Reactivity of poly(vinyl chloride) containing N-methyl dithiocarbamate toward metal ions in heterogeneous system and effect of γ-irradiation on the reactivity

The reaction of poly(vinyl chloride) containing N-methyl dithiocarbamate (PMD) with metal ions in a heterogeneous system and the effect of γ-irradiation on the reactivity were studied. PMD powder suspended in aqueous solutions did not show any reactivity toward metal ions. However, the PMD powder suspended in a methyl alcohol solution formed a chelate with various metal ions. The effects of the reaction time, pH, and the initial concentration of the metal ion were examined. PMD irradiated in methyl alcohol with γ-irradiation doses up to 28 Mrad was compared with the original PMD. The reactivity of the irradiated PMD toward the metal ions did not show any apparent decrease.     

Reactivity of poly(vinyl chloride) containing N-methyl-N-carboxymethyl dithiocarbamate toward metal ions in heterogeneous system and effect of γ-irradiation on the reactivity

The reaction of poly(vinyl chloride) containing N-methyl-N-carboxymethyl dithiocarbamate (PSDC) with metal ions in a heterogeneous system and the effects of γ-irradiation on the reactivity were studied. Slurried PSDC has an affinity for a number of metal ions in aqueous solutions. On the basis of analyses for nitrogen and sulfur and on infrared spectra, a possible chelating structure for PSDC was deduced. The gaseous products evolved during the gamma radiolysis of PSDC under vacuum were measured. Although the dithiocarbamate group bonded to the main chain gave some protection against the dehydrochlorination of poly(vinyl chloride) component, a small amount of the carboxymethyl group was decomposed. It was found that with γ-irradiation doses up to 30 Mrad, only about 1 mole-% out of 17.6 mole-% of N-methyl-N-carboxymethyl dithiocarbamate in the polymer was decomposed. It was shown that the reactivity of the irradiated PSDC in water toward metal ions was almost the same as that before irradiation.     

Synergistic combination of metal stearates and β‐diketones with hydrotalcites in poly(vinyl chloride) stabilization

A synergistic effect of synthetic hydrotalcites as long term stabilizer with metal soaps (the mixture of calcium and zinc stearate) and metal acetylacetonates on dehydrochlorination of PVC has been studied. A proper balance between color stabilization and HCl scavenging capacity has been obtained. Hydrotalcite was prepared by hydrothermal treatment and characterized by EDX, XRD, FTIR, TGA, and SEM techniques. The material is reasonably crystalline and suggests a relatively well ordered sheet arrangement with crystallite size 24.87 nm. The interlayer water content was calculated from the TGA curves and the suggested formula is Mg_0.76 Al_0.24(OH)₂(CO₃)_0.12·0.5H₂O. Synergism in PVC stabilization has been studied by measuring the HCl evolution during the processing at 180°C. Oven aging method was used to study the color stabilization at higher temperature. PVC sheet with different formulation was prepared using Labcoater and subjected to oven for different time interval. The color development (polyene formation) on oven ageing was recorded using UV–visible spectroscopy. UV–visible studies shows that an average sized polyene gives pale yellow color, whereas red or brown color was developed due to long range polyene (n = 10–14) sequences. Hence, the HCl evolution depends on the rate of dehydrochlorination but color depends on the kind of polyene formed. Mechanism of stabilization suggests that adsorption and ion exchange, both phenomenon, are responsible for hydrotalcites as long term stabilizers. The acetylacetonate complex too substitute allylic chlorides and inhibit formation of long polyene responsible for darkening. A clear effect of synergism has been observed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Radiation protection of poly(vinyl chloride) by N,N-dialkyl dithiocarbamate substitution

