Head-to-head polymers: 19. Chlorination of cis-1,4-polybutadiene

Chlorination of cis-1,4-polybutadiene (PB) has been studied in detail. It was found that chlorination must be carried out in an oxygen free atmosphere at polymer concentrations below 0.5%, and at temperatures below room temperature in mixed solvents with dichloromethane as the major component. In the initial stage of chlorine addition to the double bonds of cis-1,4-polybutadiene, block structures of chlorinated segments are formed. The chlorine addition to the cis-butadiene units was not stereospecific and the final chlorination product had nearly a 1:1 ratio of the threo- and erythro structure of the CHCICHCI-units. Microphase separation in partially chlorinated PB was observed by d.s.c., dynamic-mechanical measurement, and transmission electron microscopy. It was concluded that partially chlorinated PB, whose degree of chlorination was lower than 65 mole %, was composed of almost pure cis-1,4-PB domains and a separate phase which consists ofCH₂CHCICHCICH₂units with perhaps as much as 10% of cis-1,4-PB units incorporated in this phase. If the degree of chlorination is more than 90 mole % one phase exists.     

Studies on aluminum-isopropoxide doped poly(ethylene oxide), poly(vinyl alcohol), and poly(ethylene oxide)-poly(vinyl alcohol) blends

Poly(ethylene oxide), poly(vinyl alcohol), and their blend in a 40 : 60 mole ratio were doped with aluminum isopropoxide. Their structural, thermal, and electrical properties were studied. Aluminum isopropoxide acts as a Lewis acid and thus significantly influences the electrical properties of the polymers and the blend. It also acts as a scavanger for the trace quantities of water present in them, thereby reducing the magnitude of proton transport. It also affects the structure of polymers that manifests in the thermal transformation and decomposition characteristics. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2147–2157, 1998     

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.     

Thermal characteristics of poly(vinyl alcohol) and poly(vinylpyrrolidone) IPNs

Interpenetrating polymer network (IPN) hydrogels based on poly(vinyl alcohol) (PVA) and 1‐vinyl‐2‐pyrrolidone (VP) were prepared by radical polymerization using 2,2‐dimethyl‐2‐phenylacetophenone (DMPAP) and methylene bisacrylicamide (MBAAm) as initiator and crosslinker, respectively. The thermal characterization of the IPNs was investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dielectric analysis (DEA). Depressions of the melting temperatures of PVA segments in IPNs were observed with increasing VP content via the DSC. The DEA was employed to ascertain the glass transition temperature (T_g) of IPNs. From the result of DEA, IPNs exhibited two T_gs indicating the presence of phase separation in the IPN. The thermal decomposition of IPNs was investigated using TGA and appeared at near 270°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1844–1847, 2002     

Improving the antifouling property of poly(vinyl chloride) membranes by poly(vinyl chloride)‐g‐poly(methacrylic acid) as the additive

To improve the antifouling property of poly(vinyl chloride) (PVC) membranes, a series of poly(methacrylic acid) grafted PVC copolymers (PVC‐g‐PMAA) with different grafting degree were synthesized via one‐step atom transfer radical polymerization process utilizing the labile chlorines on PVC backbones followed by one‐step hydrolysis reaction. PVC/PVC‐g‐PMAA blend membranes with different grafting degree and copolymer content were prepared by nonsolvent induced phase separation method. The surface chemical composition, surface charge, membrane structures, wettability, permeability, separation performances and the fouling resistance of blend membranes were carefully investigated. The results indicated that the PMAA chains were segregated towards the surface and the membranes were endowed with negative charge. The hydrophilicity and permeability of the blend membranes were obviously improved. Furthermore, the antifouling ability especially at neutral or alkaline environments was also significantly increased. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42745.     

Poly(acrylic acid)–poly(vinyl alcohol) copolymers with superabsorbent properties

Biodegradable polyacrylates were produced by a series of novel copolymerization and/or crosslinking techniques using poly(vinyl alcohol) (PVA) moieties modified by the incorporation of olefinic structures. PVA was modified by a tosylation and/or detosylation reaction. The functionalized PVA was copolymerized and/or crosslinked with acrylic acid or its partially neutralized form to give crosslinked polyacrylates that could swell in water. Their swelling behavior was determined under load. Degradation studies were performed in α-chymotrypsin, trypsin, and papain solutions. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 817–829, 1998     

Influences of individual and composed poly(vinyl alcohol) suspending agents on particle morphology of suspension poly(vinyl chloride) resin

