Improvement of poly(vinyl alcohol) properties by the addition of magnesium nitrate

Aiming at the improvement of mechanical and dielectric properties of poly(vinyl alcohol) (PVA), we prepared composites of PVA and magnesium nitrate hexahydrate. It was found that the composites were very soft and rubber‐like, and the glass transition temperature decreased with increasing the salt concentration. Wide‐angle X‐ray diffraction and small‐angle X‐ray scattering revealed that the crystallites of PVA were destroyed by the additive and it was the cause of the softening. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Melt processing of poly(vinyl alcohol) through adding magnesium chloride hexahydrate and ethylene glycol as a complex plasticizer

The melt processing of poly(vinyl alcohol) (PVA) was achieved using magnesium chloride hexahydrate (MgCl₂·6H₂O) and ethylene glycol as a complex plasticizer. The interaction between the complex plasticizer and PVA was studied by Fourier transform infrared spectroscopy (FT‐IR). The PVA films were characterized using X‐ray diffraction (XRD), differential scanning calorimetry, thermogravimetric analysis (TGA), scanning electron microscope, and dynamic thermomechanical analysis (DMA) techniques. The band shift of the observed peak around 3335 cm^?1 in the FT‐IR spectra indicates that the complex plasticizer MgCl₂·6H₂O and ethylene glycol could form strong interactions with PVA and thus interrupt the intermolecular and intramolecular hydrogen bonding in PVA. The XRD results show that the addition of the complex plasticizer would significantly destroy the crystallites of PVA and result to the decrease of the degree of crystallinity of PVA. The melting point was reduced from 229°C of pure PVA to around 170°C after the plasticization. The TGA studies show that with the complex plasticizer, the thermal stability of PVA is improved. PVA plasticized by 30 wt% MgCl₂·6H₂O and 10 wt% ethylene glycol shows the tensile strength of 33 MPa and the elongation at break of 362%. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Modification of pitches by poly (vinylidene chloride) and poly (vinyl chloride)

Poly(vinylidene chloride) — PVDC — and poly(vinyl chloride) — PVC — reacted with pitches at elevated temperature with an increase in the yield of residual carbon; the greater the aromaticity and ‘fixed carbon’ of the pitch, the greater the increase. PVDC especially had a remarkable effect. This increase of residual carbon may be due to an increase in the molecular weight of pitch produced by its reaction with PVDC or PVC via dehydrochlorination. This tends to elevate the softening point and increase the insolubility in solvents. It is clearly indicated from i.r. spectra that reaction takes place mainly between aromatic hydrogen in the pitch and chlorine in PVDC. X-ray diffraction profiles of the reaction products show that the pitch forms hard (non-graphitizing) carbon as the PVDC content in the mixture increases.     

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.     

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.     

ACR抗冲改性剂对PVC的改性效果

采用乳液聚合工艺合成厂核—壳型丙烯酸酯类抗冲改性剂。该抗冲改性剂对提高聚氯乙烯(PVC)的抗冲击性能具有显著效果，同时也能改善PVC的加工性能。     

Modification of poly(vinyl alcohol) fibers by hexamethylene diisocyanate

Poly(vinyl alcohol) multifilament yarn was modified by reaction with hexamethylene diisocyanate. The effects of reaction variables such as time, temperature, concentration of reagents, solvent, and atomosphere were studied. The role of solvent appears to be very important in the reaction. Dimethylformamide, on account of its swelling power, proved better than the solvents benzene, toluene, and dioxane. Physical properties of modified fibers were compared with those of the parent. Moisture regain of the modified samples decreased with increasing add-on percent. The elastic recovery was not improved, and there was little effect of the HMDI treatment on mechanical properties. The thermal stability of poly(vinyl alcohol) modified with diisocyanate with small add-on was slightly improved.     

Modification of poly(vinyl chloride) by IPN formation with poly(ethyl acrylate)

Semi‐1 and semi‐2 interpenetrating polymer networks (IPNs) of poly(vinyl chloride) (PVC) and in situ formed poly(ethyl acrylate) (PEA) have been synthesized using diallyl phthalate and ethylene glycol dimethacrylate as the crosslinkers of PVC and PEA, respectively. These two types of IPNs have been compared with respect to their physical, mechanical, and thermal properties and an endeavor has been made to find a correlation of these properties with the morphology generated in these systems. The semi‐1 IPNs displayed a decrease in their tensile strength and modulus while in contrast; the semi‐2 IPNs exhibited a marginal increase with increasing crosslinked PEA incorporation. The semi‐1 and semi‐2 IPNs containing 10 and 30 wt % of PEA displayed a two‐stage degradation typical of PVC in their thermogravimetric and DSC studies while confirming the increased stability of the samples with higher percentages of PEA. The softening characteristics as detected by the extent of penetration of the thermomechanical probe as has been detected by thermomechanical analysis are in conformity with their mechanicals. The biphasic cocontinuous systems as explicit from the morphological studies reveal fibrillar characteristics in both the systems. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Structure of poly(vinyl alcohol)-iodine complex formed in the amorphous phase of poly(vinyl alcohol) films