The effect of N,N-dialkyl dithiocarbamate substitution on the radiation stability of poly(vinyl chloride) (PVC) film was studied. PVC containing 6.5–15.7 mole-% N,N-dimethyl dithiocarbamate (PDM) and PVC containing 8.3–17.5 mole-% N,N-diethyl dithiocarbamate (PDE) was irradiated with γ-rays from a Co-60 source at room temperature under vacuum. The evolved gaseous products were measured and analyzed with a mass spectrometer. The apparent G values for gas evolution of PDM and PDE decreased remarkably. For example, a G value of 0.10 was obtained for a PDE which contains 17.5 mole-% diethyl dithiocarbamate group. The mass spectrum of the evolved gas from the same PDE sample with 10-Mrad irradiation showed no hydrogen chloride to be present. The external protection was studied using polymer-blended films of PVC and PDE or PDM. The stabilization coefficients for internal protection and external protection in polymer blends were calculated. Although the ESR spectrum of the irradiated PDM, PDE, and PVDE which is synthesized by polymerization of S-vinyl-N,N-diethyl dithiocarbamate (VDE) showed the same sulfur radicals, they were different from those of the irradiated cysteamine hydrochloride and PVC containing N-methyl dithiocarbamate (PMD). From these results, the protection of a polymer by a covalently bound dithiocarbamate was discussed.     

Dielectric properties of poly(α-methyl α-n-propyl-β-propiolactone)/poly(vinyl chloride) blends

The dielectric properties of miscible blends of poly(vinyl chloride) (PVC) and poly(α-methyl-α-n-propy-β-propiolae-tone) (PMPPL) have been investigated at different temperatures above and below T_g. The results were analyzed using the Cole-Cole representation and lead to the conclusion that this mixture does not exhibit micro-scale heterogeneities. Dielectric constant and dielectric loss master curves were constructed using the stress relaxation shift factors determined previously; the same shift factors could be used for the homopolymers and their blends. Similarities between the dielectric master curves and the stress relaxation master curves of PVC, PMPPL, and their blends, are also discussed.     

Chelation properties of poly(β‐diketone) polymer and its oxime toward heavy metal ions

The chelation behavior of poly(β‐diketone), polymer I, and poly(β‐diketone) oxime, polymer II, toward the divalent metal ions, Cu²⁺, Zn²⁺, Ni²⁺, and Cd²⁺, and the trivalent lanthanide metal ions, La³⁺, Nd³⁺, Sm³⁺, Gd³⁺, and Tb³⁺ was investigated by a batch equilibration technique as a function of contact time, pH, and counter ion. Polymer II exhibited improved chelation characteristics toward lanthanide metal ions in comparison with polymer I and the metal‐ion uptake follows the order Tb³⁺ ≈ Gd³⁺ ≈ Sm³⁺ > Nd³⁺ ≈ La³⁺. On the other hand, polymer I showed relatively higher capacity than polymer II, toward the investigated divalent metal ions, where the metal‐ion uptake follows the order Cu²⁺ > Cd²⁺ ≈ Zn²⁺ > Ni²⁺. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermoset polyurethanes containing hydroquinone di(β-hydroxyethyl) ether

A thermoset polyurethane resin extended with hydroquinone di(β-hydroxyethyl) ether (HQEE) was found to have good thermomechanical properties suitable for external elastomeric automotive applications. A resin composed of diphenylmethane diisocyanate (MDI), ethylene glycol, and a primary polyol was found to have good mechanical properties but was too reactive for processing as a one-component resin. Replacing the liquid ethylene glycol extender with the solid HQEE substantially increased the pot life of the resin as well as improving the modulus properties. When catalyzed with zinc stearate this resin had sufficient pot life at room temperature, at least 4 hr, to be processed as a one-component system but still cure rapidly at elevated temperatures. The HQEE-extended materials required only 50% hard-block content (isocyanate plus extender) to have the same modulus at room temperature as ethylene glycol-extended materials containing 60% hard block. By using a graft or polymer polyol, the required hard-block content could be reduced to 40% The polyurethane of MDI/SAN graft polyol/HQEE containing 40% hard block had a flex modulus of 230 MPa, tensile strength of 18 MPa, and 240% elongation. The ratio of flex moduli measured at ?29 and +70°C was 2.7, which compared very favorably to conventional RIM systems. The modulus at elevated temperatures was particularly improved, which is important in painting operations.     

