Effect of Hydrogenation and Chlorination Reactions on the β Relaxation of Poly(Vinyl Chloride)

Abstract

The relaxation phenomena of polymers are very important because they play an important role in their physical properties. Dynamic mechanical analysis was used in this work in order to study the effect of tactic and compositional sequences on the relaxation processes observed in poly(vinyl chloride) (PVC). The polymers studied in this work were PVC modified by means of reductive hydrogenation and chlorination reactions at low degrees of modification. The results obtained with hydrogenated poly(vinyl chloride) indicated that the decrease in mmr tetrads at the end of the isotactic sequences in the chain by stereospecific hydrogenation led to concomitant decreases in intensity and temperature of the maximum of the β relaxation. This effect seemed to be stronger the longer the isotactic sequence associated with the said structure. On the other hand, in the case of chlorinated poly(vinyl chloride) (CPVC), the results of the evolution of the β relaxation with the degree of chlorination showed that the predominant factor was the compositional microstructure (substitution of hydrogen atoms by chlorine atoms, increasing the possibility of inter-chain interactions leading to a stiffening of the chain, with the consequent increase in the β temperature).     

Effect of the End Groups and the Solvent on the Gelation of the Hybrid Materials from Poly (Vinyl Chloride) (PVC) and Oligo Phenylene Vinylene (OPV)

Abstract

The role of the end-groups of three oligophenylene vinylene (OPV) and the solvents on the hybrid materials from poly (vinyl chloride) (PVC) and the OPV are examined. The gelation of the three organogel OPVs and of the hybrid materials in bromobenzene and benzyl alcohol was characterized. The morphology, as well as the thermodynamic properties, of these OPV and hybrid materials showed that they depended mostly on the solvent and very little on the different end-groups located on the OPV backbones.     

The Effect of High Intensity UV Irradiation on Color Behavior of Poly(Vinyl Chloride)

A detailed study of color change in poly(vinyl chloride) (PVC) sheets due to high intensity ultraviolet (UV) irradiation was undertaken, focusing on the first 50 h of change. Color changes were monitored with a Datacolor check spectrophotometer and compared with a set of controls. Measurements were taken after 1, 3, 5, 10, 15, and 20 h of irradiation, then at 10 h intervals for the next 40 h. Further measurements were conducted at 100, 240, and 480 h. Data were analyzed using the reflectance spectra (350–800 nm) as well as the CIE (International Commission on Illumination) L* a* b* color values (L*, a*, and b* are lightness value, redness-greenness value, and yellowness-blueness value, respectively) and the total color change (ΔE). The majority of color changes were found to occur within the first 50 h. After 50 h, the color change slowed and began to reverse toward 480 h. Surface microstructure properties, such as morphology, surface tension and oxidized products, were characterized to allow a comparison of sensitivity between the color monitoring methods and a comprehensive understanding of the color change. The results show that color evolution was attributable to the competition between the formations of polyene sequences (dehydrochlorination reaction) and their subsequent oxidation (photobleaching), which was slightly different from the behavior under a xenon arc lamp. According to the color behavior and the microstructure analysis a general scheme accounting for the mechanism of ageing behavior of PVC under high intensity UV irradiation is proposed.     

Preparation of Zinc Hydroxystannate Coated Dendritic-Fibrillar Barium Carbonate and its Flame Retardant Effect on Soft Poly (Vinyl Chloride)

Abstract

Zinc hydroxystannate (ZHS) coated dendritic-fibrillar barium carbonate (ZHS/BaCO_3-F) was obtained by a simple ultrasonic assisted method at room temperature without any guide reagent; the flame retardant soft poly (vinyl chloride) (S-PVC) treated with ZHS/BaCO_3-F was prepared by melt blending and studied by the limiting oxygen index (LOI), univeral tensile testing machine, thermogravimetric analyzer-Fourier transform infrared spectroscopy (TGA/FTIR), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results showed that ZHS/BaCO_3-F had a good dispersion in the PVC matrix, increased the LOI value and reinforced the S-PVC. The ZHS/BaCO_3-F played its role during the first degradation stage of S-PVC; the integrated effects of the earlier dehydrochlorination of ZHS on PVC, the reaction of ZHS/BaCO_3-F and HCl, and the thermal degradation of ZHS resulted in the production of H₂O, CO₂, olefins, aryl compounds, carboxylic compounds and alcohols, and the decrease of HCl production.     

