用于合成油酸甲酯的两类聚环糊精固相催化剂的研究  

Study on two poly-cyclodextrin-based solid phase catalysts for the preparation of methyl oleate

作　　者：赵珺[1,2] 闵书学 陈国[1] 王晓琴[1,2] 

机构地区：[1]华侨大学化工学院生物工程与技术系,福建厦门361021 [2]华侨大学油脂及天然产物研究所,福建厦门361021

出　　处：《化学研究与应用》2016年第3期331-337,共7页Chemical Research and Application

基　　金：福建省自然科学基金项目(2013J05028)资助;华侨大学引进人才科研启动项目(11BS408)资助

摘　　要：以环氧氯丙烷交联β-环糊精,制备了CroCD-H和CroCD-Cu两类固相催化剂,并分别用于油酸甲酯的合成。对CroCD-H催化油酸的酯化反应动力学进行考察,表明此反应符合油酸浓度的准一级反应,催化剂中磺酸基含量直接影响酯化反应速率,其中CroCD-H5磺酸基含量可达5.82%,催化反应8 h,油酸转化率大于90%,且多次重复使用稳定性良好。而在三油酸甘油酯与甲醇的酯交换反应中,CroCD-Cu表现出较强的催化能力,其催化机理可能与双核铜复合物的Cu桥键四元环结构有关,通过其OH-/O_2-碱性中心作用和Cu—O键可逆断裂实现酯交换。采用XRD谱对CroCD-Cu催化酯交换反应前后的结构进行研究,揭示了其失活过程可能与Cu桥键被破坏有关。Two solid phase catalysts of CroCD-H and CroCD-Cu were prepared through crosslinking of β-cyclodextrin with epichlorohydrin.They were both used for the synthesis of methyl oleate. The esterification kinetics of oleic acid with methanol catalyzed by CroCD-H was investigated.The results indicated that it was corresponded to pseudo-first-order reaction according to oleic acid concentration,and the sulfonic acid group content directly influenced the reaction rate. The sulfonic acid group content of CroCD-H5 reached to 5. 82%,through whose catalysis the oleic acid conversion was above 90%in 8 h.It also showed excellent catalytic stability for esterification with many repeats.Another catalyst CroCD-Cu showed dramatic catalytic ability to the ester exchange reaction between glycerol trioleate and methanol.The catalytic mechanism might refer to the structure of the Cu-bridge quaternary-ring in this double-copper（Ⅱ） complex,and the ester exchange reaction might be occurred according to the action of OH^-/ O^2-base-center and reversible breakage of Cu—O bond.The XRD spectra were introduced to study the structure of CroCD-Cu both before and after the ester exchange reaction.It revealed that the deactivation process was probably due to destruction of the Cu-bridge bond.

关 键 词：环糊精 环氧氯丙烷 油酸甲酯 磺酸 双核铜复合物 

分 类 号：O636.1[理学—高分子化学]