The effect of syndiotactivity of poly(vinyl alcohol) (PVA) both on the formation and thermal stability of the complex formed in the amorphous phase of PVA films is investigated, and then a model of the complex is presented. The amount of the complex formed in syndiotacticity-rich PVA is much larger than that formed in atactic PVA under a given iodine-soaking condition, and the former complex has a higher thermal stability in the soaking solution than the latter. The complex formed in the amorphous phase is proposed to have such a structure as that in which a linear polyiodine I₅^? or I₅^? with a 3.1 A? periodicity is enveloped by four PVA segments of syndiotactic configuration with extended conformation. In this model, these four PVA chains participating in a complex are supposed to be fixed by interchain hydrogen bonds. The observed X-ray meridional intensity curve of iodinated PVA film can be explained by a series of two I₅^?. © 1993 John Wiley & Sons, Inc.     

The influence of poly(vinyl alcohol) suspending agents on suspension poly(vinyl chloride) morphology

The requirements for PVC suspension resin have changed considerably in the last few years, so much so that few companies have products on their ranges that are more than 4 or 5 years old. The suspending agent has a crucial influence on the morphology of the resin, so the changes in resin characteristics have largely been achieved by changes in the suspending agent systems. After a brief review of the mechanism of PVC suspension polymerisation, the properties of polymers made using PVOH suspending agents are related to changes in the latter. The effect of variations in PVAc degree of hydrolysis and viscosity are related to changes in surface tension. Methods of achieving higher porosity by using low hydrolysis co-suspending agents are described. It is shown that higher bulk densities can be achieved by delayed addition of the PVOH. Levels of conjugated unsaturation and copolymer distributions are also shown to have important influences.     

Phosphorescence and fluorescence of poly(vinyl alcohol) films

Luminescence properties of poly(vinyl alcohol) (PVA) films were investigated at room and low (103 K) temperatures. It was estimated that the PVA films can be regarded as luminescentless matrices when excited by radiation of wavelengths greater than 420 nm (λ_exc ≥ 420 nm).     

Modification of chlorinated poly(vinyl chloride) by blending with epoxidized polybutadiene

The compatibility of epoxidized poly(cis-1,4-butadiene) (EPB) with chlorinated polyvinylchloride (CPVC) was investigated. Blends studied covered the complete composition range using EPB at two degrees of epoxidation: 20 and 43 mol % oxirane units. Tensile properties of EPB (63)/CPVC were also studied at the 50/50 composition. Dynamic mechanical analysis (DMA) showed that both sets of blends were miscible at the segmental level except for the rich CPVC compositions. All blends showed good tensile properties. even those where DMA indicated phase separation. This may be attributed to strong segmental interactions of the donnor-acceptor type between the oxirane and acidic-hydrogen-containing groups of these complementary dissimilar blend partners.     

Modification of gel-drawn poly(vinyl alcohol) fibers with formaldehyde

Poly(vinyl alcohol) fibers which were drawn from dried gels were chemically treated with formaldehyde to induce crosslinking in the amorphous phase. The room temperature storage modulus decreased early in the treatment, to an almost constant value of 50–60% of the initial modulus of the fiber. This behavior was independent of the concentration of formaldehyde used. The modulus at low temperature was also reduced, and no T_g peak could be seen in heavily treated fibers. The modulus above the original T_g, 70°C, was much less affected. The crystallinity determined by DSC fell by one third as the room temperature modulus decreased, and X-ray diffraction indicated a reduction in the crystal length along the chain direction at the same time. Thus, under the conditions of treatment used, the loss of properties due to destruction of crystals outweighs the stiffening and reduced water sensitivity of the crosslinked amorphous phase.     

Modification of poly(vinyl chloride) films by aliphatic amines to prepare anion-exchange membranes for Cr (VI) removal

ABSTRACT

A method for the synthesis of anion-exchange membranes by the grafting of ethylenediamine (EDA), diethylenetriamine (DETA) or pentaethylenehexamine (PEHA) onto poly(vinyl chloride) (PVC) film has been presented. The chemical structure was determined by means of Fourier Transform Infrared Spectroscopy (FTIR) and the membranes were characterized by ion-exchange capacity, chloride and nitrogen contents, water regain and surface energetics. The obtained membranes were evaluated in the Donnan dialysis (DD) of hexavalent chromium solutions. Among the membranes, those modified with EDA and DETA showed the best separation features: high flux and high recovery factor (RF). The highest degree of recovery was observed for membranes prepared by the casting of PVC solution in (THF), followed by grafting EDA.     

