对叔丁基苯酚羟基化反应的研究.pdf

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PETROCHEMICAL TECHNOLOGY
2011年第40卷第6期
精细化工
对叔丁基苯酚羟基化反应的研究
赵亮亮,杨元法,李艳妮,刘兰香,朱玉梅
(浙江师范大学物理化学研究所浙江省固体表百反应化学重点实验室,浙江金华321004)
「摘要采用Fe(OH)+有机络合剤+H2O:系统,对羟基化法由对叔丁基苯酚(FTBP)制备对叔丁基邻苯一酚(4ーTBC)的反应
进行了研究。探讨了反应时间、反应温度、催化剂用量、(H2O2):n(PIBP)、溶剂类型等闲素反应的影响。实验结果表明,溶
剂类型和n(H2O2):(PIBP)对催化剂的活性影响较大。在PIBP0.80g、n(H1O2):(PIBP)=1.0、乙脯水溶液(こ睛与水体
积比2:1)30mL、Fe(OH);0.058、邻苯二酚0.058、反应温度55℃、反应时间60min的条件下,PIBP转化率可达8.5%,4
TBC选择性达89.2%。对反应机理的探索表明,Fe++H22系统中的羟基白由基(?OH)不能对PTBP进行羟基化反应;Fe+
有机络合剂+H1O2系统中以活性铁氧终合物为氧化剂,与有机酚类反应物有良好的反应亲和力,能顺利完成PIBP的羟基化
关鍵词』]对叔」堪邻苯二酚;胫基化繼化剂;对叔丁基苯酚;邻苯二盼;铁氧络合物
[文章编号]1000-8144(2011)06-0624-06
中图分类号]TQ032.4
文献标识码]A
4-tert-butyl-phenol Hydroxylation
Zhao Liangliang, Yang Yuanfa, Li Yanni, Liu Lanxiang, Zhu ume
Institute of Physical Chemistry, Zhejiang Normal University, Zhejiang Key Laboratory for Reactive Chemistry on Solid urface
Jinhua Zhejiang 321004, China
Abstract]4-tert-butylcatechol(4-tbc) was synthesized from 4-tert-butyl-phenol(PTBP) by
hydroxylation with Fe(OH); +organic complexing agent+H2 O2 system. Effects of reaction time
reaction temperature, catalyst dosage, n(H, O, ) n(PTBP), solvent type and cocatalyst dosage on the
hydroxylation were investigated. The results showed that the solvent type and n(H2 2): n(PBP
played important roles in the hydroxylation. Under the conditions: PTBP 0.80 g, n(H2 O2
n(PTBP)=1.0, acetonitrile-water mixture( volume ratio 2: 1)as the solvent 30 ML, Fe(OH), 0.05
and catechol as the cocatalyst and complexing agent 0.05 g, reaction temperature 55 C and reaction
time 60 min. PTBP conversion was 18.5% and selectivity to 4-TBC reached 89.2%. Discussion o
the reaction mechanism showed that PTRP could not be hydroxylated by hydroxyl radical(OH)
formed in Fe"+H, O, system: in Fe"+organic complexing agent +H, O, system, an active iron.
oxygen complex was formed, which had good affinity with the reactant PTBP
I Keywords] 4-tert-butylcatechol; hydroxylation catalyst; 4-tert-butyl-phenol; catechol; iron-oxygen
complex
对叔丁基邻苯二酚(4-TBC)是一种重要的精成4-TBC。根据烷基化试剂不同,可分为叔丁醇
细化工产品,主要用作烯烃单体蒸馏或贮运时的高法、异丁烯法和甲基叔丁基醚法。在适当催化剂存
效阻聚剂,特别适用于苯乙烯、丁二烯以及其他乙在下,烷基化法的产品收率很高,具有很好的工业
烯单体。目前4-TBC已被美国ASTM指定为苯
乙烯等通用的阻聚剂山。此外,4-TBC也可作为
收稿日期12010-12-09;[修改稿日期]2011-04-01
作者简介]赵亮亮(1984-),男,河北省正定县人,项土生,电邮
抗氧剂和杀虫剂的稳定剂
zhaoliang3205@163,com。联系人:杨元法,电话0579-8282234,电
目前国内外基本采用邻苯二酚烷基化法2合郎sky689 Z]nu. chn