A novel method for determination of polyester end-groups by NMR spectroscopy

An efficient, convenient and quantitative method for characterising polyester end-groups is described. We have found that trichloroacetyl isocyanate (TAI) reacts rapidly and quantitatively with both carboxyl [C(O)OH] and hydroxyl (OH) chain ends to form derivatives that can be readily determined by 1H NMR spectroscopy. The TAI capped end-groups give rise to characteristic imidic NH resonances in a normally clear region of the 1H NMR spectrum [δ∼10-11.5 for C(O)-O-C(O)-NH-C(O)CCl3 from C(O)OH, δ∼8-9 for O-C(O)-NH-C(O)CCl3 from OH]. The method has been successfully applied to quantitative determination of the end-groups of a wide variety of oligomeric polyesters. It has also been applied to higher molecular weight polyesters including commercial, bottle grade, poly(ethylene terephthalate) (PET) and PET based copolyesters (e.g. PETG).