Effects of individual and composed poly(vinyl alcohol) (PVA) suspending agents on the particle morphology of poly(vinyl chloride) (PVC) resins were investigated and discussed in the view of PVA absorption at the oil/water interface and interfacial behavior. It was shown that the percentage and surface coverage of PVA at the oil/water interface decreased with the increase of the degree of hydrolysis (DH) of PVA in the DH range of 70–98 mol %, while the interfacial tension of VC/PVA aqueous solution increased linearly with the increase of DH of PVA. PVC resin with more regular particle shape, increased agglomeration and fusion of primary particles, lower porosity and higher bulk density, was prepared by using PVA with a higher DH as a suspending agent. This was caused by the occurrence of drop coalescence at the very early stage of VC polymerization, the increase of particle shrinkage, and the lower colloidal protection to primary particles. It was also shown that the interfacial tension of VC/water in the presence of composed PVA suspending agents varied linearly with the weight composition of the composed PVA suspending agents. The particle properties of PVC resin prepared by using the composed PVC suspending agents were usually situated in between the properties of PVC resins prepared by using the corresponding individual PVA suspending agent. The particle morphology and properties of PVC resin could be controlled by the suitable choice of the composed PVA suspending agents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3848–3855, 2003     

Surface treatment of plasticized poly(vinyl chloride) to prevent plasticizer migration

In this investigation, plasticized poly(vinyl chloride) (PVC) was treated with poly(azido acrylate)s to prevent plasticizer migration. This was achieved by modification of PVC sheets with poly(azido acrylate)s in a dichloromethane solution followed by irradiation under UV light. The surface‐modified PVC sheets with poly (azido acrylate)s were characterized with Fourier transform infrared spectroscopy and scanning electron microscopy analyses. The migration of the plasticizer was prevented to a large extent from modified PVC in comparison with unmodified PVC. The amount of plasticizer migration with respect to the irradiation time, incubation time, and number of dipping times was evaluated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Solvent effect on structural change of poly(vinyl alcohol) physical gels

In this study, the relationship between the polymer–solvent interaction and the network structure of poly(vinyl alcohol) (PVA) gels prepared with organic solvents such as N-methylpyrrolidone (NMP) and ethylene glycol (EG) are investigated. The values of the intrinsic viscosity [η] and Huggins constant k′ of dilute PVA solutions indicate that the attractive interaction between PVA and NMP is higher than that between PVA and EG. The X-ray result shows that PVA–EG gels have a (101) diffraction peak of PVA crystal that appeared at about 2θ = 19°, while PVA–NMP gels only show a broad amorphous scattering peak. On the other hand, Fourier transform infrared results of PVA/EG gels also clearly show an intense peak at 1141 cm⁻¹ due to the crystalline absorption. The results of H¹ pulsed nuclear magnetic resonance show that the spin–spin relaxation time, and respectively, related to the polymer-rich and polymer-poor components decrease, and the fractional amount of the polymer-rich component, f^s, increases, while that of the polymer-poor component, f^l, decreases with an increase in the concentration of polymer. At a given concentration, the value of f^s in the PVA–EG gel is larger than that in the PVA–NMP one. These facts indicate that the crystallinity in the PVA–EG gel is higher than that in the PVA–NMP gel, implying that the aggregation of PVA chains is much easier in the poor solvent, EG, than in the good solvent, NMP. The structural change with aging time in the PVA–EG gel is very remarkable because of the significant syneresis, indicating that the opaque PVA–EG gel with higher crystallinity has a comparatively heterogeneous and unstable network structure than the PVA–NMP gel does. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2477–2486, 1998     

Synthesis of poly(vinyl propionate) from poly(vinyl alcohol) in nonaqueous medium using ethyl nitrate dimethyl sulfoxide as a catalyst

Poly(vinyl alcohol) (PVA) can be dissolved in a nonaqueous medium in the presence of catalytic concentration of ethyl nitrate dimethyl sulfoxide, C₂H₅ONO₂·DMSO. From the PVA solution, poly(vinyl propionate), PVPR was prepared by the homogeneous esterification of PVA with propionic acid. The ester thus formed contained some unconverted hydroxyl group. The formation of the ester was confirmed by the IR and ¹H‐NMR spectra. The molecular weight of the ester was determined by GPC and intrinsic viscosity (η) was determined by viscometric method. Glass transition temperature, T_g, was obtained from differential scanning calorimetric (DSC) analysis. Thermal stabilities of the ester were checked by thermogravimetric analysis (TGA) and differential thermogravimetric (DTG) analysis. The efficiency of the ester as a flow improver of crude oil was also examined. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5675–5679, 2006     