用瑞利散射研究聚氯乙烯/橡胶共混物的两相分布

用瑞利散射研究聚氯乙烯/橡胶共混物两相尺寸,测定了聚氯乙烯/顺丁橡胶和聚氯乙烯/丁睛橡胶共混物的V_v光散射强度,用Debys——Bueche方程计算了相关距离a_c,讨论了a_c的变化规律。     

In Situ Dynamic Vulcanization of Poly(Vinyl Chloride)/Acrylonitrile-butadiene Rubber Blends

Poly(vinyl chloride) (PVC)/acrylonitrile-butadiene rubber (NBR) blends can be obtained through a dynamic vulcanization process as a melt-processible thermoplastic elastomer which produces parts that look, feel and perform like vulcanized rubber with the advantage of being processible as a thermoplastic material. In this study, a vulcanized thermoplastic was obtained by in situ dynamic vulcanization of PVC/NBR blends using a sulphur/ tetramethylthiuram disulphide (TMTD) and mercaptobenzothiazyl disulphide (MBTS) curative system during processing at the melt state. The blends were melt-mixed using a Haake Rheomix 600. The curing behavior of NBR was then investigated by a Monsanto rheometer. The thermal analyses were performed and the cross-linking at different mixing times was calculated using DSC. FT-IR was also performed for characterization of the blends. The cross-link densities of the samples were measured by a swelling method. The degree of cure increases with the mixing time. The cross-linking formation was verified through the formation of C─ S bonds in the blends.     

Thermal Degradation Kinetics of Plasticized Poly (Vinyl Chloride) with Six Different Plasticizers

Plasticized PVC formulated with different kinds of normally used plasticizers, including bis(2-ethylhexyl) phthalate (DOP), dioctyl terephthalate (DOTP), acetyl tri-n-butyl citrate (ATBC), acetyl trioctyl citrate (ATOC), trioctyl trimellitate (TOTM), and a new vegetable devived plasticizer, isosorbide ester (ID-37), were prepared by a melt blending method. The effect of plasticizer on the thermal degradation behavior of plasticized PVC was investigated by thermal gravimetric analysis (TGA). The activation energies were calculated by three well known methods, developed by Flynn-Wall-Ozawa (FWO), Friedman and Kissinger, respectively. The TGA conducted in N₂ atmosphere showed that the type of plasticizer had an obvious influence on the thermal stability of plasticized PVC. It was found that the peak temperatures (T_P) of the thermal degradation processes shifted to higher temperature with the increase of the heating rate, with two processes being shown. The activation energy of the first thermal decomposition process (E₁), calculated by the Kissinger method, was between 118 and 130 kJ/mol, while the activation energy of the second thermal decomposition process (E₂) was between 261 and 305 kJ/mol, except 499 kJ/mol for the PVC/TOTM formulation. The corresponding values of E₁ and E₂ obtained by the Flynn-Wall-Ozawa method were similar to the above data. E of the sample with TOTM also showed a higher value than the others; the results demonstrated that the PVC plasticized with TOTM was more thermally stable than with the others. The activation energies for certain conversion degrees were calculated by the Friedman method and the FWO method. The value of activation energy for 20%, 50%, and 80% conversion calculated by the Friedman method, exhibited an apparent difference from that calculated by the Flynn-Wall-Ozawa method; the results showed that the value of E obtained by the Friedman method was much more reasonable than that obtained by the Flynn-Wall-Ozawa method.     