Mechanochemical synthesis and characterization of poly(vinyl chloride)-block-poly(vinyl alcohol) copolymers by ultrasonic irradiation

Mechanical degradation and mechanochemical reaction in heterogeneous systems of the solid poly(vinyl chloride)-poly(vinyl alcohol) aqueous solutions have been studied by ultrasonic irradiation at 30 °C. The rate of decrease in the viscosity-average degree of polymerization of the degraded poly(vinyl chloride) was much faster than that of the degraded poly(vinyl alcohol). Mechanochemical reaction occurred by free radicals produced from the chain scissions of both polymers by ultrasonic waves. The copolymer was obtained and the molar ratio of the vinyl chloride and the vinyl alcohol units in its copolymer can be determined. In addition, the changes in the composition of the total block copolymer, the unreacted poly(vinyl chloride), and the unreacted poly(vinyl alcohol) were obtained. Received: 1 October 1998/Revised version: 9 January 1999/Accepted: 13 January 1999     

Photothermal imaging of dehydrochlorination in poly(vinyl chloride) films

Impulse (time domain) laser photopyroelectric effect spectrometry uses the time dependence of heat diffusion in an irradiated sample to infer optical and thermal property depth distributions in the sample. This method was used in conjunction with a recently reported method of inverse problem theory to recover the depth dependence of optical absorption in photodegraded thin films of poly(vinyl chloride) (PVC) on a depth scale of a few tens of microns. The thin films were photodegraded under broadband ultraviolet light prior to photothermal analysis to induce subsurface profiles of visible absorption arising from the depth dependence of light initiated dehydrochlorination reactions in the films. Optical depth profile reconstructions could be made in samples that had undergone mild degradation only and where the absence of significant thermal effusivity changes accompanying degradation could be confirmed. Reconstructed optical transmission profiles were compared with optical transmission micrographs and were shown to resolve features that arise from the depth dependence of photo-induced dehydrochlorination reactions in the films. The extent of these latter reactions is controlled by the depth dependence of the oxygen concentration in the films.     

Mechanical properties of films of poly(vinyl alcohol) derived from vinyl trifluoroacetate

In order to study the influence of the stereoreguralities of polymer chains on the mechanical properties of films of poly(vinyl alcohol) (PVA)_(VTFA) derived from vinyl trifluoroacetate, the strength of the film was measured. In the case of undrawn PVA_(VTFA) films, Young's modulus and strength at break were the smallest at the annealing temperature of about 100°C. It is considered to be due to the melt of small microcrystals and the increase in mobility of chains in amorphous parts. Young's moduli of undrawn PVA_(VTFA) films were in the range of 1.50–3.75 GPs and the values were higher than that (0.17–0.36 GPa) of undrawn film of commercial PVA with the low concentration of syndiotacticity and the high concentration of head-to-head bounds. In the case of drawn, annealed PVA_(VTFA) films, the maximum Young's modulus was about 20 GPa.     

Effective methodology for the production of novel nanocomposite films based on poly(vinyl chloride) and zinc oxide nanoparticles modified with green poly(vinyl alcohol)

Ultrasonic irradiation and solution dispersion methods were used to organize transparent worthwhile poly(vinyl chloride) (PVC) nanocomposite (NC) films which contain different amounts of modified zinc oxide nanoparticles (NP)s. First, modification of ZnO NPs was accomplished by biocompatible poly(vinyl alcohol) (PVA) to increase NCs compatibility and dispersity in the PVC matrix. The investigation followed by the fabrication and characterization of PVC/ZnO‐PVA NCs which obtained via fast and facile ultrasonication irradiation. The measurements of X‐ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and field emission scanning electron microscopy were used for the characterization of properties, structure and morphology of the obtained NPs and their NCs. Furthermore, thermal and optical properties of the resulting NCs were also carried out by thermogravimetric analysis, ultraviolet‐visible transmission, and absorption spectra. Morphology results demonstrate well‐dispersed characteristics of ZnO‐PVA NPs incorporated in the PVC matrix which resulted from modification. Also, modified ZnO NPs enhanced mechanical properties of prepared NC films. Prepared NCs could be categorized as self‐extinguishing materials on the basis of the limiting oxygen index values. POLYM. COMPOS., 38:1800–1809, 2017. © 2015 Society of Plastics Engineers