Poly(vinyl alcohol) and poly(vinyl amine) blend membranes for isopropanol dehydration

Blended membranes of hydrophilic polymers poly(vinyl alcohol) (PVA) and poly(vinyl amine) (PVAm) were prepared and crosslinked with glutaraldehyde. The prepared membranes were characterized using infrared (attenuated total reflection mode) spectroscopy, differential scanning calorimetry, X‐ray diffractometry, and scanning electron microscopy measurements. Pervaporation performances of the membranes were evaluated for the separation of water‐isopropanol (IPA) mixtures. As the PVAm content increased from PVAm0 to PVAm1.5, the flux through a 70 μm film increased from 0.023 to 0.10 kg/m² h at an IPA/water feed ratio of 85/15 at 30 °C. The driving force for permeation of water increased due to the temperature but it has no effect on IPA permeation. Activation energies for the permeation of IPA and water were calculated to be 17.11 and 12.46 kJ/mol, respectively. Controlling the thickness of the blend membrane could improve the permeation flux with only a marginal reduction in the separation factor. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45572.     

Preparation of poly(acrylic acid)/poly(vinyl alcohol) membrane for the facilitated transport of CO2

Poly(acrylic acid) (PAA)/poly(vinyl alcohol) (PVA) membrane was prepared for the facilitated transport of CO₂. The carrier of CO₂ was monoprotonated ethylenediamine and was introduced in the membrane by ion exchange. The ion‐exchange capacity of the membrane was 4.5 meq/g, which was much higher than that of the Nafion 117 membrane. The membrane was highly swollen by the aqueous solution. Much higher selectivity of CO₂ over N₂ and higher CO₂ permeability were obtained in the PAA/PVA membrane than in the Nafion membrane because of the higher ion‐exchange capacity and solvent content. The highest selectivity was more than 1900 when the CO₂ partial pressure in the feed gas was 0.061 atm. Effects of ion‐exchange capacity, membrane thickness, and annealing temperature in conditions of membrane preparation on membrane performance were investigated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 936–942, 2001     

Diffusion of solvents in poly(vinyl acetate) and partially and fully hydrolyzed poly(vinyl alcohol)

Diffusivities of methyl acetate, methanol and water in poly(vinyl acetate) and fully and partially hydrolyzed poly(vinyl alcohol) have been measured by capillary column inverse gas chromatography and/or gravimetric sorption. Data from the literature have been used when available for comparison. Overall the diffusivities show good consistency in terms of their temperature and concentration dependences. The free‐volume model has been applied to all the data with excellent results. In most cases the dramatic changes in diffusivities with temperature and concentration can be captured using only a few experimental data points and two regression parameters. This demonstrates that the free‐volume theory is a valuable tool for the design of equipment for processing and devolatilization of polymer ? solvent systems. © 2013 Society of Chemical Industry     

Thermal and spectroscopic studies of poly(N‐vinyl pyrrolidone)/poly(vinyl alcohol) blend films

Poly(N‐vinyl pyrrolidone) (PVP) and poly (vinyl alcohol) (PVA) homopolymers and their blended samples with different compositions were prepared using cast technique and subjected to X‐ray diffraction (XRD) measurements, infrared (IR) spectroscopy, ultraviolet/visible spectroscopy, and thermogravimetric analysis (TGA). XRD patterns of homopolymers and their blended samples indicated that blending amorphous materials, such as PVP, with semicrystalline polymer, such as PVA, gives rise to an amorphous structure with two halo peaks at positions identical to those found in pure PVP. Identification of structure and assignments of the most evident IR ‐ absorption bands of PVP and PVA as well as their blends in the range 400–2000 cm^?1 were studied. UV–vis spectra were used to study absorption spectra and estimate the values of absorption edge, E_g, and band tail, E_e, for all samples. Making use of Coats‐Redfern relation, thermogravimetric (TG) data allowed the calculation of the values of some thermodynamic parameters, such as activation energy E, entropy ΔS^#, enthalpy ΔH, and free energy of activation ΔG^# for different decomposition steps in the samples under investigation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of poly(vinyl alcohol)‐poly(vinyl pyrrolidone) blend: A biomaterial with latent medical applications