The Peculiar Temperature Response of Dynamic Rheological Behaviors of Poly (Vinyl Chloride)/trioctyl Trimellitate (100/70) System

The dynamic rheological behavior, application of time-temperature superposition (TTS) and the failure mechanism of TTS are studied for the poly(vinyl chloride) (PVC)/trioctyl trimellitate (TOTM) (100/70) system. The Arrhenius equation, Williams–Landel—Ferry (WLF) equation, mathematical non-linear fitting and manual shift are applied to TTS fitting. For the PVC/TOTM (100/70) system, none of those methods can give well-superimposed master curves with either single horizontal shift or two-dimensional (horizontal and vertical) shift. The failure reason is attributed to the thermorheological complexity of the PVC/TOTM (100/70) system. Curves of the storage modulus versus the frequency can be well fitted with an empirical equation (G′=G′₀+Kω ⁿ ) usually used to describe filled polymer systems, indicating the multilevel flowing unit characteristic in this system. With the increase of test temperature, the structure of the PVC/TOTM (100/70) system changes and an apparent transition appears in the rheological behavior. Differential scanning calorimetry (DSC) results reveal that for the PVC/TOTM (100/70) system there are microcrystallites present below 220°C, but above the rheological transition temperature (190°C) the bulk of the microcrystallites melted, which corresponds to the appearance of viscous flow participating in the rheological behavior. It verifies the fact that the gel networks crosslinked by microcrystallites dominate the rheological behavior below the transition temperature in the PVC/TOTM (100/70) system. The quantity of microcrystallites remaining in the melt determines the perfection of the physical gel networks. With the increase of test temperature, the microcrystallites melted gradually and the gel networks are broken up.     

Thermal Stabilities of Poly(Vinyl Chloride)/Calcium Carbonate (PVC/CaCO3) Composites

Poly(vinyl chloride)/calcium carbonate (PVC/CaCO₃) composites with micrometer or nanometer CaCO₃ as fillers were prepared by the solution blending method. The thermogravimetric analysis (TGA) of the composite films conducted in N₂ atmosphere showed that the addition of the CaCO₃ fillers could improve their thermal stabilities. It was also found that the nanometer CaCO₃ filler provided better thermal stabilities than the micrometer fillers even with a smaller amount. The mechanism of the improvements was investigated by a facile chemical analysis developed to examine the thermal stabilizing effect of calcium carbonate particles with different sizes in PVC/CaCO₃ composites after the pyrolysis of the samples in an air atmosphere in an oven.     

Effect of Alkyl Side Chain Length on Relaxation Behaviors in Poly(n-alkyl Acrylates) and Poly(n-alkyl Methacrylates)

Dynamic mechanical analysis (DMA) is used to investigate the effect of alkyl side chain length on the relaxation behavior of poly(n-alkyl acrylates) (PnAA) and poly(n-alkyl methacrylates) (PnAMA) above the glass transition temperature (T_g). Master curves and shift factors (log a_T) were obtained using the time–temperature superposition (TTS) principle. The log a_T curves of PnAA and PnAMA exhibit a dynamic crossover from one Vogel–Fulcher–Tammann–Hesse (VFTH) equation to another above T_g. The corresponding temperature was designated as the dynamic crossover temperature (T_c). It is found that T_c/T_g and the apparent activation energy (E_g) increases, e whereas the fragility index (m) decreases with increasing alkyl side chain length. Further analysis shows that m ∝ T_g, E_g∝ , and E_g∝ m² for both PnAA and PnAMA.     

Fabrication and Characterization of Ultrathin Graphene Oxide/Poly(Vinyl Alcohol) Composite Films via Layer-by-Layer Assembly

Novel multilayer ultrathin films comprised of graphene oxide (GO) and poly(vinyl alcohol) (PVA) were fabricated through a layer-by-layer (LBL) assembly technique. GO could self-assemble onto quartz substrates alternately with PVA via hydrogen-bonding interactions. X-ray diffraction, atomic force microscopy, and transmission electron microscopy analysis revealed that GO was exfoliated to monolayers. The ultrathin films, with PVA/GO multilayer structures fabricated by LBL assembly, were characterized by ultraviolet-visible spectroscopy and X-ray diffraction analysis, confirming that the assembly of the multilayer films was quantitative and reproducible.     

