Mass Spectrometric Behaviour of Carboxylated Polyethylene Glycols and Carboxylated Octylphenol Ethoxylates

The mass spectrometric behaviour of mono- and di-carboxylated polyethylene glycols (PEGCs and CPEGCs) and carboxylated octylphenol ethoxylates (OPECs) is discussed. The tendency for ionisation (deprotonation, protonation and cationisation by alkali–metal cations) of carboxylated PEGs was compared with that of non-carboxylated analogues by using both secondary-ion mass spectrometry (SIMS) and electrospray ionisation (ESI). The fragmentation of the PEGCs and CPEGCs is discussed and also compared with their neutral analogues, PEGs. B/E linked-scan mass spectra were recorded, using secondary-ion mass spectrometry as a method for ion generation, for deprotonated and protonated molecules as well as for molecules cationised by alkali–metal cations. The fragmentation behaviour of PEGs is found to be different from that of CPEGCs, The presence of carboxyl groups may be confirmed not only by the determination of molecular weights of the ethoxylates studied, but also on the basis of the fragment ions formed. The metastable decomposition of the [OPEC-H]− ions proceeds through the cleavage of the bond between the octylphenol moiety and the ethoxylene chain and leads to the octylphenoxyl anions. It permits determination of the mass of the hydrophobic moiety of the studied carboxylated alkylphenol ethoxylate. ESI mass spectra recorded in the negative-ion mode were found to be more suitable than SI mass spectra for the determination of the average molecular weight of carboxylated ethoxylates.