Thermal degradation of ternary blends of poly(ε‐caprolactone)/poly(vinyl acetate)/poly(vinyl chloride)

The thermal degradation of ternary blends of poly(ε‐caprolactone) (PCL), poly(vinyl acetate) (PVAC), and poly(vinyl chloride) (PVC) was studied using a thermogravimetry analyzer under dynamic heating in flowing nitrogen atmosphere. PCL degraded in a single stage, whereas the PVAC and PVC degraded in two stages during which acid is released in the first stage followed by backbone breakage in the second stage. The addition of PVC to either PCL or PVAC affected the thermal stability of the blend, whereas the addition of PVAC to PCL did not alter the thermal stability of the blend. In ternary blends, the addition of PVC affected the degradation of PVAC but did not influence the degradation of PCL in the range investigated. The increased addition of PCL to the binary blends of PVC/PVAC decreased the extent of thermal instability of PVAC because of the addition of PVC. The addition of even 10% PVAC to the PCL/PVC blend removed the thermal instability of PCL resulting from the addition of PVC and can be attributed to the ease of chlorine or hydrogen chloride capture of PVAC over PCL. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1378–1383, 2004     

Preparation and characterization of electrospun poly(ε‐caprolactone)/poly(vinyl pyrrolidone) nanofiber composites containing silver particles

A nanofiber membrane composed of poly(ε‐caprolactone) (PCL), poly(vinyl pyrrolidone) (PVP), and silver nanoparticles was prepared via electrospinning technique. The morphology and structure of the PCL/PVP/Ag nanofibers composite were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR), X‐ray diffraction (XRD), and X‐ray photoelectron spectroscopy (XPS). The SEM images showed that various composites of PCL/PVP/Ag could be electrospun to yield continuous and uniform nanofibers. FTIR spectra indicated that the molecular interactions between PCL and PVP are weak. The hydrophilicity, mechanical property, and swelling behavior of the as‐spun composites can be manipulated by altering the blend ratio of PCL/PVP. XRD patterns and XPS spectra showed that the Ag nanoparticles were dispersed in the PCL/PVP nanofiber composites; and the Ag nanoparticles endowed the PCL/PVP/Ag composite with antibacterial activities. The obtained PCL/PVP/Ag nanofiber composites with the morphology similar to that of native extracellular matrix have the potential to create a moist environment and to kill bacteria, which make it possible to be used for wound dressing application. POLYM. COMPOS., 37:2847–2854, 2016. © 2015 Society of Plastics Engineers     

Preparation and properties of blends from poly(3‐hydroxybutyrate) with poly(vinyl acetate)‐modified starch

This research used the ceric ion to initiate the graft‐polymerization of vinyl acetate (VAc) to a soluble potato starch. Fourier transform infrared spectra confirmed the formation of starch graft copolymer. After 4 h of reaction at 50°C, total monomer conversion, grafting efficiency, and grafting ratio were measured as 91%, 12.5%, and 0.223, respectively. The synthesized PVAc‐modified starch was then blended with poly(3‐hydroxybutyrate) (PHB). Structures, thermal and mechanical properties of the prepared blends were examined. The results showed the PHB and PVAc‐modified starch were miscible in all compositions. In addition, thermal gravimetric analysis revealed that the addition of PVAc‐modified starch increased the thermal stability of the PHB component. Further evidence also showed that the addition of PVAc‐modified starch reduced the extent of decrease in molecular weight of PHB in a melt‐mixer. PHB/PVAc‐modified starch blends exhibit higher toughness than pure PHB because of increased compatibility and the leathery PVAc‐modified starch. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Photosensitivities and rates of photocrosslinking of poly(vinyl α-cyanocinnamate) and poly(vinyl α-cyanocinnamoxy acetate)

The photosensitivities and the rates of photocrosslinking of poly(vinyl α-cyanocinamate) and poly(vinyl α-cyanocinnamoxyacetate) were investigated. The photocrosslinkings of these polymers proceeded mainly through radical addition, and these polymers showed higher photosensitivities than poly(vinyl cinnamate) and poly(vinyl cinnamoxyacetate), in spite of lower rates of photocrosslinking of the former polymers.     

