Catalytic characteristics of N-hydroxyphthalimide immobilized on polymer microspheres in oxidation of benzyl alcohol by molecular oxygen

doi:10.11949/j.issn.0438-1157.20141572

Abstract

Abstract:

Crosslinked polymeric microspheres GMA/MMA of glycidyl methacrylate (GMA) and methyl methacrylate (MMA) were prepared, and then N-hydroxyphthalimide (NHPI) was synthesized and immobilized on GMA/MMA microspheres through several polymer reaction steps, resulting in the functionalized microspheres GMA/MMA-NHPI. The solid catalyst GMA/MMA-NHPI in combination with Co(OAc)₂ was used in aerobic oxidation of benzyl alcohol. Experimental results showed that the composite catalyst consisting of GMA/MMA-NHPI and Co(OAc)₂ could effectively catalyze aerobic oxidation of benzyl alcohol by molecular oxygen under mild conditions (65℃ and normal pressure). Benzyl alcohol was deeply oxidized to benzoic acid. Although benzyl alcohol conversion rate was not very high, catalytic activity was satisfactory and benzoic acid selectivity was as high as 96%. The appropriate molar ratio of immobilized NHPI on GMA/MMA-NHPI microspheres to Co(OAc)₂ was 20:1, and the appropriate amount of GMA/MMA-NHPI was 10% (mol) of the substrate. The solid catalyst GMA/MMA-NHPI microspheres showed good recycling and reusing performance.

Key words: N-hydroxyphthalimide, benzyl alcohol, oxidation, catalysis, catalyst support

摘要：

以甲基丙烯酸缩水甘油酯(GMA)和甲基丙烯酸甲酯(MMA)的交联共聚微球GMA/MMA为基质,经过几步大分子反应在微球表面合成与固载了N-羟基邻苯二甲酰亚胺(NHPI),形成固载有NHPI的聚合物微球GMA/MMA-NHPI。将GMA/MMA-NHPI与Co(OAc)₂组成共催化体系,用于分子氧氧化苯甲醇的反应过程。研究结果表明,GMA/MMA-NHPI与Co(OAc)₂所构成的共催化体系在温和条件(65℃和常压氧气)下可有效地实现苯甲醇的分子氧氧化过程,将其深度氧化为苯甲酸,显示出较好的催化活性和高的选择性(苯甲酸的选择性为96%)。主催化剂GMA/MMA-NHPI固载的NHPI与助催化剂Co(OAc)₂适宜的摩尔比为20:1;主催化剂所含NHPI的摩尔分数为底物的10%时催化剂的用量比较适宜。固体催化剂GMA/MMA-NHPI还具有良好的再循环使用性能。

关键词: N-羟基邻苯二甲酰亚胺, 苯甲醇, 氧化, 催化, 催化剂载体

CLC Number:

O632

YANG Xiaolin, HUANG Jianlong, GAO Baojiao, MEN Jiying. Catalytic characteristics of N-hydroxyphthalimide immobilized on polymer microspheres in oxidation of benzyl alcohol by molecular oxygen[J]. CIESC Journal, 2015, 66(4): 1318-1323.

杨晓林, 黄建龙, 高保娇, 门吉英. 聚合物微球固载的N-羟基邻苯二甲酰亚胺在分子氧氧化苯甲醇反应过程中的催化特性[J]. 化工学报, 2015, 66(4): 1318-1323.

