Polyarylates (I): Investigation of the interfacial polycondensation reaction by UV

The interfacial polycondensation of bisphenol A with isophthaloyl chloride and terephthaloyl chloride in dichloromethane with triethylbenzylammonium chloride as the catalyst was described. A well-defined two-phase system had been observed, so the concentration of bisphenolate in the aqueous phase could be determined by UV spectrometer. The conversion was found to increase rapidly with reaction time, but the rate of increase in molecular weight was slow. At the initial stage with conversion up to 95%, the reaction proceeded similarly to that of solution polycon-densation because the synthesized polyarylate could be dissolved in dichloromethane, and a polymer with a low molecular weight resulted. At the final stage of the reaction, the molecular weight was increased to a very high value due to the local concentration effect. The mole ratio of bisphenol A to diacid chlorides was found to affect the molecular weight very much. In the case of a mole ratio less than 1, the reaction remained in the initial stage mostly, and the molecular weight was low. However, for a mole ratio greater than 1, polyarylate with a very high molecular weight could be obtained because the local concentration effect was much more significant owing to the high concentration of bisphenolate that remained in the aqueous phase at the final stage.     

Polyarylates. IV. Synthesis of block copolymers via two-step interfacial polycondensation

A new method for preparing block copolyarylates via two-step interfacial polycondensation is proposed. First, oligomers with acid chloride end groups were obtained from interfacial polycondensation with a mole ratio of bisphenol A to diacid chloride(s) less than I. In the second step, two reaction systems containing various oligomers were mixed thoroughly and more bisphenolate was charged into this mixture. The synthesis of the block copolyarylates was justified from the viewpoint of statistics, and of differences in molecular weight between oligomers and block copolymers. These block copolyarylates could be differentiated from polyarylates through crystal-line behavior and solubility in m-cresol analyses.     

Persulfate Oxidation and Diphenylcarbazide Photometric Determination of Chromium in Super Alloys

The quantitative analysis of Cr in super alloys with the presence of a wide variety of elements, Al, B, C, Co, Cu, Hf, Fe, Mn, Mo, Ni, Nb, P, Si, S, Ti, Ta, W, Zr; and trace amounts (a few ppm) of Pb, Se, Bi, Tl and Te has been studied. Persulfate oxidation and diphenylcarbazide photometric method were studied with the purpose of developing a relatively fast and reliable measurement for Cr by wet chemical analysis. The results indicate that the latter is supperior to the former in practical view. In the photometric method, solid sample (0.1g alloys) when treated with HClO₄ and H₂SO₄ took ca. 72 hrs. for complete dissolution. When treated with HCl followed by HNO₃, 0.1 g alloys were completely dissolved within 1&1/2; hours. The best experimental conditions for diphenylcarbazide photometric determination of Cr was thus established. Photometric determination of Cr complexes was made at 540 nm.     

Mass spectra of aryl substituted N-t- butylbenzamides: Substituent effects on unimolecular ion decomposition

The major reactions of aryl substituted N-t-butylbenzamides upon electron-impact involve direct cleavage of a methyl radical, the loss of a butene molecule with the transfer of one hydrogen, or the loss of a butenyl radical with the transfer of two hydrogens. The last of these processes parallels the mass spectral behavior of aliphatic amides. Substituent effects indicate that electron-withdrawing groups on the aromatic ring enhance the two hydrogen transfer process, while electron-donating groups enhance the single hydrogen transfer process. Ion abundances, ionization potentials and appearance potentials are discussed with respect to correlation with σ⁺ values.     

