Dielectric and mechanical properties of poly(vinyl chloride)–dioctylphthalate systems

The mechanical properties, tensile strength, and elongation were investigated for poly(vinyl chloride) (PVC) samples mixed with dioctylphthalate (DOP) at concentrations from 0 to 100 parts per hundred parts PVC at 23°C. It was found that the tensile strength decreased with the increase of concentration, and the elongation was increased until a concentration of 30 DOP content, and then decreased. This leads to the suggestion that intermolecular plasticization is dominant until 30 DOP content, while interstructural plasticization is prevailing for higher concentrations. The permittivity ε′ and the dielectric loss factor ε″ of the same samples have been measured in the frequency range 10²–10⁵ Hz at temperatures from 3 to 96°C. Results show that as the DOP content increases in PVC, the dielectric absorption becomes broader, and the glass transition temperature T_g is lowered. The magnitude of the loss peak decreases with an increase of DOP content to a minimum at concentrations from 40 to 60 DOP content. At higher concentrations the loss peak is increased and T_g is unaltered. Another absorption was observed at 100 Hz and at high temperatures, which was attributed to Maxwell–Wagner effect or direct current conductivity or both of them. It was found that the sample containing 40 parts DOP in 100 parts PVC possesses the best mechanical and electrical properties.     

Stabilization of poly(vinyl chloride). V. Synergism between metal soaps and polyols upon stabilization of poly(vinyl chloride)

The marked discolorations observed on aged poly(vinyl chloride) (PVC) containing synergetic metal soaps, in the early heating stage, were due to the excessive coloration of π complex of metal chloride and double bonds in the polyene chain. These excessive colorations were inhibited by masking the excessive metal chloride with some masking agents, thereby slowing down the abrupt discoloration of PVC. In this paper, the masking effect of various alcohols such as 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, hexylene glycol, glycerol, 1,2,4-butanetriol, trimethylolethane, trimethylolpropane, meso-erythritol, pentaerythritol, sorbitol, and dipentaerythritol is investigated. The polyhydric alcohols, except dihydric alcohols, showed superior masking effect and markedly improved the thermal stabilization effects of synergetic metal soaps. The mechanism for the synergetic effects between polyols and metal soaps should be based on the masking effect of polyols, owing to the formation of the colorless complex of polyols with excess metal chlorides obtained from the metal soap.     

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.     

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.     

Stabilization of poly(vinyl chloride). X. Synergisms between epoxidized polybutadienes and metal soaps on the stabilization of poly(vinyl chloride)

Effects of epoxidized 1,2- or 1,4-polybutadienes on the zinc stearate/calcium stearate synergetic soap-induced thermal stabilization of poly(vinyl chloride) (PVC) were investigated by colorimetry. The remarkable stabilization effects of epoxidized polybutadienes could not be observed on the PVC films without synergetic soaps, while the stabilization of PVC was markedly enhanced by combined use of epoxidized polybutadienes with synergetic soaps. Excessive coloration of cool color-producing zinc chloride-polyene complexes that were the source of abrupt discoloration of stabilized PVC was retarded by using epoxidized polybutadienes together with synergetic soap. The synergism of epoxidized polybutadienes was enhanced with increasing epoxy contents. Moreover, the effect is also clearly dependent on degree of dispersion of epoxidized polybutadienes in PVC. Further colorimetries, infrared (IR), and X-ray photoelectron spectroscopies on the various PVC-containing epoxidized polybutadienes and zinc chloride indicated that the epoxy groups capture the zinc chloride. The synergistic effect between epoxidized polybutadienes and metal soap was ascribed to epoxidized polybutadienes serving as acceptors for the excessive cool color-producing zinc chloride produced by zinc stearate to retard the abrupt discoloration of stabilized PVC. The plate-out phenomenon appeared during the molding process of PVC-containing epoxy compounds was considerably retarded by epoxidized polybutadienes which modified polyols. The polyol-modifying epoxidized polybutadienes also exhibited a marked effect on PVC stabilization with metal soap.     

Stabilization of poly(vinyl chloride). III. Synergism between metal soaps and masking agents on the stabilization of poly(vinyl chloride)

The stabilization mechanism by synergetic metal soaps containing complementary colors was previously reported. With increased heating times, the color of heated poly(vinyl chloride) (PVC) films containing Cd/Ba and Zn/Ca synergetic soaps markedly deviated from the polyene color. These color deviations usually decreased the thermal stability of PVC. Discoloration from polyene color to blue appeared especially on PVC films containing Zn/Ca synergetic soap and was concomitant with a marked decrease in thermal stability. The stabilization of PVC containing synergetic metal soaps can be improved by masking or removing the excessive color. In this work, the addition of various masking agents, such as ethylenediaminetetraacetic acid, o-phenanthroline, triethanolamine, urea, N,N′ -dimethylolurea, melamine, stearylamide, and lactams, to PVC containing synergetic metal soaps was investigated. It was shown that these masking agents do markedly slow down the discoloration of PVC.     

