树脂催化甲基丙烯酸与环己烯反应合成甲基丙烯酸环己酯.pdf

油化
?1042
PETROCHEMICAL TECHNOLOGY
2011年第40卷第10期
树脂催化甲基丙烯酸与环己烯反应合成
甲基丙烯酸环己酯
许燕,汤吉海,崔咪芬,陈献,周峰,乔旭
(南京工业大学化学化工学院,江苏南京21000
摘要』以大孔磺化苯乙烯阳离子交换树脂为催化剂,催化甲基丙烯酸与环已烯进行酯化反应,合成了甲基丙烯酸环已酯
( HMA);考察了反应温度、反应时间、催化剂用量、原料配比对酯化反应的影响;研究了催化剂的重复使用性能,并对倮化剂进行
了FTIR和BET表征。实验结果表明,大孔碳化苯乙烯系阳离子交换树脂具有较好的催化活性:合成CHMA的最佳条件为:甲基
内烯酸用量51.2g,n(甲基内烯酸)m(环己烯)=4.0,催化剂用量3%(相对于甲基丙烯酸和环己烯的总质量),巸聚剂对萃二酚
用量1%(相对于甲基丙烯胶的质量),反应温度90℃,反应时间7h:在此条件下,环己烯的转化率为89.0%,CHMA的选择性为
95.3%。该催化剂重复使用10次后,催化活性和结构基本不变。
关键词甲基丙烯酸;环己烯;甲基丙烯酸环已酯;阳离子交换树脂催化剂;酯化反应
[文章编号]1000-8144(2011)10-1042-0
L中图分类号」TQ223.16
文献标识码]A
Synthesis of Cyclohexyl Methacrylate from Methacrylic Acid and
Cyclohexene over Resin Catalyst
Xu Yan, Tang thai, Cui Mifen, Chen Xian, Zhou Feng, Qiao Xu
College of Chemistry and Chemical Engineering, Nanjing University of Technology, Nanjing Jiangsu 210009, China
Abstract Cyclohexyl methacrylate(CHMA was synthesized by the esterification of methacrylic
acid and cyclohexene over a macroporous polystyrene sulfonate cation exchange resin catalyst. The
effects of reaction temperature, reaction time, catalyst dosage and mole ratio of methacrylic acid to
cyclohexene on the esterification were investigated. The results showed that the cation exchange resin
was an efficient catalyst for the synthesis of CHMA. Under the optimum conditions of ethacrynic acid
dosage 51. 2 g, (methacrylic acid): n(cyclohexene)4.0, w(resin catalyst)(based on the total mass
of methacrylic acid and cyclohexene 3%, w(hydroquinone as inhibitor)(based on the mass of
methacrylic acid ) 1%, reaction temperature 90 C and reaction time 7 h, the conversion of cyclohexene
and the selectivity to CHMA could reach 89.0% and 95.3%, respectively. The resin catal yst could be
reused 10 times, and its activity and structure were unchanged essentially
Keywords J methacrylic acid; cyclohexene; cyclohexyl methacrylate; cation exchange resin catalyst
esterification
甲基丙烯酸环已酯(CHMA)是一种无色透明化剂催化环已醇与羧酸反应合成羧酸环己脂2。
液体,可用于制备透镜等光学材料、电器包封材料、由于浓H2SO.的腐蚀性强且化学性质活泼,因此易
胶黏剂、涂料等高性能材料。它与甲基丙烯酸甲发生炭化、重排、聚合等副反应,产品收率不高;同
酯的共聚物不但保持了聚甲基丙烯酸甲酯的光学
特性,而且降低了聚甲基丙烯酸甲酯的吸湿率,可『收稿日期!2011-04-12;[修改稿日期:2011-08-0
用于制作信息记录磁盘。以CHMA为甲基丙烯酸
作者简介]许燕(1985一),女,江苏省宜兴市人,硕士生,电邮
系树脂单体,能赋予聚合物可挠性和大的折射率
xuyan85460163.com。联系人:乔旭,电话025-83172298,电邮
qct@niut.edu.cn。
因此近年来引起人们的广泛关注。
基金项目;江苏省高校自然科学研究项日(O8KJB53000,
目前工业上普遍以无机酸(如浓H2SO4)为催W9KJA5300:南京工业大学青年教师学术基金资助项日