Blends of poly(3‐hydroxybutyrate) with poly(β‐alanine) and its derivatives

Nanofibers and films of poly(3‐hydroxybutyrate) (PHB)/nylon 3 [poly(β‐alanine) (N3)], PHB/poly(α‐methyl‐β‐alanine) (2mN3), and PHB/poly(β‐methyl‐β‐alanine) (3mN3) blends were prepared by electrospinning and film‐casting techniques, respectively. The miscibility of the blends was studied by Fourier transform infrared spectrometry, differential scanning calorimetry, thermogravimetric analysis, and X‐ray diffraction (XRD). The electrospinnability of the blends was studied by scanning electron microscopy. Some characteristic IR absorption bands of the components in the blends shifted gradually with changes in the compositions. The melting temperature and decomposition temperature of PHB decreased gradually with increasing fractions of N3, 2mN3, and 3mN3. The XRD spectra of all of the blends exhibited peaks with lower intensities compared to those of the neat species. The suppression of PHB crystallinity in the blends after blending was attributed to the disruption of its crystal lattice and the prevention of recrystallization of each component by means of other components and segmental interactions between the components in the amorphous phase. Thermal, spectroscopic, and optical analyses of the polymer blends revealed that the polymers were miscible with good compatibility, and this could have improved the scaffold properties of PHB. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40484.     

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.     

Radiation protection of poly(vinyl chloride) by N-methyl dithiocarbamate substitution

The effect of N-methyl dithiocarbamate substitution on the radiation stability of poly-(vinyl chloride) (PVC) films was studied. PVC containing between 2 and 11 mole-% N-methyl dithiocarbamate (PMD) was irradiated with γ-rays from a ⁶⁰Co source at 40°C and the evolved gaseous products were measured and analyzed with a mass spectrometer. The apparent G values for gas evolution for PMD decreased remarkably. For example, a G value of 0.28 was obtained for a PMD which contains 11 mole-% dithiocarbamate group compared with a G value of 10.8 for unmodified poly(vinyl chloride). Furthermore, the mass spectrum of the evolved gas from the same PMD sample (PMD-44) with 10 Mrad irradiation showed no hydrogen chloride to be present. The external protection was studied using polymer-blended films of PVC and PMD-44. The stabilization coefficients for internal protection and external protection in polymer blends were calculated. The ESR spectrum of the irradiated PMD-44 showed a strong anisotropy with high g values which differed significantly from the spectrum of the irradiated PVC. A suggested mechanism for radiation protection of PVC against γ-rays irradiation by the N-methyl dithiocarbamate group is discussed.     

Studies on graft copolymerization of 2-hydroxyethyl methacrylate onto poly(vinyl chloride)

Poly(vinyl chloride) was dehydrochlorinated in alkali solution and then grafted with 2-hydroxyethyl methacrylate (HEMA) using benzoyl peroxide as a free-radical initiator under a nitrogen atmosphere. The investigations involved examining the effects of grafting efficiency on various conditions, such as degree of dehydrochlorination, HEMA concentration, solvent effect, and reaction time. Maximum grafting to the extent of 57.2% was obtained. The mixed solvent grafting was attempted. © 1994 John Wiley & Sons, Inc.     

Interfacial and mechanical properties of γ‐Fe2O3/segmented polyurethane/poly(vinyl chloride) composites

Segmented polyurethane (SPU)/poly(vinyl chloride) (PVC) blends were particulated with γ‐Fe₂O₃. Interfacial properties of the composite were studied through the adsorption behaviors of SPU and PVC and their blends on γ‐Fe₂O₃ particles surface. Mechanical properties of the composite were measured with dynamic mechanical analysis and tensile test measurements. PVC with functional groups (FPVC), because of strong interactions, showed preferential adsorption on γ‐Fe₂O₃ compared with SPU and PVC. Moreover, the γ‐Fe₂O₃ particles were covered by FPVC in the γ‐Fe₂O₃/SPU/FPVC composite. The adsorption layer of FPVC protected SPU from catalytic degradation by γ‐Fe₂O₃, resulting in increasing hydrolytic stability for SPU. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3030–3035, 2001     

