Recrystallization peak

An initial run on a 76 ug sample of Nylon 6, 6 yarn (seen in fig. 14) shows a processing effect at about 210°C, the same temperature at which this material displayed a break in the TMA extension curve. After shock cooling, the processing mark has been erased and the cold recrystallization peak appears--an indication that the glass transition is about 25°C lower. Figure 15 shows the effect of program-cooling and the characteristic nylon double peak in the subsequent melt (9). 

FIGURE 2.2 DSC trace for amorphous salbutamol sulfate, showing the glass transition, recrystallization peak, and melting/degradation peak. 

This study showed that chemiluminescence method is a useful technique to sense temperature-dependent morphological changes, that is, annealing processes, and to determine relaxation temperatures and exothermic recrystallization peaks. The use of a fluorescent molecule to amplify the chemiluminescence emission allows to application of the innovative method to all types of polymers including those with low intensity emission. 

J.K. Kruger (Universitat des Saarlandes, Saarbrucken, Federal Republic of Germany) Poly(4-methyl pentene-1) was one of the polymers that showed one of the strongest T effects. I claim that perhaps one possibility for this effect would be that between and T there are still helices existing. Would you reject this idea or could this partly be an explanation for your finding that you do not find the recrystallization peak ... 

The structure of the last eluting peak (Fig. ID, peak 10), structure is easily deduced to be 2,2, 3,3, 4,4, 5,5, 6,6 decabromo DPF from the bromine content of the pure sample, lack of proton spectrum and long retention time. Indeed, a recrystallized standard serves as reference material for a quantitative HPLC assay to be described elsewhere. 

The dichlorodibenzo-p-dioxin component was isolated by passing a dioxane solution of the mixture through acetate ion exchange resin to remove phenolics. The eluted product was recrystallized from benzene. The x-ray powder diffraction pattern of the precipitate was identical with that of 2,7-dichlorodibenzo-p-dioxin. Analysis of the mother liquor by GLC showed a singular peak consistent with 2,7-dichlorodibenzo-p-dioxin. The mother liquor was cooled to 5°C and yielded transparent crystals. This material had an x-ray diffraction pattern congruent to a sample of 2,8-dichlorodibenzo-p-dioxin obtained from A. E. Pohland (FDA). The two patterns were quite distinct from each other 14, 15). 

Tetrachlorodiben2o- >-dioxin. Purified 2,4,5-trichlorophenol (50 grams, 0.26 mole) was converted to its potassium salt and dissolved in 100 ml of bEEE. After addition of the copper catalyst and ethylene diacetate, the mixture was transferred to the bottom of a 300-ml sub-limer with chloroform. Sublimation (200°C/2 mm) yielded 14 grams (39% yield) of 2,3,7,8-tetrachlorodibenzo-p-dioxin. Mass spectral analysis revealed trace quantities of pentachlorodibenzo-p-dioxin, tetrachloro-dibenzofuran, and several unidentified substances of similar molecular weight. The combined impurity peaks were estimated to be <1% of the total integrated GLC area. The product was further purified by recrystallizations from o-dichlorobenzene and anisole. The final product had an estimated 260 ppm of trichlorodibenzo-p-dioxin as the only detected impurity. 

The o-dichlorobenzene extracts were combined and analyzed by GLC. Four peaks were observed under standard GLC conditions in the 10 to 15 min retention time range which is characteristic of hexachloro-dibenzo-p-dioxins (sample 1 in Table IV). The mixture was fractionally sublimed (120° to 175°G/1 mm). The major crop was harvested at 175 °G and recrystallized from anisole. Analysis of this material by GLG indicated that two isomeric hexachlorodibenzo-p-dioxins were present (sample 2). Overall yield (1.5 grams) of the product was 1-3% at 99+% purity, as determined by GLG and mass spectrometry. 

