Copolymers of vinyl-containing benzoxazine with vinyl monomers as precursors for high performance thermosets.

A benzoxazine containing a vinyl group (P-4va) was prepared by the reaction of phenol, 4-vinylaniline, and paraformaldehyde. A differential scanning calorimetry (DSC) study revealed that ring-opening polymerization of the benzoxazine and chain polymerization of the vinyl group occurred in the same temperature range. When 2,2'-azobisisobutyronitrile was added as a radical initiator to P-4va, however, only the vinyl groups were polymerized at lower temperature, giving oligo(P-4va) that contains pendent benzoxazine units. Radical copolymerization of P-4va with various vinyl monomers such as styrene, methyl methacrylate (MMA), and n-butyl acrylate (BuA) was examined. The chemical structure of the copolymers was confirmed by FT-IR and 1H-NMR to be one of polyolefins bearing benzoxazine units as the pendant groups. The weight-average molecular weights of the copolymers determined by size exclusion chromatography were to be in the range of 1900-51,500 depending on the comonomers. DSC of the copolymers showed that the maxima of the exothermic peaks corresponding to the ring-opening polymerization of the pendent benzoxazine units were observed in the temperature range of 229-250 °C. Thermal cure up to 240 °C of the copolymer films afforded homogenous transparent films with improved thermal properties. Tough cured film was obtained by the copolymerization with MMA, while a tough and flexible film was obtained by the copolymerization with BuA.

Separation of C70 over C60 and selective extraction and resolution of higher fullerenes by syndiotactic helical poly(methyl methacrylate).

A one-handed helical polymer, syndiotactic poly(methyl methacrylate) (st-PMMA), recognizes the size and chirality of higher fullerenes through an induced-fit mechanism and can selectively extract enantiomers of the higher fullerenes, such as C(76), C(80), C(84), C(86), C(88,) C(90), C(92), C(94), and C(96). This discovery will generate a practical and valuable method for selectively extracting the elusive higher fullerenes and their enantiomers and opens the way to developing novel carbon cage materials with optical activities.

Development of novel fiber-packed needle interface for off-line reversed-phase liquid chromatography-capillary gas chromatography.

For two-dimensional reversed-phase liquid chromatography-gas chromatography (2D RPLC-GC), a specially-designed needle packed with a polymer-coated fibrous stationary phase was introduced as a novel interface. The bundle of synthetic fibers coated with polydimethylsiloxane (PDMS) was packed into the head section of the needle, and served as the extraction medium. Using the post-column dilution of the LC eluent by water and subsequent extraction with the needle interface, the analyte was successfully concentrated to the PDMS phase on the fibrous support in the needle. The concentrated analytes were directly injected to GC system by inserting the needle to a heated GC injector. 2D separations of aliphatic and aromatic hydrocarbons, and also kerosene-extract were performed with the off-line RPLC-GC system interfaced by the needle extractor. The results suggested that the fiber-packed needle interface could be one of the simple and effective approaches to develop an on-line coupled LC-GC system.

High performance wood composites based on benzoxazine-epoxy alloys.

Wood-substituted composites from matrices based on ternary mixtures of benzoxazine, epoxy, and phenolic novolac resins (BEP resins) using woodflour (Hevea brasiliensis) as filler are developed. The results reveal that the addition of epoxy resin into benzoxazine resin can lower the liquefying temperature of the ternary systems whereas rheological characterization of the gel points indicates an evident delay of the vitrification time as epoxy content increased. The gelation of the ternary mixtures shows an Arrhenius-typed behavior and the gel time can be well predicted by an Arrhenius equation with activation energy of 35-40kJ/mol. For wood-substituted composites from highly filled BEP alloys i.e. at 70% by weight of woodflour, the reinforcing effect of the woodflour shows a substantial enhancement in the composite stiffness i.e. 8.3GPa of the filled BEP811 vs 5.9GPa of the unfilled BEP811. The relatively high flexural strength of the BEP wood composites up to 70MPa can also be obtained. The outstanding compatibility between the woodflour and the ternary matrices attributed to the modulus and thermal stability enhancement of the wood composites particularly with an increase of the polybenzoxazine fraction in the BEP alloys.

Surface derivatization of poly(p-phenylene terephthalamide) fiber designed for novel separation and extraction media.

The surface derivatization of poly(p-phenylene terephthalamide) fiber was studied. The obtained surface-derivatized filaments were packed into a fused-silica capillary to evaluate its surface characteristics by using GC. As the stationary phase for GC the surface-derivatized fibers showed higher retention for alkanes and alkylbenzenes than that with the untreated Kevlar fiber. The improvements on the retention power and the peak shape were observed on the benzyl-modified fibrous stationary phase. The derivatized fibrous materials were also evaluated as the extraction medium in fiber-in-tube SPE, and the effect of the surface modification on the extraction power was compared to the parent fiber. The results indicated that the modified fiber possessed a higher extraction power than the untreated fiber. Based on the facts, the successful modification of the fiber surface was estimated.

High-temperature separation with polymer-coated fiber in packed capillary gas chromatography.