Miscibility,morphology and tensile properties of vinyl chloride polymer and poly(ε‐caprolactone) blends

The miscibility, morphology and tensile properties of three blend systems of poly(ε‐caprolactone) (PCL) with poly(vinyl chloride) (PVC) and with two chlorinated PVCs (CPVCs) with different chlorine contents (63 wt% and 67 wt% of Cl) have been studied. Based on the shifts of single glass transition temperature, the Gordon–Taylor K parameter is calculated as a measurement of interaction strength between PCL and (C)PVCs. Higher K values are found for blends of (C)PVCs with higher chlorine content, together with the interaction χ parameters estimated from the melting point depression results. The morphology observed with polarized light microscopy shows that spherulites exist in blends rich in PCL (≥50 wt%) only. Wide angle X‐ray diffraction studies indicate that the crystal structure of PCL is independent of the Cl content of (C)PVCs. The tensile properties of various blends exhibit a minimum as the PCL content increases. The elongation at break increases with increasing PCL content. © 2000 Society of Chemical Industry     

Preparation,glass transition temperature,and δ relaxation effect of poly(vinyl isonicotinate)

Poly(vinyl isonicotinate) was prepared by esterification of poly(vinyl alcohol) with isonicotinoyl chloride in pyridine solution. Poly(vinyl nicotinate) was also prepared. Density, refractive index, and glass transition of the polymers were determined. The low temperature dynamic mechanical properties of poly(vinyl isonicotinate) are characterized by a relaxation effect which is associated with thermally excited motions of the pyridine rings (δ relaxation). The strong displacement of such a phenomenon toward higher temperatures, with respect to poly(vinyl benzoate), is interpreted as due to the elevated polarity of the pyridine ring.     

Network of γ-irradiated poly(vinyl alcohol) beads

The crosslinking of poly(vinyl alcohol) beads was performed by γ-ray irradiation. The maximum molecular size, M_lim, which can permeate through beads, was obtained by eluting poly(ethylene glycol) through a column packed with beads. The root-mean-square of the end-to-end distance $\text{(}\text{r}{}^2\text{)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and that of the hydrodynamic radius $\text{(}\text{s}{}^2\text{)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ were also calculated. Meanwhile, the average size of the network of the beads, r_c, was estimated from the average molecular weight between crosslinkages, M_c, which was derived from the glass transition temperatures of crosslinked and non-crosslinked poly(vinyl alcohol) beads. r_c values of poly(vinyl alcohol) beads decreased as the total dose of γ-irradiation increased when dry poly(vinyl alcohol) beads were γ-irradiated, while the values were almost constant when poly(vinyl alcohol) beads swollen in water were γ-irradiated. Further, linear relations were obtained among r_c, $\text{(}\text{r}{}^2\text{)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, and $\text{(}\text{s}{}^2\text{)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ covering the wide range of total dose.     

Infrared study of combined effect of γ-radiation and elevated temperature on poly(vinyl chloride)

Infrared absorption spectroscopy has been used to investigate the combined effect of γ-radiation and heat on poly(vinyl chloride) (PVC). The recorded spectra showed that exposure of PVC samples to gamma doses from 0.5 to 15 Mrad results in remarkable changes in the absorbances of their absorption bands. Also, the exposure to doses from 3 to 15 Mrad results in an appearance of a C?O band at 1720 cm^?1 and O? H band at 3450 cm^?1. The nature of the formation of these bands was discussed in terms of peroxide-mediated oxidative degradation mechanism. Moreover, it was found that heat treatment of PVC samples over the temperature range 25–180°C causes no noticeable changes in their spectra apart from slight changes in the absorbances of the bands. On other hand, it was found that heat treatment of the irradiated samples causes considerable increase in the intensity of the C?O band. In addition to the well-defined and sharp band appearing at 1720 cm^?1, the spectra of the samples irradiated with 10 and 15 Mrad exhibited two bands at 1070 and 1120 cm^?1. The obtained data led also to the conclusion that the C? Cl bands cannot be used as a measure of crystallinity of PVC.