Synthesis Of Polyether And Its Components Identifycation

As an important member of nonion surfactant, polyethers are nontoxic, have a good stability for its existing in water in the form of molecule, behaves well dissolution with other kinds of surfactants, and shows wonderful capability of antifoam, emulsification and detergent. It has been widely used in many household and industrial for these superiorities, and the kinds and the capacities of it are increasing with the development of the petroleum industry. Usually, the polyethers have a relatively large molecular weight, and are very complex in its components and structure. However, some of these differences will arouse great difference in the polymer's properties. So far, the structural analysis of nonion surfactants is either a challenge work for analysts.In this paper, polyoxyethylene 4-tert-butyl-cresol, polyoxyethylene 2-tert-butyl-benzene-1,2-diol and oxyethylene- oxypropylene copolymer(EP3) are synthesized, and identified roundly by many modern methods as follows:1. The samples of 4-ter-butyl — benzene-1,2-diol poly oxyethylene and 2-ter-butyl-benzenz-1,2-diol poly oxyethylene were analyzed by using FT-ICR-MS. It was found that FT-ICR-MS is a good method for identifying the oligomer with relative sample components. The molecular formulas of the peaks in the spectra were obtained by taking the super mass accuracy of FT-MS. From the plot of mass weight of each series of peaks in the spectra Vs its polymerization degree, the accurate mass of the repeat unit was attained, and the real polymerization degree of each peak was obtained according to the mass of the end groups. A series of peaks raised from the impurity of polyoxyethylene di-tert-butyl-benzene-diol were detected in both of the spectra. The polymerization parameter and the content of main component in the samples were acquired on the basis of the data in the mass spectra.2. The copolymer sample EP3 was seperated by liquid column chromatography, which used silicon gel (300 mesh) as stationary phase and chloroform - ethanol as the mobile phase gradient eluantion program. The components were eluted according to its polarity from the weak to the strong. Besides, the components of polyoxypropythene and the PO/EO/PO block copolymer were separated from the sample, which were identified by IR, ~1H-NMR and13C-NMR.3. The EO/PO molar ratio of the two components of EP3, which were separated by liquid column chromatography, was acquired by using 'H-NMR data. The assignment of the 13C-NMR peaks of the EP3 components were made with the help of its DEPT spectra and reference data. And from the 13C-NMR data, many structure information were obtained: the sample was identified to be a block copolymer, and its sequence to be PO/EO/PO, and some two block of the copolymer PO/EO components were also detected; the molar ratios of EO/PO were calculated either.4. The two components of EP3 were analyzed by using FT-ICR-MS. The molecular formulas of the peaks in the mass spectra were obtained according to the super mass accuracy of FT-MS, and two components with molecular weight difference at 0.03amu were separated and identified by taking the advantage of its the super mass resolution. It was found that some of the end group in the polymer has lost hydroxyl and formed double carbon bond —O— CH=CH—CH3, which was confirmed by IR spectra, and that the more content of EO, the more easily it loses hydroxyl. Besides, great difference of the ratio and serious mass discrimination was found to be in the measurement of the intricate copolymer by ESI-MS.