Preparation of Poly (L-lactic Acid) Microsphere

Poly (L-lactic acid) (PLLA) microspheres were prepared by a solvent evaporation method based on an oil/water emulsion. The effect of the mass ratio of PLLA and poly(vinyl alcohol) (PVA) on the formation of the microspheres was discussed, and the influence of extraction speed of dichloromethane on the microsphere morphology was also studied. Moreover, the influences of the PLLA concentration and the volume ratio of water phase to dichloromethane phase were investigated. The results showed that stable microspheres can be obtained under the conditions that the mass ratio of PLLA to PVA is 20:1. Porous microspheres were obtained under faster evaporating speed of dichloromethane. The microsphere size increased with increasing PLLA concentration. The microsphere size also increased with the increase of the volume ratio of water phase to dichloromethane phase.     

Thermal Decomposition Behavior of Poly (Vinyl Alcohol) with Different Hydroxyl Content

The thermal decomposition behavior of poly(vinyl alcohol) (PVA) with two different hydroxyl contents, 88 and 99%, was investigated. UV-Vis spectroscopy, thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and TGA-FTIR were used to detect the volatile and nonvolatile products of the thermal decomposition of PVA. The results suggest that the PVA, after thermal treatment, can form chromophoric polyene structure, as well as carbonyl groups. The PVA with 88% hydroxyl content underwent slower decomposition below 280°C and generated water and carboxyl acid as the dominant volatile products, however, as for the PVA with 99% hydroxyl content, the dominant volatile products were water, unsaturated aldehydes, and other unsaturated compounds.     

Characterization of Poly(Vinyl Alcohol) Membranes Cross-Linked by Aldehyde-Substituting Cyclotriphosphazene

A new type of cross-linker, based on cyclotriphosphazene with six aldehyde groups, was used for the cross-linking of poly(vinyl alcohol) membranes. FTIR-ATR analysis indicated that cyclophosphazene reacted with poly(vinyl alcohol) by forming C–O–C bonds. TGA and DTG analysis showed that cross-linking improved the thermal stability. The swelling degree and pervaporation properties of cross-linked PVA membranes were also characterized. With increasing cross-linker concentration, swelling degrees and flux decrease while separation factors increase. Compared with PVA membranes cross-linked by glutaraldehyde, PVA membranes cross-linked by cyclophosphazene exhibited better selectivity and permeation rate.     

Mechanical and Thermal Behavior of Blends of Poly(hydroxybutyrate-co-hydroxyvalerate) with Ethylene Vinyl Acetate Copolymer

Ethylene vinyl acetate copolymer (EVA), with vinyl acetate contents of 60% or 80%, was used to improve the mechanical properties of poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV). Blends of PHBV/EVA were prepared with the ratios of 90:10, 70:30, and 50:50. Stress–strain results indicated that the tensile strength, elongation at break, Young's modulus, and toughness of PHBV blends could be adjusted by changing the composition of blends and miscibility. It was found that high elongation at break, ca. 200%, was obtained for PHBV/EVA80 (50:50).     

In Vitro Assessment of Poly (Vinyl Alcohol) Film Incorporating Aloe Vera for Potential Application as a Wound Dressing

Since skin tissue acts as a vital protective barrier between the body and the external atmosphere, the repair or regeneration of skin injuries serves as a great challenge in regenerative medicine. Herein, hydrogel films composed of poly vinyl alcohol (PVA) and aloe vera (AV) extracted gel were prepared and characterized for wound dressing application. The physical and morphological properties, water absorption capacity, biodegradation behavior, and water transmission rate were characterized for several variations in the AV content (0–50%). The cytocompatibility of the films, as well as cell morphology in response to different films, was assessed using MTT assay and SEM, respectively. According to the results, AV incorporation improved the surface morphology, water absorption capacity, in vitro degradation rate, and water vapor permeability of the PVA films. However, these properties were affected by the AV content. The mechanical properties of the films were enhanced by introducing AV up to 30%, and then decreased significantly with further AV increase. Evaluation of fibroblast proliferation showed that AV can positively improve the bioactivity of the films without any cytotoxicity. In conclusion, the results demonstrated that PVA/AV optimized hydrogel film can be suggested as promising wound dressings for improving wound treatment.     

