these blends were studied at different temperatures below, near, and above the T_S, the temperature of phase separation, and in a frequency range from 0.01 to 100 rad/s. It is shown that the time–temperature superposition principle is suitable in all investigated temperature ranges. G′ versus G″ representations for the blends were found to be independent of temperature and varying weakly with the composition. Changes in the relaxation spectra H(τ) were discovered which depend on the prehistory of the blend preparation and on thermal conditions in the working unit of a rheometer (increasing the temperature from 140 to 180°C or decreasing the temperature from 180 to 140°C). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1911–1918, 2003     

Compatibilization of regenerated low density polyethylene/poly(vinyl chloride) blends

The aim of this work is to study the valorization of regenerated low density polyethylene (rLDPE) by blending with PVC in the presence of chlorinated polyethylene (CPE) as compatibilizer. For this purpose, four rLDPE samples coming from neat or dirty wastes were used. They were obtained after milling, washing, and extrusion in a conventional recycling plant. They were first characterized in terms of physicochemical (density, melt flow index, water absorption, and level of oxidation by Fourier transform infrared spectroscopy) and mechanical (tensile and shore D hardness) properties. The effect of the ratio of PVC on these physical and mechanical properties was then investigated. These binary blends exhibited lower properties than those of the separated polymers. The addition of CPE to the binary blend with weight proportion of 50/50 leads to a substantial improvement of the considered properties which is due to a better interfacial adhesion between rLDPE and PVC as evidenced by the analysis of the morphology of the blends by scanning electron microscopy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Chlorinated poly(vinyl chloride) and plasticized chlorinated poly(vinyl chloride)—thermal decomposition studies

The thermal decomposition of chlorinated poly(vinyl chloride) and three plasticized chlorinated poly(vinyl chloride) systems has been investigated. The routes of decomposition of these systems have been elucidated by investigating char formation and by using a combination of thermogravimetric analysis (TGA) and prolysis/gas chromatography/mass spectroscopy methods (Py/GC/MS). The effects of the charforming/smoke‐suppressing iron(III) compound FeOOH in these polymer systems has also been investigated. The structure of both CPVC polymer and plasticzer determine the path of thermal decomposition and also the quantity and nature of the decomposition compunds formed. Changes in oxygen index and the formation of smoke during burning in these systems have been related to the char that is formed and also to the chemical nature of the decomposition products.     

Compatibilization of poly(vinyl chloride) and polystyrene blends with poly(styrene‐co‐n‐methylolacrylamide)

In this work, the compatibilization of blends of plasticized polyvinyl chloride (PVC) and polystyrene (PS) with poly(styrene‐co‐n‐methylolacrylamide) (PSnMA) was investigated. The PSnMA was synthesized by emulsion polymerization with different amounts of n‐methylolacrylamide (nMA). Particle size and phase behavior was determined by scanning electron microscopy, and mechanical properties were determined in an Universal Testing Machine. Micrographs revealed that an appreciable size reduction of the dispersed phase was achieved when small amounts of PSnMA were added to the blend, and as the amount of nMA was increased, particle size decreased. When the (PVC/PS/PSnMA) blend was subjected to solvent extraction to remove PS and unreacted PVC, the residue showed a single T_g. Tensile modulus and the ultimate strength of the blends increased with PSnMA content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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.     

A Fourier transform infra-red study of the phase behaviour of polymer blends. Ethylene-vinyl acetate copolymer blends with poly(vinyl chloride) and chlorinated polyethylene

Fourier transform infra-red studies of ethylene-vinyl acetate (EVA) blends with poly(vinyl chloride) (PVC) and chlorinated polyethylene (CPE) are presented. Previous studies have demonstrated that these blends are compatible at ambient temperature and exhibit lower critical solution temperatures (LCST) in a range that is readily accessible and below the onset of significant polymer degradation. Infra-red spectra of EVA-PVC and EVA-CPE films cast from solution and recorded at room temperature exhibit the familiar frequency shifts and band broadenings of the carbonyl stretching vibration that are consistent with compatible blend systems. Significantly, at temperatures above the LCST, these spectral features are not observed, which implies phase separation. By monitoring the frequency of the EVA carbonyl stretching vibration in samples of the blends, an estimation of the relative strength of the intermolecular interactions has been obtained as a function of temperature. A non-linear relationship is observed and the temperature at which the relative strength of the intermolecular interaction appears very weak correlates with the LCST. The implications of these results are discussed.