Preparative isolation of terpene trilactones from Ginkgo biloba leaves

This study investigated and compared some techniques for the preparative isolation of terpene trilactones, including ginkgolides (GA and GB, etc.) and bilobalide (BB), from Ginkgo biloba leaves. The crude Ginkgo biloba L. extracts (GBE) were prepared using an extractor with solvent refluxing operated under an optimal extraction condition. The extraction yield was 20-23% and the purity of terpene trilactones was about 1.0-1.4 wt%. Before the isolation operations, the extracts were dissolved in de-ionized water. The isolation procedures included the method of liquid-liquid extraction and the method of column chromatography. For the method of liquid-liquid extraction using ethyl acetate as the organic solvent operated under the optimal extraction conditions, the purity, concentration ratio, and yield of terpene trilactones were 13.5-18.0%, 15-16, and >99%. For the method of column chromatography, XAD-7HP, XAD-4, and C-18 adsorbents with different polarities were used as the packing materials. Only for the XAD-7HP column, a part of more polar impurities was efficiently separated with the majority of terpene trilactones by a proper step-gradient elution, which resulted in an efficient isolation: the purity, concentration ratio, and yield of terpene trilactones were approximately 20, approximately 15, and approximately 80%. In comparison, the XAD-7HP column achieved the highest purity, but at the expense of the yield of terpene trilactones; on the contrary, the liquid-liquid extraction method, achieving the highest yield but with a slightly lower purity, was proved to be superior to the method of column chromatography in the current isolation stage.     

Impurity analysis of 1,4-dioxane in nonionic surfactants and cosmetics using headspace solid-phase microextraction coupled with gas chromatography and gas chromatography-mass spectrometry

1,4-Dioxane impurity in nonionic surfactants and cosmetics were analyzed using solid-phase microextraction (SPME) coupled with gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). Experimental results show that there is no significant difference using SPME-GC and SPME-GC-MS for analysis of 1,4-dioxane in three types of nonionic surfactants at the 95% confidence level. The relative standard deviation (R.S.D.) values of each analytical method were smaller than 3%. The amount of 1,4-dioxane was found to vary from 11.6 +/- 0.3 ppm to 73.5 +/- 0.5 ppm in 30% of nonionic surfactants from manufacturers in Taiwan. These methods were linear over the studied range of 3-150 ppm with correlation coefficients higher than 0.995. The recoveries of 1,4-dioxane for these nonionic surfactants following SPME were all higher than 96 +/- 1% (n = 3). The detection limits of 1,4-dioxane for these nonionic surfactants following SPME were from 0.06 ppm to 0.51 ppm. The experimentally determined level of 1,4-dioxane in cosmetics from manufacturers in Taiwan varied from 4.2 +/- 0.1 ppm to 41.1 +/- 0.6 ppm in 22% of daily used cosmetics following SPME coupled with GC and GC-MS. Conventional solvent extraction takes around 1 h for extraction and reconcentration but SPME takes only around 10 min. SPME provides better analyses of 1,4-dioxane in nonionic surfactants and cosmetics than conventional solvent extraction and head space pretreatments in term of simplicity, speed, precision, detection limit, and solvent consumption.     

Spectrophotometric Determination of Titanium in Super Alloys with Diantipyrylmethane and Tiron

Diantipyrylmethane and tiron spectrophotometric determinations of Ti in the super alloys, Inconel 718 and Inconel 600, have been studied thoroughly. Both reagents formed stable yellow complexes with Ti(IV) in acidic medium. The possible interference from Ni, Fe and Cr was examined. Interference from Fe(III) was eliminated by the reduction of Fe(III) to Fe(II). Cr was removed as chromyl chloride which led to a dramatic improvement in the analytical results for Ti by the tiron photometric method. However, the removal of Cr was not necessary when the diantipyrylmethane method was employed. Consequently, lengthy manipulation of super alloys was required for the tiron determination. These two spectrophotometric methods are compared in terms of simplicity, reproducibility and accuracy.     

Solution behavior of ampholytic styrene ionomers

In this article are described the solution properties of ampholytic ionomers obtained by the radical copolymerization of styrene with the ion-pair comonomer 3-methacrylamidopropyltrimethylammonium, 2-acrylamido-2-methylpropanesulfonate. The solution properties were studied in mixed solvents, with a good solvent for the polystyrene backbone and another for the ionic moieties, and in the individual good solvent of benzyl alcohol. The data obtained strongly support extensive intermolecular ionic interactions in solution.