双酚芴丙烯酸酯清洁生产工艺研究

Study on cleaner production process for bisphenol fluorene acrylate

双酚芴丙烯酸酯是合成光学树脂材料的重要单体,以芴酮和苯酚为起始原料,经缩合反应生成9,9-双(4-羟苯基)芴(双酚芴,Ⅰ);Ⅰ与环氧氯丙烷经醚化、消除反应制得9,9-双[4-(2,3-环氧丙氧基)苯基]芴(双酚芴二缩水甘油醚环氧树脂,Ⅱ);Ⅱ与丙烯酸经亲核加成制得9,9-双[4-(2'-羟基-3'-丙烯酰-丙氧基)苯基]芴(双酚芴丙烯酸树脂,Ⅲ)。研究结果表明:采用强酸催化工艺和弱碱中和的后处理方法,可高收率(>95.6%)、高纯度(>99.0%)和无污染的得到Ⅰ;以二甲基咪唑为催化剂合成Ⅱ,产物纯度>96.5%,收率可达92.8%;以四丁基溴化铵为催化剂,对甲氧基苯酚为阻聚剂合成产品Ⅲ,产品纯度达96.0%,收率为93.0%。三步反应的总收率可达83.0%。通过考察影响各步反应的主要因素,获得了较佳的工艺条件和清洁化生产工艺方法。

Bisphenol fluorene acrylate plays an important role in the synthesis of the optical resin material. In this study,9,9′-bis （4-hydroxyphenyl） fluorene （bisphenol fluorene, I ） is synthesized with fluorenone and phenol as raw material. 9,9′-Bis（4-oxiranylmethoxyphenyl） fluorene （bisphenol fluorene diglycidyl ether epoxy resin, I] ） is prepared by the reaction of I with epichlorohudrin. Finally, ii reacts with acrylic acid to get 9,9′-bis[4-（2′-hydroxy-3hcryloyloxy- propoxy） phenyl ] fluorene （Bisphenol fluorene acrylic resin, Ⅲ ）. The results indicate that the yield of I is more than 95.6% and the purity is up to 99.0% when using the acid catalyzed process and the weak base in the post-process. Moreover,in the presence of dimethylimidazole, the yield of II is up to 92. 8% and the purity is more than 96. 5%. Finally ,when using tetrabutylammonium bromide as the catalyst and methoxyphenol as the inhibitor agent, the purity of Ⅲ is 96. 0% and the yield is 93.0%. The total yield of three steps is 83.0%. The clean production technology is optimized by studying the main factors affecting the reactions.