Ionic naphthalene thermotropic copolyesters with para-linked ion-containing units

Novel ionic naphthalene thermotropic polymers (NTPs) based on wholly aromatic copolyesters were synthesized, in which ionic monomer was introduced in the form of para-linked metal hydroquinone disulfonate (HQDS). These ionic NTPs contained ionic groups of up to 4 mol%, with counterions of either monovalent K or divalent Ca, and exhibited thermotropic liquid crystallinity. The K-salts exhibited the crystalline and liquid crystalline behaviors, typically observed for a non-ionic NTP; and they developed excellent thermal and mechanical properties. Testing was made as a function of ionic content under similar processing and testing conditions. The value of glass transition temperature rose as the average molecular weight increased. Both the melting temperature, T_m, and the crystallization temperature, T_c, remained nearly constant over the composition range studied. All the K-salt ionic NTPs showed enhanced tensile properties over a non-ionic NTP. The strength increased significantly as the ionic content increased despite the decrease in the molecular weight, reflecting the dominant effect of ionic interactions over the effect of molecular weight. Enhanced tensile properties arise from enhanced interchain interactions via ionic bonds (cross-links) between highly aligned NTP chains. The incorporation of HQDS-type ‘straight’ ionic units into a NTP copolyester can provide useful information about the effect of ionic interactions on the thermal/mechanical properties of NTPs.     

Superabsorbent hydrogel based on modified polysaccharide for removal of Pb2+ and Cu2+ from water with excellent performance

This contribution describes the absorption percentage of Pb²⁺ and Cu²⁺ from water by a superabsorbent hydrogel matrix (SH) made from an anionic polysaccharide copolymerized with acrylic acid (AAc) and acrylamide (AAm). Metal‐absorption tests, upon sequential pH variation, indicated that the SH has pH‐sensitivity for the absorption of both metals from solution, attributed to the functional ionic groups (? COOH) present in the AAc and arabic gum (AG) segments. At the pH 5.0, the SH exhibited good absorption capacity: 73.10% for Pb²⁺, 81.99% for Cu²⁺ in water and 63.64% for Pb²⁺, and 76.67% for Cu²⁺ in saline water with 0.1 mol kg^?1 ionic strength. A replicated 2² full factorial design with a central point was built to evaluate the maximum absorption capacity of the metals into the SH. It was found that both the interaction and main effects of the pH and the initial concentration of metal solution on absorption percentage of the metals were statistically significant. Surface response plots indicated that the absorption capacity of both metals into the SH may be appreciably improved by using the solutions with lower initial concentration of metal and with higher pH values. Metal‐absorption results demonstrated that the SH is a convenient material for absorption of Pb²⁺ and Cu²⁺ from pure aqueous and saline aqueous environments. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and characterization of surfactant‐free stimuli‐sensitive microgel dispersions

A surfactant‐free method to produce responsive polymer microgels is introduced. As an example, poly(methacrylic acid) hydrogels with varying crosslinking density have been synthesized in bulk and then chopped using a high shear mechanical cutter to form microgel particles dispersed in water. The mechanical cutting technique enables the concentration and particle size distribution of the microgel suspensions to be easily controlled, therefore making the rheology of the suspensions tuneable. The particle size distribution of the dispersions, characterized using light scattering, was dependent on the speed and duration of mechanical cutting. The particle size distribution also depended on the degree of crosslinking of the hydrogel. The higher the crosslinking density, the lower the average mean diameter of the resulting microgel particles. The lower the crosslinking density of the hydrogel, the larger the difference between the maximum and minimum particle size. The time to complete swelling of the particles upon change in pH was measured to be up to 45 s, depending on the particle size. The rheology of the resulting suspensions as a function of pH was investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 104: 1912–1919, 2007     

Conformation of polyacrylamide in aqueous solution with interactive additives and cosolvents

The viscosity of polyacrylamide (PAM) dilute aqueous solutions with NaCl, glucose, and SDS as additives was measured by Ubbelohde viscometry. There was linear relationship between reduced viscosity vs. PAM concentration in aqueous solutions. The Huggins constant k and intrinsic viscosity [η] were used to study the conformation of the polymer chains and the degree of polymer–solvent interaction. In addition, the viscosity of diluted PAM solutions in water with acetone, ethanol, DMF, and ethylene glycol as cosolvent was measured. It was found that the polymer chain conformation contracted as the acetone, ethanol, and DMF cosolvent composition ratio increased, but there was no distinguishing difference between water–ethylene glycol compositions. The solution properties of PAM were used to estimate the swelling properties of PAM gel in the same external conditions, as gel is formed by crosslinking of linear polymer. In good solvent the polymer chain should be expanded, and gel is expected to have large swelling ratio. In water cosolvent systems, when the linear polymer chain underwent coil–globule transition, PAM gel should have volume phase transition under corresponding external conditions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3122–3129, 2003     

