INDEX amines, addition

Figure 2. (a) Time dependence ofln(m(/m) for MATA polymerization without amine additive (1) and in the presence of tert-butylamine (2) (b) dependence of M (1) and the polydispersity index (2) on the conversion for polyMATA samples synthesized in the presence of complex 4 and CCI4 at 80 °C. 

There have been some examples of the use of LDMS applied to the analysis of compounds separated via TLC, although not specifically dealing with polymer additives [852]. Dewey and Finney [838] have described direct TLC-spectroscopy and TLC-LMMS as applied to the analysis of lubricating oil additives (phenolic and amine antioxidants, detergents, dispersants, viscosity index improvers, corrosion inhibitors and metal deactivators). Also a series of general organics and ionic surfactants were analysed by means of direct normal-phase HPTLC-LMMS [837]. Novak and Hercules [858] have... 

Since both molar volume and refractive index are influenced by the actual molecular species present in a solution, molar refraction has some potential value for studying association equilibria. Giles and co-workers (65-68) correlated the method with dielectric constant measurements, and have been the most active users of refractive index for studying compound formation. Reference 68 reviews earlier work (which is sketchy) and lists about forty systems (mostly oxygen containing compounds) that were studied. References 65-67 deal with amide, amine, and azo compounds, plus esters and additional work on alcohols, aldehydes, ketones, and carbohydrates. The method is simple the refractive index of a series of mixtures of varying composition but constant concentration in a solvent is measured. Compound formation is shown by a change in the slope of the n vs. mole fraction plot, such as in Fig. 2-15. 

Properties Yellow crystals or light-yellow liquid mild odor. Mp 15C, bp 51C, d 1.14 (20/20C), bulkd 10.0 lb/gal (20C), vapor has a green color and burns with a violet flame, refr index 1.3826 (20C). Polymerizes on standing or in presence of a trace of water. An aqueous solution contains monomolecu-lar glyoxal and reacts weakly to acid. Undergoes many addition and condensation reactions with amines, amides, aldehydes and hydroxyl-containing materials. Glyoxal VP resists discoloration. 

Vanadium(IV) oxy(acetylacetonate) is a blue to blue-green compound, crystallizing in the monoclinic system with refractive indexes of a, 1.520 0, 1.676 y, 1.739.7 The compound was originally believed to be a 1-hydrate but is now known to be anhydrous. It forms addition compounds with pyridine, methylamine, and other amines.8 Vanadium(IV) oxy(acetylacetonate) decomposes at elevated temperatures and has no definite melting point. The compound is soluble in ethanol, benzene, chloroform, and acetylacetone but is only moderately soluble in acetone or ethyl ether. 

Amines introduction into the polymerization mixture led also to a slight increase of polydispersity indexes, when c/o5o-rathenacarboranes were used as catalysts. Polydispersity of the formed polymers remained narrow (<1.5) in spite of little decrease of control over polymerization. The best control over polymerization was achieved in the presence of complexes 4 and 5, which are the most effective catalysts without additives. 

The rates of loss do not correlate with the rates of increase in the hydroxyl index for these systems or with the photoyellowing and uv phenomena. This indicates that the mechanism of oxidation of the amine functionality is complex. An additional feature of interest is the profile of this band loss as related to terminal amine structure. In the simple alkyl substituted systems namely diethyl, dimethyl and dibutyl there is an initial rapid loss followed by a slowing down of the rate of decrease on prolonged irradiation. However, with the oxygen containing systems namely morpholine, N-ethyl ethanolamine and N-methyl ethanolamine the rate of decrease is linear with irradiation time. Evidently, there must be two different mechanisms in operation here. The loss of these infra-red absorption bands may be due to a process of dealkylation via oxidation (see reactions later). The band situated at 2978 cm"l exhibited similar behaviour although the extent of the loss was less than that observed with the previous band and the order of rate loss was marginally different. 

Post-polymerization functionalization has also been applied to the synthesis of terpyridine-modified polymers [ 126]. In a recent approach, Schubert and colleagues employed this method to prepare poly(pentafluorostyrene) with terpyridines in the side chains [127]. First, poly(pentafluorostyrene) with a narrow polydispersity index of just 1.08 was synthesized by nitroxide-mediated polymerization. In a second step, this polymer was converted with amine-functionalized terpyridine under microwave heating, selectively substituting the para-fluorines. Addition of iron(II) sulfate to a solution of the terpyridine-functionalized polymer in a mixture of chloroform and methanol leads to gelation at a polymer concentration of 33 g In another work, Schubert and coworkers prepared metal-cross-Iinked polymer networks from linear and tri-arm PEG precursors, both functionalized with terpyridine at their OH-termini [128]. Quantitative functionalization of these precursors was achieved by conversion of the hydroxy-functionalized PEG derivatives with 4-chloro-2,2 6, 2"-terpyridine under basic conditions. However, quantitative cross-linking with iron(II) chloride was not observed in methanol solutions, neither at room temperature nor at elevated temperature, but only a small quantity of cross-linked material precipitated from the solution. This observation was attributed to a strong tendency of the tri-arm PEG to form intramolecular complexes, acting as a chain stopper rather than as a cross-linker. 

Classification Tertiary amine Empirical C12H27N Formula CH3(CH2)9N(CH3)2 Properties M.w. 185.36 dens. 0.778 (20/4 C) b.p. 234 C ref. index 1.431 cationic Storage Keep under argon sensitive to air Uses Intermediate for quat. ammonium compds., amine oxides, betaines for household prods., disinfectants, sanitizers, industrial hand cleaners, cosmetics, bubble baths, deodorants, polymer additives, PU foam catalysis, epoxy curing agent Manuf./Distrib. Fluka http //www.sigma-aldrich.com... 

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