Molar mass determination by end group analysis ‐ amino group determination in aliphatic and partially aromatic polyamides with 1‐fluoro‐2,4‐dinitrobenzene in benzyl alcohol

Abstract

AbstractEnd group analysis is the most important absolute method of obtaining number‐average molar mass values for polymers of the step‐growth polymerization type. A great number of methods are available which primarily differ in the detection of the end group concerned. Special chemical methods based on the formation of covalent derivatives of the end groups (e.g. introduction of UV/VIS chromophores) are important if there is a need to demonstrate, with the aid of gel permeation chromatography, that damage to the polymer (e.g. onset of cross‐linking) has occurred.In the case of fibre‐forming polycondensation products, the applicability of end group analysis is often restricted by the lack of suitable reagents and solvents. This is also true of the determination of amino end groups in polyamides by means of 1‐fluoro‐2,4‐dinitrobenzene, as is already contained in the German Standards specification (DIN 54 274) ‐ albeit only for polyamide 6 and 6,6. This contribution describes a modified version of the 1‐fluoro‐2,4‐dinitrobenzene method. The analytical principle and practical procedure correspond to those of DIN 54 274, but the solvent used for the reaction with the reagent is benzyl alcohol, and that for the photometric evaluation is 1,1,1,3,3,3‐hexafluoro‐2‐propanol. The scope of the method is thus increased. Examples of applications for this method are commercial products based on aliphatic polyamides (6; 11; 12; 6,6; 6, 12), partially aromatic polyamides (2,4,4‐trimethylhexamethylenediamine, terephthalic acid; copolyamides with bis‐(4‐aminocyclohexyl)propane(2), isophthalic acid, ω‐aminododecanoic acid) and multicomponent systems with the abovementioned polyamides (bicomponent fibres, blends). It is shown that large differences may arise between the value determined by titration and the actual amino end group content. In addition, the presence of secondary amino groups can be demonstrated in polyamides of the Trogamid T type.