Acidity constants imides

The authors [1] studied kinetics of poly (amic acid) (PAA) solid-state imidization both in the presence of nanofiller (layered silicate Na+-montmorillonite) and without it. It was found, that temperature imidization 1] raising in range 423-523 K and nanofiller contents Wc increase in range 0-7 phr result to essential imidization kinetics changes expressed by two aspects by essential increase of reaction rate (reaction rate constant of first order k increases about on two order) and by raising of conversion (imidization) limiting degree Q im from about 0,25 for imidization reaction without filler at 7 i=423 K up to 1,0 at Na -montmorillonite content 7... 

In comparison, no structural modification of model B was seen before 120 h of aging (80 °C). However, after 120 h two small doublets appeared in the NMR spectrum and several additional peaks became noticeable in the NMR spectrum. It was determined by NMR and IR spectroscopy that the hydrolysis products were an imide/carboxylic acid and an imide/anhydride. Model B was then aged for 1200 h at 80 °C to quantitatively determine the amount of hydrolysis products as a function of time. The relative intensity of the peaks due to carboxylic acid is constant after some time. The authors suggest that an equilibrium occurs between model B and the products formed during hydrolysis, and therefore, the conversion to hydrolysis products is limited to about 12%. This critical fraction is probably enough to cause some degradation of polymeric materials, but research on six-membered polyimides has remained active. 

There are, however, a number of observations which argue against the viability of such a string of transfers. Firstly, the imidic acid resulting from the tautomerism is considerably higher in energy than the amide. Theoretical and experimental data provide an estimate of an 11-12 kcal/mol energy difference in formamide. The tautomeric equilibrium constant is only some The proton transfer would be impossibly slow it would take more... 

The second group of hydroxy compound derivatization reactions includes acylation of OH groups with the formation of esters. The most important are listed below (for the table of physicochemical and gas chromatographic constants of acylation reagents refer to the entry Derivatization of Amines, Amino Acids, Amides, and Imides for GC Analysis). 

Aromatic polyimides have glass transition temperatures in excess of 400 °C, excellent toughness and elongation properties and dielectric constants comparable to that of inorganic dielectrics, about 3.5. An important feature relative to these applications is their ability to planarize the topography when spun on as the soluble precursor polyamic acid. The subsequent intramolecular condensation reaction to form the heterocyclic imide is typically a thermal "curing" process. 

Lewis et al. [44] presented experimental evidence for such an assumption after measurement of the dependence of rate constants on temperature for the unimo-lecular imidization of a polyamic acid (Eq. (1), Fig. 4.2, Table 4.2). 

Another polypyrrole/polyamide composite film was obtained by the electrode coating method [84]. In this work the polyamide film was obtained in situ by coating a stainless steel electrode with a polyamic acid film followed by imidization with pyridine and acetic anhydride. The coated electrode was submitted to a constant current in a pyrrole/LiC104 solution in acetonitrile. The surface conductivity measured after detaching the composite film from the electrode showed a strong dependence on the charge density used in the synthesis, i.e. on the amount of pyrrole polymerized in the composite. The maximum value obtained was 2 S cm . Combination of polypyrrole with this polyamide was shown to increase markedly its thermal and environmental stability. 

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