High-temperature gas chromatographic separation of several synthetic polymer mixtures with Dexsil-coated fiber-packed columns was studied. A bundle of heat-resistant filaments, Zylon, was longitudinally packed into a short metal capillary, followed by the conventional coating process with Dexsil 300 material. Prior to the packing process the metal capillary was deactivated by the formation of a silica layer. The typical size of the resulting column was 0.3-mm i.d., 0.5-mm o.d., 1-m length, and packed with about 170 filaments of the Dexsil-coated Zylon. The column temperature could be elevated up to 450 degrees C owing to the good thermal stability of the fiber, Dexsil coating, and metal capillary; furthermore, this allowed the separation of low-volatile compounds to be studied.

Short metal capillary columns packed with polymer-coated fibrous materials in high-temperature gas chromatography.

The high-temperature gas chromatographic (GC) separation of several semivolatile compounds is studied with a short metal capillary column packed with fibrous material, having a polydimethylsiloxane coating thereon. Taking advantage of the excellent heat-resistance of the fiber and also the combination of the surface-deactivated metal capillary, a temperature-programmed separation up to 450 degrees C is successfully demonstrated for the separation of polymer standard samples. The average molecular weight of the commercially-available polymer standard samples for size exclusion chromatography (SEC) is estimated by high-temperature GC analysis and compared with the nominal value determined by a conventional SEC method. Although a slight deviation for the number-average molecular weight is observed between the GC and SEC analysis, the data for the weight-average molecular weight shows a good agreement in these methods. The results also suggest the future possibility of the fiber-packed metal capillary as a miniaturized GC column with an increased sample loading capacity.

Polymer-coated fibrous extraction medium for sample preparation coupled to microcolumn liquid-phase separations.

Polymer-coated fibrous material has been introduced as the extraction medium for a miniaturized sample preparation method being coupled with microcolumn liquid chromatography. The preconcentration and the subsequent liquid chromatographic separation of tricyclic antidepressants (TCAs) drugs, amitriptyline, imipramine, nortriptyline and desipramine, was carried out with the hyphenated system. Several basic experimental parameters, such as extraction and separation conditions, were investigated along with the applicability of the method for the analysis of biological fluids. The results clearly showed that the on-line coupled system could be a powerful tool for the analysis of complex mixtures in biological matrix without a large solvent consumption and specially designed instruments. The lowest limit of quantification was quite acceptable for the analysis of TCAs in clinical and forensic situations.

Polymer-coated fibrous materials as the stationary phase in packed capillary gas chromatography.

Synthetic polymer filaments have been introduced as the support material in packed capillary gas chromatography (GC). The filaments of the heat-resistant polymers, Zylon, Kevlar, Nomex, and Technora, were longitudinally packed into a short fused-silica capillary, followed by the conventional coating process for open-tubular GC columns. The separation of several test mixtures such as n-alkylbenzenes and n-alkanes was carried out with these polymer-coated fiber-packed capillary columns. With the coating by various polymeric materials on the surface of these filaments, the retentivity was significantly improved over the parent fiber-packed column (without polymer coating) as well as a conventional open-tubular capillary of the same length. The results demonstrated a good combination of Zylon as the support and poly(dimethylsiloxane)-based materials as the coating liquid-phase for the successful GC separation of n-alkanes and polycyclic aromatic hydrocarbons (PAHs), while successful applications for other separations such as poly(ethylene glycol) coating for the separation of alcohols were also obtained. From the results it has been suggested that the selectivity of the fiber-packed column could be tuned by selecting different coating materials, indicating the promising possibility for a novel usage of fine fibrous polymers as the support material that can be combined with newly synthesized coating materials specially designed for particular separations. Taking advantage of good thermal stability of the fibers, the column temperature could be elevated to higher than 350 degrees C with the combination of a short metallic capillary.

Miniaturized fiber-in-tube solid-phase extraction as the sample preconcentration method for microcolumn liquid-phase separations.

Miniaturized fiber-in-tube solid-phase extraction (fiber-in-tube SPE) has been developed as a solventless sample preconcentration technique for microcolumn liquid-phase separation methods. Short capillaries packed with polymer filaments were employed as the extraction tube and the preconcentration power for phthalates in aqueous solutions was studied. On the basis of the successful on-line coupling of this preconcentration method with liquid chromatography (LC), a more miniaturized extraction cartridge, which is installed in the rotor of the micro-injector, has been developed. With a modified commercially available valve, on-line coupling of this sample preconcentration method to capillary electrochromatography (CEC) was also investigated.

An attempt directed toward enhanced shape selectivity in reversed-phase liquid chromatography: preparation of the dodecylaminated beta-cyclodextrin-bonded phase.

With the aim of preparing a stationary phase with a high shape-recognition ability for liquid chromatography, a new bonded phase was synthesized by coupling multiply dodecylamino-substituted beta-cyclodextrin (beta-CD) to 3-glycidoxypropyl-derivatized silica gel. The stationary phase prepared in this way was expected to have increased shape selectivity compared with that of conventional reversed-phase materials, due to solute interactions with the alkyl chain piles built up on the beta-CDs bonded to silica. The separation characteristics of the bonded phase were investigated using polycyclic aromatic hydrocarbons (PAHs) with different molecular shapes and compared with those of monomeric ODS and native beta-cyclodextrin-bonded phases. The newly developed stationary phase was found to be highly selective for PAHs.