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

作　　者：王辉[1,2] 朱健 沈俭一[1] 

机构地区：[1]南京大学化学化工学院,教育部介观化学重点实验室,江苏南京210093 [2]盐城通海生物科技有限公司,江苏盐城224300

出　　处：《精细化工》2016年第1期86-91,共6页Fine Chemicals

基　　金：江苏省科技型企业技术创新资金-科技创业园内企业项目(BC2014193)

摘　　要：采用多聚甲醛二甲基醚（PODE_n）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,PODE_n同系物中PODE_2最适合代替甲醛合成双酚F。该文还考察了苯酚投料比n（Ph）∶n（PODE_2）、磷酸投料比n（PA）∶n（PODE_2）、反应温度（θ）和反应时间（Time）对以PODE_2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（PODE_2）=16.4∶1和n（PA）∶n（PODE_2）=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%。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 PODE_2 reached the maximum of 95. 8%. The selectivity decreased with the increase of n. However,the selectivity of BPF synthesis from PODEnhad obvious advantage compared with traditional synthesis technology from FA.By comprehensive consideration,PODE_2 is the best starting material for substituting FA to synthesize BPF. Meanwhile,the effects of mole ratio of phenol（ Ph） to PODE_2,mole ratio of PA to PODE_2,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 PODE_2,which were mole ratio of Ph to PODE_2 of 16. 4,mole ratio of PA to PODE_2 of 5. 49 and reaction temperature of 90 ℃. At the optimum conditions,the yield reached 99. 0% and the selectivity reached95. 8%.

关 键 词：多聚甲醛二甲基醚 双酚F 响应面优化 橡塑助剂 

分 类 号：TQ325[化学工程—合成树脂塑料工业]