Aqueous solutions of poly(vinyl alcohol) and poly(vinyl pyrrolidone) are blended and films are produced by casting method with the further intention of being used as bio‐materials with latent medical application. Glutaraldehyde, 4,4′‐diazido‐2,2′‐stilbenedisulfonic acid disodium salt tetra‐hydrate are used as crosslinker agents, whereas lactic acid is the plasticizer in the blend. The obtained films are characterized by differential scanning calorimetry (DSC), mechanical properties, swelling and solubility behavior. DSC measurements show that the blends exhibit a single glass transition temperature indicating that they are miscible, even in the presence of the plasticizer and crosslinker agents. By the combination of all mentioned additives, a relevant enhancement of the swelling is observed, accompanied by a stabilization of the solubility during the tested time. Finally, mechanical properties show an appropriate performance in the studied parameters. As a consequence, the obtained films could be suitable for use as medium or long‐term implants. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of tacticity of poly(methyl methacrylate) on the miscibility with poly(vinyl pyrrolidone)

Isotactic, atactic, and syndiotactic poly(methyl methacrylates) (PMMA) (designated iPMMA, aPMMA, and sPMMA) with approximately the same molecular weight were mixed separately with poly(vinyl pyrrolidone) (PVP) primarily in chloroform to make three polymer blend systems. Differential scanning calorimetry (DSC) was used to study the miscibility of these blends. The results showed that the tacticity of PMMA has a definite impact on its miscibility with PVP. The aPMMA/PVP and sPMMA/PVP blends were found to be miscible because all the prepared films showed composition-dependent glass-transition temperatures (T_g). The glass-transition temperatures of the aPMMA/PVP blends are equal to or lower than weight average and can be qualitatively described by the Gordon–Taylor equation. The glass-transition temperatures of the other miscible blends (i.e., sPMMA/PVP blends) are mostly higher than weight average and can be approximately fitted by the simplified Kwei equation. The iPMMA/PVP blends were found to be immiscible or partially miscible based on the observation of two glass-transition temperatures. The immiscibility is probably attributable to a stronger interaction among isotactic MMA segments because its ordination and molecular packing contribute to form a rigid domain. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3190–3197, 2001     

Synthesis and characterization of poly(pyridylurea) and poly(pyridylthiourea), potentially semiconducting polymers

Poly(pyridylureas) and poly(pyridylthioureas) were synthesized by reacting 2,6‐diaminopyridine with phosgene and thiophosgene, respectively, using THF and pyridine as solvent. The synthesized polymers were characterized by IR‐spectroscopy, elemental analysis, and X‐ray photoelectron spectroscopy. Thermal stability of the polymers was determined by thermal degradation between 35°C and 700°C. The 50% weight loss of polypyridylureas was above 400°C while for the polypyridylthioureas it was above 450°C. Undoped poly(pyridylureas) and poly(pyridylthioureas) behave as semiconductors, σ = 10^?9 (Ω cm)^?1. After doping with I₂ and SbF₅, the electrical conductivity increases several orders of magnitude, σ = 10^?7(Ω cm)^?1. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Properties of branched and network poly(vinyl alcohols) prepared with poly(vinyl alcohol) having aldehyde groups at the chain ends

Branched and network poly(vinyl alcohols) (PVAs) were prepared with inter-acetalization of the PVA with aldehyde groups at the chain ends which was prepared by the cleavage of 1,2 glycol bonds in commercial PVA. The numbers of branches estimated from molecular weights were compared with those estimated by theory. Huggins' constant and crystallinity decreased with increasing branch number. Dissolution of branched PVAs into dimethylsulphoxide was not so easy compared with commercial PVA. The colour of branched PVA–iodine complex decreased rapidly with standing while that of commercial PVA decreased gradually. Network PVAs with Young's modulus of 1–8 MPa were prepared.     

In-situ polymerization of n-butyl acrylate in poly(vinyl chloride)

The in situ polymerization of n-butyl acrylate with poly(vinyl chloride) has been studied. Butyl acrylate was polymerized using a peroxydicarbonate initiator and a thiol chain transfer agent in the presence of poly (vinyl chloride) beads suspended in water. The products were examined, after pressing into sheets, for optical clarity and by dynamic mechanical analysis. It was found that if 10% butyl acrylate was peesent in the mixture homogeneous blends were formed but if 15% or more butyl acrylate was present two phase mixtures were formed. If homogeneous blends prepared as above were reswollen in butyl acrylate, and the latter then polymerized, homogeneous blends containing more poly(butyl acrylate) could be prepared. The interaction parameters between both poly(vinyl chloride' and poly(butyl acrylate) and butyl acrylate were estimated by inverse gas chromatography. Using these and an estimate of the polymer/polymer interaction parameter the three component phase diagram could be qualitatively explained.