聚苯乙烯微球固载2,6-双(2-苯并咪唑)吡啶的Fe(Ⅲ)配合物催化氧化活性研究

Catalytic Oxidation of Fe( Ⅲ) Complex of 2,6-Bis-( 2-benzimidazole) Pyridine Immobilized on Polystyrene Microspheres

2,6-双(2-苯并咪唑)吡啶(bbp)在氯甲基化交联聚苯乙烯(CPS)微球上进行烷基化反应制得CPS-bbp,然后与FeCl_3·6H_2O进行配合得到配合物CPS-Fe(Ⅲ)-bbp.以该配合物为催化剂分别使用过氧化氢(H_2O_2)和叔丁基过氧化氢(TBHP)作氧化剂对苯乙烯、α-甲基苯乙烯和环己烯进行了催化氧化反应研究.过氧化氢氧化能力强,15 min内反应基本完成,α-甲基苯乙烯和苯乙烯的氧化产物苯乙酮和苯甲醛选择性分别高达98.49%和95.87%;TBHP的氧化缓慢而平稳,24 h后反应基本完成,对α-甲基苯乙烯和环己烯的氧化选择性较好,分别达到97.44%,和94.82%.

CPS-bbp was prepared by alkylation of 2,6-bis（ 2-benzimidazole） pyridine（ bbp） and crosslinked chloromethylpolystyrene microspheres（ CPS-Cl）,which was then coordinated with FeCl3·6 H2O to obtain a supported substance of Fe（ Ⅲ）-CPS-bbp. The catalytic activities of the iron-complex were studied in the oxidation of styrene,α-methylstyrene and cyclohexene in CH3CN,hydrogen peroxide（ H2O2） and t-butyl peroxide（ TBHP） used as the oxidants respectively. H2O2 showed strong oxidative ability and the reactions finished within 15 minutes. The selectivity of the major products prepared from α-methylstyrene and styrene were 98.49% and 95.87% ,respectively for acetophenone and benzaldehyde. Oxidation with TBHP was slow and steady,the reactions finished after 24 hours,with favorable values of selectivity on α-methylstyrene and cyclohexene obtained,97.44% and 94. 82% for acetophenone and α-cyclohexenone respectively.