References 20

[1]	Ferreira P, Phillips E, Rippon D, Tsang S C. Catalytic oxidation of alcohols using molecular oxygen mediated by poly(ethylene glycol)- supported nitroxyl radicals [J]. Applied Catalysis B:Environmental, 2005, 61 (3/4): 206-211
[2]	Lahtinen P, Lankinen E, Leskelä M, Repo T. Insight into copper oxidation catalysts: kinetics, catalytic active species and their deactivation [J].Applied Catalysis A:General, 2005, 295 (2): 177-184
[3]	Shen H Y, Mao H L, Ying L Y, Xia Q H. Photocatalytic selective aerobic oxidation of alcohols to aldehydes and ketones by HPW/MCM-41 in ionic liquids [J].Journal of Molecular Catalysis A:Chemical, 2007, 276 (1/2): 73-79
[4]	Yoshida A, Takahashi Y, Ikeda T, Azemoto K, Naito S. Catalytic oxidation of aromatic alcohols and alkylarenes with molecular oxygen over Ir/TiO2 [J]. Catalysis Today, 2011, 164 (1): 332-335
[5]	Gilhespy M, Lok M, Baucherel X. Polymer-supported nitroxyl radical catalysts for the hypochlorite and aerobic oxidation of alcohols [J]. Catalysis Today, 2006, 117 (1/2/3): 114-119
[6]	Lin L, Ji L Y, Wei Y Y. Base promoted aerobic oxidation of alcohols to corresponding aldehydes or ketones catalyzed by CuCl/TEMPO [J].Catalysis Communications, 2008, 9 (6):1379-1382
[7]	Suzuki M, Ishikawa T, Harada A, Ohba S, Sakamoto M, Nishida Y. Chemical mechanism of dioxygen activation by manganese (Ⅲ) Schiff base compound in the presence of aliphatic aldehydes [J].Polyhedron, 1997, 16 (15): 2553-2561
[8]	Lahtinen P, Ahmad J U, Lankinen E, Pihko P, Leskelä M, Repo T. Organocatalyzed oxidation of alcohols to aldehydes with molecular oxygen [J].Journal of Molecular Catalysis A:Chemical, 2007, 275 (1/2): 228-232
[9]	Seyedi S M, Sandaroos R, Zohuri G H. Novel cobalt (Ⅱ) complexes of amino acids-Schiff bases catalyzed aerobic oxidation of various alcohols to ketones and aldehyde [J]. Chinese Chemical Letters, 2010, 21 (11): 1303-1306
[10]	Ahmad J U, Figiel P J, Räisänen M T, Leskelä M, Repo T. Aerobic oxidation of benzylic alcohols with bis(3,5-di-tert-butylsalicylaldimine) copper (Ⅱ) complexes [J]. Applied Catalysis A:General, 2009, 371 (1/2): 17-21
[11]	Wang X L, Liang X M. Aerobic oxidation of alcohols to carbonyl compounds catalyzed by Fe(NO3)3/4-OH-TEMPO under mild conditions [J]. Chinese Journal of Catalysis, 2008, 29 (9): 935-939
[12]	Rajabi F, Karimi B. Efficient aerobic oxidation of alcohols using a novel combination N-hydroxy phthalimide (NHPI) and a recyclable heterogeneous cobalt complex [J]. Journal of Molecular Catalysis A: Chemical, 2005, 232 (1/2): 95-99
[13]	Kishioka S-ya, Yamada A. Kinetic study of the catalytic oxidation of benzyl alcohols by phthalimide-N-oxyl radical electrogenerated in acetonitrile using rotating disk electrode voltammetry [J]. Journal of Electroanalytical Chemistry, 2005, 578 (1): 71-77
[14]	Sheldon R A, Arends I W C E. Catalytic oxidations mediated by metal ions and nitroxyl radicals [J]. Journal of Molecular Catalysis A:Chemical, 2006, 251 (1/2): 200-214
[15]	Ishii Y, Sakaguchi S, Iwahara T. Innovation of hydrocarbon oxidation with molecular oxygen and related reactions [J]. Advanced Synthesis and Catalysis, 2001, 343 (5): 393-427
[16]	Gilhespy M, Lok M, Baucherel X. Polymer-supported nitroxyl radical catalysts for the hypochlorite and aerobic oxidation of alcohols [J]. Catalysis Today, 2006, 117 (1/2/3): 114-119
[17]	Wang F, Ueda W. Selective oxidation of alcohols using novel crystalline Mo-V-O oxide as heterogeneous catalyst in liquid phase with molecular oxygen [J]. Catalysis Today, 2009, 144 (3/4): 358-361
[18]	Yang Xiaolin (杨晓林), Gao Baojiao (高保娇), Huang Jianlong (黄建龙). Preparation of immobilized N-hydroxyphthalimide catalyst on polymeric microspheres and primarily investigating its catalytic property in oxidation reaction [J]. Journal of Functional Polymers (功能高分子学报), 2014, 27 (3): 35-41
[19]	Fatemeh R, Babak K. Efficient aerobic oxidation of alcohols using a novel combination N-hydroxy phthalimide (NHPI) and a recyclable heterogeneous cobalt complex [J]. Journal of Molecular Catalysis A: Chemical, 2005, 232(1/2): 95-99
[20]	Yang G, Wang L Y, Li J, Zhang Y, Dong X L,Lv Y, Gao S. Aerobic oxidation of alcohols using a novel combination of N-hydroxyphthalimide (NHPI) and CuBr [J]. Research on Chemical Intermediates, 2012, 38 (3/4/5): 775-783