Otsuka et al. (107) describe [Ni(CNBu )2], as a reddish brown microcrystalline substance, which is extremely air-sensitive. It can be recrystallized from ether at —78°C, and is soluble in benzene in the latter solution the infrared spectrum (2020s, br, 1603m, 1210m) and proton NMR (three peaks of equal intensity at t8.17, 8.81, and 8.94) were obtained. Neither analytical data nor molecular weight is available on this complex. The metal-ligand stoichiometry is presumably established by virtue of the molar ratio of reactants and by the stoichiometries of various reaction products. 

Other hand, when an equimolar mixture of 2,5-DSP and l OEt is recrystallized from benzene, yellow crystals, comprising 2,5-DSP and l OEt in a molar ratio of 1 2, deposit. In the DSC curve of this crystal, a single endothermic peak is observed at 166°C, which is different from the melting point of either 2,5-DSP (223°C) or l OEt (156°C). Furthermore, the X-ray powder diffraction pattern of the crystal is quite different from those of the homocrystals 2,5-DSP and l OEt. Upon irradiation the cocrystal 2,5-DSP-l OEt affords a crystalline polymer (77i h = 1.0 dl g in trifluoroacetic acid). The nmr spectrum of the polymer coincides perfectly with that of a 1 2 mixture of poly-2,5-DSP and poly-1 OEt. In the dimer, only 2,5-DSP-dimer and l OEt-dimer are detected by hplc analysis, but the corresponding cross-dimer consisting of 2,5-DSP and l OEt is not detected at all (Hasegawa et al., 1993). These observations by nmr and hplc indicate that the photoproduct obtained from the cocrystal 2,5-DSP-l OEt is not a copolymer but a mixture of poly-2,5-DSP and poly-l OEt in the ratio 1 2. 

After the completion of the reaction, the solution was acidified to a pH of 4 with 2N sulfuric acid, followed by the addition of 50 ml of water. The solution was then extracted several times with ether. The extractant was dried over magnesium sulfate and the solvent was removed by evaporation at reduced pressure. Cold petroleum ether was then added to the resultant oily material to precipitate the product. The product was further washed with cold (10° C) petroleum ether and recrystallized several times from warm petroleum ether. The melting point of the final product was 73.5° C. Infrared spectrum of the product showed major absorption peaks relevant to the pure monomer (Figure 1). Under UV radiation, white flakes of the monomer solid turned deep blue (partial polymerization). 

X-ray diffraction studies are usually carried out at room temperature under ambient conditions. It is possible, however, to perform variable-temperature XPD, wherein powder patterns are obtained while the sample is heated or cooled. Such studies are invaluable for identifying thermally induced or subambient phase transitions. Variable-temperature XPD was used to study the solid state properties of lactose [20], Fawcett et al. have developed an instrument that permits simultaneous XPD and differential scanning calorimetry on the same sample [21], The instrument was used to characterize a compound that was capable of existing in two polymorphic forms, whose melting points were 146°C (form II) and 150°C (form I). Form II was heated, and x-ray powder patterns were obtained at room temperature, at 145°C (form II had just started to melt), and at 148°C (Fig. 2 one characteristic peak each of form I and form II are identified). The x-ray pattern obtained at 148°C revealed melting of form II but partial recrystallization of form I. When the sample was cooled to 110°C and reheated to 146°C, only crystalline form I was observed. Through these experiments, the authors established that melting of form II was accompanied by recrystallization of form I. 

Figure 3.2. Differential calorimetric curves for the molecular glasses (a) Spiro-sexiphenyl (second heating curve) and (b) Spiro-PBD (first and second heating curve). The glass transition is indicated by a characteristic step, the melting point by an endothermic peak. In (a) recrystallization occurs above Tg, which can be seen by an exothermic peak. The material in (b) forms a stable amorphous glass without recrystallization. The melting point from the first heating curve of a crystalline sample (dotted line) disappears in the second heating cycle (solid line). Only the glass transition is visible.

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