多聚甲醛二甲基醚在双酚F合成中的应用

Application of Polyoxymethylene Dimethyl Ethers in the Synthesis of Bisphenol F

摘要:

采用多聚甲醛二甲基醚（PODEn）代替甲醛与苯酚(Ph)在磷酸（PA）催化下反应合成双酚F。结果显示，随着n（n=1～5）的增加，双酚F的收率呈现为抛物线型，先增加后减小。当n为2时，双酚F的收率达到最大，为95.8%。而双酚F的选择性随n的增加而逐渐减小。与传统的以甲醛为原料合成双酚F相比，以PODEn为原料合成双酚F具有显著的高选择性优点。综合比较，PODEn同系物中PODE2最适合代替甲醛合成双酚F。本文还考察了苯酚投料比〔n(Ph):n(PODE2)〕、磷酸投料比〔n(PA):n(PODE2)〕、反应温度（T）和反应时间（Time）对以PODE2为原料合成双酚F的收率、选择性和产物分布的影响。在单因素实验基础上，采用响应面法优化，建立了双酚F收率的二次线性回归方程，获得了最佳的工艺条件。在反应温度90 ℃、n(Ph):n(PODE2)=16.4:1和n(PA):n(PODE2)=5.49:1操作条件下，双酚F的收率和选择性分别可达99.0%和95.8%。

Abstract:

Bisphenol F (BPF) was synthesized from polyoxymethylene dimethyl ethers (PODEn, n=1～5) instead of formaldehyde (FA) of traditional process catalyzed by phosphorous acid (PA). Results showed that the yield of BPF was parabolic with the increase of n under the same temperature, that is, the yield firstly increased and then decreased. And the yield of BPF synthesis from PODE2 reached the maximum of 95.8%. The selectivity decreased with the increase of n. However, the selectivity of BPF synthesis from PODEn had obvious advantage compared with traditional synthesis technology from FA. By comprehensive consideration, PODE2 is the best starting material for substituting FA to synthesize BPF. Meanwhile, the effects of mole ratio of phenol (Ph) to PODE2, mole ratio of PA to PODE2, reaction temperature and reaction time on yield, selectivity and isomer distribution were also investigated. Based on single factor experiments, response surface methodology (RSM) was conducted to create a quadratic regression equation and obtain the optimal conditions of BPF synthesis from PODE2, which were mole ratio of Ph to PODE2 of 16.4, mole ratio of PA to PODE2 of 5.49 and reaction temperature of 90 ℃. At the optimum conditions, the yield reached 99.0% and the selectivity reached 95.8%.