制备了甲基丙烯酸缩水甘油酯(GMA)与甲基丙烯酸甲酯(MMA)共聚微球GMA/MMA,并通过键合有对羟基苯甲醛(HBA)的改性微球HBA-GMA/MMA与苯甲醛(或取代苯甲醛)以及吡咯间的Adler反应,实现了卟啉在共聚微球GMA/MMA表面的同步合成与固载,制得了因载有苯基卟啉(PP)、对氯苯基卟啉(CPP)、对硝基苯基卟啉(NPP)的功能化微球PP-GMA/MMA,CPP-GMA/MMA和NPP-GMA/MMA.重点考察了影响卟啉同步合成与固载过程的因素.制备了固载有钴卟啉的催化剂,并以分子氧氧化乙苯为模型反应,考察了催化剂的活性.结果表明,苯甲醛取代基的结构、催化剂的酸性和溶剂的极性对卟啉的同步合成与固载都有较人的影响;钴卟啉催化剂对分子氧氧化乙苯反应具有较高的催化活性,且当钴卟啉外环上含有强吸电子基团硝基时,催化剂活性最高.
The suspension polymerization of glycidyl methacrylate (GMA) and methyl methacrylate (MMA) was conducted, resulting in polymeric microspheres GMA/MMA. Subsequently, p-hydroxybenzaldebyde (HBA) was bonded on GMA/MMA, obtaining modified mi-crospheres HBA-GMA/MMA. Adler reaction was performed by using microspheres HBA-GMA/MMA, benzaldehyde derivatives, and pyr-role in solution, so that the synchronistic synthesis and immobilization of porphyrins on the microspheres GMA/MMA were realized suc-cessfully, resulting in three kinds of porphyrin-supported microspheres. The effects of main factors on the process of synchronistic synthesis and immobilization of porphyrin were studied. Via the coordination reaction between the functional microspheres and cobalt salt, poly-mer-supported cobalt porphyrin was prepared. The catalytic activity of the catalysts was tested in the oxidation reaction of ethyl benzene by oxygen molecules. The results showed that the substitute structure of benzaldehyde derivatives, the acidity of the catalysts, and the polarity of solvents affected the synchronistic synthesis and immobilization of porphyrin greatly. The porphyrin-supported catalysts had obvious catalytic activity for the oxidation reaction. The immobilized cobalt porphyrin with strong electron-withdrawing substitute on phenyl ring has higher catalytic activity.
参考文献
| [1] | Moghadam M;Tangestaninejad S;Mirkhani V;Mohammadpoor-Baltork I Moosavifar M .[J].Journal of Molecular Catalysis A:Chemical,2009,302:68. |
| [2] | Rahiman A K;Bharathi K S;Sreedaran S;Rajesh K Narayanan V .[J].Inorganica Chimica Acta,2009,362:1810. |
| [3] | Rahiman, AK;Rajesh, K;Bharathi, KS;Sreedaran, S;Narayanan, V .Catalytic oxidation of alkenes by manganese(III) porphyrin-encapsulated Al, V, Si-mesoporous molecular sieves[J].Inorganica Chimica Acta,2009(5):1491-1500. |
| [4] | Rayati S;Zakavi S;Noroozi V;Motlagh S H .[J].Catalysis Communications,2008,10:221. |
| [5] | Giri N G;Chauhan S M S .[J].CATALYSIS COMMUNICATIONS,2009,10:383. |
| [6] | Ferreira ADQ;Vinhado FS;Iamamoto Y .Characterization of Mn(III)porphyrin immobilized on modified silica surfaces by EXAFS spectroscopy: A promising tool for analysis of supported metalloporphyrin catalysts[J].Journal of molecular catalysis, A. Chemical,2006(1):111-119. |
| [7] | Moreira MSM;Martins PR;Curi RB;Nascimento OR;Iamamoto Y .Iron porphyrins immobilised on silica surface and encapsulated in silica matrix: a comparison of their catalytic activity in hydrocarbon oxidation[J].Journal of molecular catalysis, A. Chemical,2005(1/2):73-81. |
| [8] | Halma M;Bail A;Wypych F;Nakagaki S .Catalytic activity of anionic iron(III) porphyrins immobilized on grafted disordered silica obtained from acidic leached chrysotile[J].Journal of molecular catalysis, A. Chemical,2006(1):44-51. |
| [9] | Fu B;Yu H C;Huang J W;Zhao P,Liu J,Ji L N .[J].Journal of Molecular Catalysis A:Chemical,2009,298:74. |
| [10] | Rahiman AK;Rajesh K;Bharathi KS;Sreedaran S;Narayanan V .Manganese(III) porphyrin-encapsulated Ti,Si-mesoporous molecular sieves as heterogeneous catalysts for the epoxidation of alkenes[J].Applied Catalysis, A. General: An International Journal Devoted to Catalytic Science and Its Applications,2006(2):216-225. |
| [11] | Smith JRL;Iamamoto Y;Vinhado FS .Oxidation of alkanes by iodosylbenzene (PhIO) catalysed by supported Mn(III) porphyrins: Activity and mechanism[J].Journal of molecular catalysis, A. Chemical,2006(1/2):23-30. |
| [12] | Rebeio S L H;Goncalves A R;Pereira M M;Simoes M M Q Neves M G P M S Cavaleiro J A S .[J].Journal of Molecular Catalysis A:Chemical,2006,256:321. |
| [13] | Crestini C;Pastorini A;Tagliatesta P .[J].Journal of Molecular Catalysis A:Chemical,2004,208:195. |
| [14] | Moghadam M;Tangestaninejad S;Habibi M H;Mirkhani V .[J].Journal of Molecular Catalysis A:Chemical,2004,217:9. |
| [15] | Mukherjee M;Ray AR .Biomimetic oxidation of L-arginine with hydrogen peroxide catalyzed by the resin-supported iron (III) porphyrin[J].Journal of molecular catalysis, A. Chemical,2007(1/2):207-214. |
| [16] | Moghadam M;Nasr Esfahani M;Tangestaninejad S;Mirkhani V .Mild and efficient oxidation of Hantzsch 1,4-dihydropyridines with sodium periodate catalyzed by a new polystyrene-bound Mn(TPP)Cl.[J].Bioorganic and Medicinal Chemistry Letters,2006(7):2026-2030. |
| [17] | Liu ST;Reddy KV;Lai RY .Oxidative cleavage of alkenes catalyzed by a water/organic soluble manganese porphyrin complex[J].Tetrahedron,2007(8):1821-1825. |
| [18] | Brule E;de Miguel YR;Hii KK .Chemoselective epoxidation of dienes using polymer-supported manganese porphyrin catalysts[J].Tetrahedron,2004(28):5913-5918. |
| [19] | Ribeiro S M;Serra A C;Gonsalves A M d'A R .[J].Tetrahedron,2007,63:7885. |
| [20] | 赵婧,高保娇.交联微球GMA/MMA的表面化学改性及卟啉在其上的固载化[J].化学通报(印刷版),2010(01):37-43. |
| [21] | 张国海,高保娇,王蕊欣,王飞宇.在交联聚苯乙烯微球表面实现苯基卟啉的同步合成与固载[J].高等学校化学学报,2009(03):607-612. |
| [22] | 王君文;何明威 .[J].化学试剂,2001,23(09) |
| [23] | Poitowicz J;Pamin K;Haber J .[J].Journal of Molecular Catalysis A:Chemical,2006,257:154. |
| [24] | 章艳,高保娇,王蕊欣.固载MnP-PGMA/SiO2催化剂的制备及其对乙苯氧化反应的催化性能[J].催化学报,2008(03):247-252. |
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