Study of dynamic mechanical properties of poly(vinyl chloride)–ethylene vinyl acetate copolymer and poly(vinyl chloride)–chlorinated ethylene vinyl acetate copolymer mixtures

The compatibility of the mixtures poly(vinyl chloride)—ethylene vinyl acetate copolymer and poly(vinyl chloride)—chlorinated ethylene vinyl acetate copolymer was studied by the method of dynamic mechanical testing. The character of G′ and G″ was confronted with the Takayanagi model. In all cases a limited compatibility of the components was observed.     

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.     

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.     

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.     

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     

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.     

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     

Investigation on multiphase polymeric systems of poly(vinyl chloride). I. PVC–chlororubber-20-gp-styrene–acrylonitrile (2 : 1) blends

A graft copolymer [chlororubber-20-gp-styrene–acrylonitrile (2 : 1)] has been synthesized by a solution precipitation polymerization technique grafting styrene and acrylonitrile onto chlororubber-20 main chain. The graft copolymer has been characterised by elemental analysis, IR spectroscopy, and viscometry. It has been blended with PVC by melt mixing using a Brabender plasticorder and extrusiograph. The mechanical properties such as flexural and tensile strengths and impact strength of the blends have been studied to evaluate its performance as an impact modifier. The behavior of PVC–chlororubber-20-gp–styrene-acrylonitrile (2 : 1) blends has also been compared with PVC–chlororubber-20 and PVC–KM-365B (a commercial acrylate modifier) blends. The thermal behavior of these blends has also been studied. It has been found that PVC–chlororubber-20-gp-styrene–acrylonitrile (2 : 1) blends have higher impact strength than PVC–chlororubber-20-gp blends though the PVC–KM-365B blends have the highest impact strength. Based on the authors' previous compatibility studies along with present X-ray diffraction studies and the morphological investigation of the fractured surface by scanning electron microscopy, the mechanical behavior of these blends have been explained in the framework of existing theories. A model has been proposed to account for the optimum dispersion and adhesion of graft polyblends of chlororubber-20 in PVC matrix.     

Stabilization of poly(vinyl chloride). II. Stabilization mechanism through metal soaps by complementary color action

In a previous paper, it was pointed out that the stabilization mechanism through metal soaps might be affected by an effect of complementary color. In this work, the colors of heated poly(vinyl chloride) (PVC) films mixed with various metal soaps were investigated by using a differential colorimeter and a spectrophotometer. Monochromatic coloration was observed with PVC, PVC–Ca stearate, and PVC–Ba stearate systems. On the other hand, the phenomenon of color mixing was observed with PVC–Zn stearate, PVC–Cd stearate, PVC–Zn/Ca stearate, and PVC–Cd/Ba stearate systems. In particular, achromatic color remained with PVC–Zn/Ca stearate and Cd/Ba stearate systems for longer heating periods. This means that the stabilization mechanism for PVC compounded with metal soaps should be effected finally by subtractive complementary colors situated between polyene color and the color effected with the metal complex, in addition to being subject to the usual chemical stabilization mechanisms.     

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.     

Thermal behavior of poly(acrylic acid)–poly(vinyl pyrrolidone) and poly(acrylic acid)–metal–poly(vinyl pyrrolidone) complexes

Thermal analysis (TGA and DTA) of samples of PAA, PVP, PAA–PVP complexes, containing different weight fractions of PAA and ternary polymer–metal–polymer complexes, were studied. The activation energy parameters for the thermal degradation were also calculated. The study of the effect of FeCl₃, NiCl₂, and Ni(NO₃)₂ on the TGA and DTA curves of the complexes showed that the decompositions are dependent on the concentrations and the nature of the metal ions. The DTA traces of PAA–PVP complex containing FeCl₃, NiCl₂, and Ni(NO₃)₂ showed that the treatment of the complex with these metal ions causes considerable changes in the thermal decomposition of PAA–PVP complex. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4049–4057, 2006     

Dynamic mechanical properties of poly(vinyl chloride)–xonotlite composite system

The filler effect of xonotlite (6CaO.6SiO₂.H₂O; needle-shaped) on dynamic mechanical properties, such as storage modulus (E′), loss modulus (E″), and tan δ was studied for the PVC—xonotlite composite system. And the properties of the system containing mechanically or chemically disaggregated particle of xonotlite were compared with those of the system-filled aggregates. The dynamic mechanical properties obviously depends on the dispersion condition of xonotlite particle. The aggregates of xonotlite produces a remarkably high modulus, an increase in T_g, and a decrease in mechanical damping near T_g in the system. On the other hand, the disaggregates, especially the chemical disaggregate one, bring softer or more rubbery properties in these systems. The interaction between matrix and filler was the strongest in the aggregates system and decreases in the order, mechanical disaggregates system, chemical disaggregates system.