Preparation and Characterization of Poly(Vinyl Alcohol) (PVA)/SiO2, PVA/Sulfosuccinic Acid (SSA) and PVA/SiO2/SSA Membranes: A Comparative Study

Abstract

New organic–inorganic nanocomposites based on PVA, SiO₂ and SSA were prepared in a single step using a solution casting method, with the aim to improve the thermomechanical properties and ionic conductivity of PVA membranes. The structure, morphology, and properties of these membranes were characterized by Raman spectroscopy, small- and wide-angle X-ray scattering (SAXS/WAXS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), water uptake (Wu) measurements and ionic conductivity measurements. The SAXS/WAXS analysis showed that the silica deposited in the form of small nanoparticles (～ 10?nm) in the PVA composites and it also revealed an appreciable crystallinity of pristine PVA membrane and PVA/SiO₂ membranes (decreasing with increasing silica loading), and an amorphous structure of PVA/SSA and PVA/SSA/SiO₂ membranes with high SSA loadings. The thermal and mechanical stability of the nanocomposite membranes increased with the increasing silica loading, and silica also decreased the water uptake of membranes. As expected, the ionic conductivity increased with increasing content of the SSA crosslinker, which is a donor of the hydrophilic sulfonic groups. Some of the PVA/SSA/SiO₂ membranes had a good balance between stability in aqueous environment (water uptake), thermomechanical stability and ionic conductivity and could be potential candidates for proton exchange membranes (PEM) in fuel cells.     

Nonisothermal Crystallization Kinetics of Ethylene Vinyl Alcohol Copolymer with Poly(oxypropylene)diamine Intercalated Montmorrilonite

Films of ethylene vinyl alcohol copolymer (EVOH) and EVOH containing poly(oxypropylene)diamine intercalated montmorrilonite were prepared by solution casting. The nanostructures and viscosity were characterized by small angle x-ray scattering (SAXS), transmission electron microscopy (TEM) and rheological testing. The nonisothermal crystallization kinetics of the samples were investigated by the Ozawa's and Mo's methods and the crystallization activation energy by Kissinger's model. The SAXS and TEM analysis demonstrated that the nanoplatelets, with an intercalated structure, were dispersed in the EVOH matrix. The rheological tests showed that the incorporation of the modified clay could increase the viscosity of the composite system. The Mo's method more successfully described the nonisothermal ctystallization behavior of neat EVOH and its nanocomposites as compared with the Ozawa's method. Adding the nanoclays had a heterogeneous nucleation effect to accelerate the crystallization of EVOH despite hindering the macromolecular chains movement.     

Structure and Properties of Poly(vinyl chloride)/Halloysite Nanotubes Nanocomposites

Poly(vinyl chloride)(PVC)/halloysite nanotubes (HNTs) nanocomposites were prepared by melt blending. The effects of HNT content on the mechanical properties, morphology, and rheological properties of the nanocomposites were investigated. The results showed that HNTs were effective in toughening and reinforcing PVC nanocomposites. The notched impact, tensile and flexural strength, and flexural modulus of the nanocomposites were remarkably increased compared with those for the pure PVC. Scanning electron microscopy (SEM) results illustrated the ductile behavior of the nanocomposites, with a possible cavitation mechanism. Transmission electron microscopy (TEM) results showed that HNTs were uniformly dispersed in the PVC matrix. Interfacial interaction of hydrogen bonding between the HNTs and PVC matrix was substantiated. The plasticization times of PVC/HNTs nanocomposites were found to be shorter and the equilibrium torque was higher than that for the pure PVC.     

A Comparative Study on In vitro Degradation Behaviors of Poly(L-lactide-co-glycolide) Scaffolds and Films

In vitro degradation behaviors of three-dimensional porous scaffolds and films made from amorphous poly(L-lactide-co-glycolide) (85/15) were systematically investigated up to 12 weeks in phosphate buffer saline (PBS) solution at 37°C. The following properties of the scaffolds and films were compared as a function of degradation time: pH value of PBS, water uptake, weight, molecular mass and its distribution, and morphology. The results show that the films degraded much faster than the scaffolds. The film's degradation was heterogenous due to the increased concentration of the acidic degradation products inside. However, owing to much thinner pore walls, heterogenous degradation due to the autocatalytic effect was not observed in the scaffolds.