Biomimetic Polymer Nanostructures by Injection Molding

The nanometer scale topography of self‐assembling structural protein complexes in animals is believed to induce favorable cell responses. An important example of such nanostructured biological complexes is fibrillar collagen that possesses a cross‐striation structure with a periodicity of 69 nm and a peak‐to‐valley distance of 4–6 nm. Bovine collagen type I was assembled into fibrillar structures in vitro and sedimented onto solid supports. Their structural motif was transferred into a nickel replica by physical vapor deposition of a small‐grained metal layer followed by galvanic plating. The resulting inverted nickel structure was found to faithfully present most of the micrometer and nanometer scale topography of the biological original. This nickel replica was used as a die for the injection molding of a range of different thermoplastic polymers. Total injection molding cycle times were in the range of 30–45 seconds. One of the polymer materials investigated, polyethylene, displayed poor replication of the biological nanotopographical motif. However, the majority of the polymers showed very high replication fidelity as witnessed by their ability to replicate the cross‐striation features of less than 5 nm height difference. The latter group of materials includes poly(propylene), poly(methyl methacrylate), poly(L ‐lactic acid), polycaprolactone, and a copolymer of cyclic and linear olefins (COC). This work suggests that the current limiting factor for the injection molding of nanometer scale topography in thermoplastic polymers lies with the grain size of the initial metal coating of the mold rather than the polymers themselves.

     

Stochastic defect diffusion model for relaxation effects in crystalline polyethylene

It is suggested that some relaxation processes observed in crystalline polyethylene are consequences of the diffusive motion of a particular defect called a point dislocation or twist dispiration loop along the polyethylene stems in lamellar crystals. The motion of the defect, characterized by a diffusion coefficient and a mobility, is described by solutions of the Smoluchowski diffusion equation with boundary conditions that constrain the defect to move along routes that produce experimentally observable results. The fact that passage of the defect causes both a 180° rotation of the chain and moves an extra CH₂ group in the direction of the chain axis is important to the interpretation of the data according to this model. The diffusion coefficient for a defect is estimated to be around 2 × 10^?9 cm² s^?1 at 70°C. This value is shown to be reasonable both from the viewpoint of detailed computer modelling of defect motion and contemporary ideas about scaling.     

The Polymerization of Metal-Containing Vinylic Monomers of Iron and Tungsten with Metal–Carbon σ Bonds

A series of metal-containing vinylic monomers of the type and was homopolymerized using 2,2-azobisisobutyronitrile (AIBN) as the free-radical initiator. These monomers were also copolymerized with styrene in the presence of AIBN. These compounds represent a class of organometallic polymers in which the metal is bonded to the polymer backbone via a metal–carbon bond. The new compounds were characterized by IR and ¹H NMR spectroscopy as well as scanning electron microscopy, gel permeation chromatography, and thermoanalytical studies (DSC and TGA). The properties of the new organometallic polymers are discussed.     

Fabrication of poly(PEGMA) surface with controllable thickness gradient and its mediation on the gradient adhesion of cells

The gradient surface shows enormous potential in the development of tissue engineering, biosensor, microfluidic control, and particle sorting. In this work, a poly(polyethyleneglycol methacrylate) (poly(PEGMA)) gradient surface was prepared through surface-initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-AGRET ATRP). The effect of various parameters on the thickness growth of poly(PEGMA) film were analyzed, among which the excessive reducing agent was utmost important. The reducing agents supported the regeneration of Cu^I and eliminated the disturbance of air, maintaining the "living polymerization" of poly(PEGMA) up to 73.1 nm under tested conditions. The physicochemical properties of the fabricated surfaces were characterized by ellipsometry, X-ray photoelectron spectroscopy, water contact angle. The thickness slope of gradient poly(PEGMA) was controllable in a nanoscale range. The gradient surface was further grafted with CRGD (Cys-Arg-Gly-Asp) peptides onto the poly(PEGMA-co-[glycidyl methacrylate]) blocks via the ring-opening reaction between epoxy and amino groups, which showed a gradient change in water contact angle and adhesion of endothelial cells.     

Controlled release of insecticide carbaryl from sodium alginate,sodium alginate/gelatin,and sodium alginate/sodium carboxymethyl cellulose blend beads crosslinked with glutaraldehyde

Interpenetrating network polymeric beads of sodium alginate (NaAlg) and its blend with gelatin (gels) or sodium carboxymethyl cellulose (NaCMC) have been prepared by crosslinking with a common crosslinking agent, glutaraldehyde (GA), for the release of insecticide carbaryl (Carb). The prepared beads were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. Scanning electron microscopy confirmed the spherical nature and surface morphology of the particles. Bead characteristics, such as carbaryl entrapment efficiency, particle size, equilibrium swelling degree, and carbaryl release kinetics, were determined. The effects of the preparation conditions, such as Carb/NaAlg ratio, time of exposure to GA, blend ratio, and temperature of release medium on the carbaryl release, were investigated for 25 days at 25°C. It was observed that the carbaryl release decreased with increase in crosslinking of network, while it increased with increase in Carb/NaAlg ratio and temperature. The release of carbaryl also increased with increase in Gel or NaCMC content in the blend beads. The highest carbaryl release was found to be 100%, for the beads that were prepared with 1 : 1 NaAlg/Gel at 16 days. The diffusion coefficients have been calculated for the transport of insecticide through the polymeric beads, using initial time approximation method. These values were also consistent with the carbaryl release data. The carbaryl release from most of the bead formulations followed the Fickian trend. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1310–1319, 2006