Thermal analysis of styrene–alkyl methacrylate polymers. I. Glass transition temperatures

The glass transition temperatures (T_g's) of several polystyrenes and styrene–alkyl methacrylate copolymers and terpolymers were measured using thermomechanical analysis (TMA) and differential scanning calorimetry (DSC). The polymers studied had number-average molecular weights from 3000 to 250,000 g/mole. The results indicate that the composition dependence of the T_g's for the copolymers and terpolymers can be satisfactorily described by a general Fox equation. In general, the measured T_g's of the copolymer and terpolymer samples depend more on the steric effects of the constituent pendent groups than on their molecular weights. The chain flexibility rather than the size of the pendent group is the determining factor in the glass transition properties of the styrene polymers.     

A Synthetic Approach to Star‐Like Polymers of Styrene and Butyl Acrylate by Linking Reactions using Functionalized Methacrylates

Summary: Coupling reactions between terminal functionalized polymer chains were chosen for the synthesis of star‐like polymers consisting of polystyrene and polystyrene‐block‐poly[styrene‐co‐(butyl acrylate)] arms. For the preparation of terminal functionalized polymer chains a side reaction of the 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) mediated free radical polymerization of methacrylates could be used successfully to convert TEMPO terminated polymers into end functionalized polymers. The number of functionalized monomer units attached to the polymer chain is directly related to the TEMPO concentration during this reaction. Different polystyrenes and polystyrene‐block‐poly[styrene‐co‐(butyl acrylate)] block copolymers were functionalized with a variable number of epoxide and alcohol groups at the chain end. For the determination of the optimal reaction parameters for the coupling reactions between these polymer chains, epoxy functionalized polystyrenes were converted with hydroxy functionalized polystyrenes under basic and acidic conditions. By activation with sodium hydride or boron trifluoride star‐like polymers were synthesized under mild conditions. The transfer of the reaction conditions to coupling reactions between end functionalized polystyrene‐block‐poly[styrene‐co‐(butyl acrylate)] copolymers showed that star‐like polymers with more than 12 arms were formed using boron trifluoride as activating agent.

     

Recycling of ethylene propylene diene monomer (EPDM) waste. III. Processability of EPDM rubber compound containing ground EPDM vulcanizates

The rheological behavior of ethylene propylene diene monomer (EPDM) compounds containing ground EPDM waste (W‐EPDM) of known composition was studied by using a Monsanto processability tester in a temperature range of 90–110°C and a shear rate range of 306.7–1533.24 s^?1. It is found that the shear viscosity decreases slightly with increasing W‐EPDM loading because of wall slip that results from the migration of lubricants from the W‐EPDM. The addition of W‐EPDM to raw EPDM results in a decreased die swell at all temperatures and shear rates. SEM photomicrographs of the EPDM extrudate surface show improved surface smoothness and reduced extrudate distortion when EPDM is blended with W‐EPDM. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2204–2215, 2003     

Ablation of ice-solids and wax-solids mixtures in turbulent axisymmetric water jets

The ablation rate of frozen mixtures of water or wax with finely divided solids subjected to a turbulent axisymmetric water jet was investigated both experimentally and theoretically. The range of the water jet Reynolds number was 8700–29300 and the jet temperature varied between 22 and 60°C. The solids used were very fine kaolinite clay, titanium oxide and aluminium powder. The type of solids and their concentration were found to affect the ablation rate of ice-solids and wax-solids mixtures. This is mainly due to changes in the physical properties of the melt layer of the water-solids or wax-solids mixtures which forms between the impinging jet and the frozen mixtures.     

Investigations on the adhesion and interfacial properties of polyurethane foam/thermoplastic materials

The adhesion and interfacial properties of polyurethane (PU) foams with thermoplastic (TP) materials were investigated using different techniques. The adhesion performance of PU foam with TP materials was evaluated using the peel test method, and the adhesion durability was checked after different climate treatments. X‐ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and contact angle measurements were used to study the surface and interface morphology of PU foam and TP material system. Three types of PU foam samples which differ in their composition and also five commercially available TP blends systems, based on poly(carbonate), poly(styrene‐co‐maleic anhydride), poly(acrylonitrile‐butadiene‐styrene), and silicone acrylate rubber have been used. The slow reacting foam shows the best adhesion properties with all the TP materials. The climate treatments strongly effected the PU foam adhesion durability with poly(carbonate) containing TP materials (70–80% loss in adhesion), but nearly no effect with poly(styrene‐co‐maleic anhydride). The samples with lowered adhesion could be separated by peeling without visible foam residues on the TP surface. AFM, XPS, and surface tension studies have shown that the surface properties of the TP material are still governed by the PU foam. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 479–488, 2007     

Allelochemical resistance of bald cypress,Taxodium distichum,heartwood to the subterranean termite,Coptotermes formosanus

The heartwood of bald cypress,Taxodium distichum (L.) Rich., resisted feeding attack by the Formosan subterranean termite,Coptotermes formosanus Shiraki. Hexane-extracted heartwood, however, was consumed at > 12 times the amount of sound heartwood eaten. A bioassay usingT. distichum sapwood as a feeding substrate was employed to assess the antitermitic activity of successive hexane, acetone, and methanol extracts of heartwood shavings and isolates derived from the active hexane extract. Two fractions, eluted from the crude hexane extract by liquid chromatography, significantly reduced termite feeding compared to the parent extract, while a third fraction was less active than the original hexane extract. Each fraction contained one major component. All three components were structurally related diterpenes. The two most active heartwood constituents were identified by GC-MS and NMR as ferruginol and manool, while the third and least active, but most prevalent, compound in heartwood was identified as nezukol. Results of bioassays suggest that these allelochemicals act principally as feeding deterrents with accompanying termite mortality due to starvation.     

The lipids of the oriental hornet,Vespa orientalis F.

Analysis of the hornet’s hemolymph revealed the presence of C₁₆ and C₁₈ fatty acids (70%), which were accompanied by minor quantities (ranging from 0.1% to 0.6%) of the following acids: C_10∶0, C_11∶0, C_12∶0, C_13∶0, C_14∶0, C_15∶0, C_16∶0, and C_17∶0. The hemolymph of the queen larvae contained more C_18∶1 than the hemolymph of the worker larvae, and the percentage of C_16∶1 was higher in the fat body and the midgut than in the hemolymph. The significance of these results is discussed.     

Kinetic analysis of cellular internalization and expulsion of unstructured D-chirality cell penetrating peptides

Most cell penetrating peptides (CPPs) are unstructured and susceptible to proteolytic degradation. One alternative is to incorporate D-chirality amino acids into unstructured CPPs to allow for enhanced uptake and intracellular stability. This work investigates CPP internalization using a series of time, concentration, temperature, and energy dependent studies, resulting in a three-fold increase in uptake and 50-fold increase in stability of D-chirality peptides over L-chirality counterparts. CPP internalization occurred via a combination of direct penetration and endocytosis, with a percentage of internalized CPP expelling from cells in a time-dependent manner. Mechanistic studies identified that cells exported the intact internalized D-chirality CPPs via an exocytosis independent pathway, analogous to a direct penetration method out of the cells. These findings highlight the potential of a D-chirality CPP as bio-vector in therapeutic and biosensing applications, but also identify a new expulsion method suggesting a relationship between uptake kinetics, intracellular stability, and export kinetics.