Study On The Reaction Mechanism And Synthesis Of Bis(Hydroxylethyl Ether) Of Bisphenol A

Bis(hydroxyethyl ether) of bisphenol A(BHE-BPA) is an important chemical with hydroxyls, which can be used to produce polyesters, polyurethanes, polycarbonates and some other kinds of function polymers. The aromatic ring and the carbon oxygen chain structure in BHE-BPA can provide special strength and tenacity respectively for the polymers to improve properties. As a result BHE-BPA shows a very broad application prospect. In this dissertation, the reaction was carried out with bisphenol A(BPA) and ethylene oxide(EO) as reactants and BPA and ethylene carbonate(EC) as reactants. The effects of reaction conditions on the reaction had been studied through experiments, and the reaction mechanisms had been studied through theory calculations.Firstly, BHE-BPA was synthesized with BPA and EO catalyzed by triphenylphosphine at125℃. The di-butyl ether had been considered as the better reaction solvent. On this basis, the effects of BPA and EO molar ratio, di-butyl ether and BPA mass ratio, solvent reuses on the BHE-BPA selectivity had been studied. The results showed that the optimum BPA and EO molar ratio is1:2.3, the optimum di-butyl ether and BPA mass ratio is1.25:1, the solvent can be reused for many times and shows no significant effect on reaction selectivity, which would be of great experimental and theoretical importance to develop continous BHE-BPA synthesis technology.Secondly, BHE-BPA was synthesized with BPA and EC catalyzed by triphenylphosphine at160℃, and the reaction was confirmed to be a reaction in series by analytical experiments. The effects of temperature and catalyst types on BPA conversion and BHE-BPA selectivity had been studied. The results showed that BPA conversion increases as the reaction temperature increases, BPA conversion is larger when catalyzed by potassium carbonate and BPA conversion is lower when trioctylamine or triphenylphosphine is used as catalysts. The effect of temperature and catalyst types on the reaction selectivity is not significant, the relationships between BHE-BPA selectivity and BPA conversion under different reaction conditions are similar, which indicates that the reactions catalyzed by different catalysts follow the same mechanism.Lastly, the reaction mechanism had been studied by quantum chemistry calculation methods and the results indicated the related mechanisms are as following:With the action of catalyst, BPA dissociated to form BPA phenol anion that acted as the nucleophile, which attacked the methylene carbon atom of EO molecule to produce the ring-opening product, which then reacted with BPA to get mono(hydroxyethyl ether) of BPA(MHE-BPA). And BHE-BPA can be synthesized from MHE-BPA through above reaction processes. On the other hand, BHE-BPA alcohol anion coud also act as the nucleophile attacking EO to finally produce the by-products tri(hydroxyethyl ether) of BPA(THE-BPA). While the other by-product named o-THE-BPA was produced from isomerized MHE-BPA and EO.When BPA reacted with EC, BPA dissociated to form BPA phenol anion which acted as the nucleophile with the function of catalyst, the nucleophile attacked the methylene carbon atom of EC molecule to produce the ring-opening product, which eliminated CO2molecule through decarboxylation and reacted with BPA to form MHE-BPA. BHE-BPA can be synthesized from MHE-BPA through above reaction processes. The by-product THE-BPA was produced when BHE-BPA alcohol anion reacted with EC. In addition, BHE-BPA alcohol anion could also attack the carbonyl carbon atom of EC and produced another by-product which contained the carbonate structure and named BHE-BPA-C.