SiO_2/N-羟基酰亚胺复合物的制备及其催化性能
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摘要
采用硅烷偶联剂KH570对纳米SiO2进行表面改性,并以改性后的SiO2为种子,马来酸酐为单体,成功制备了固载型SiO2/N-羟基酰亚胺复合物催化剂。采用红外光谱、扫描电镜、X射线衍射和X射线能谱对催化剂进行了表征。将该催化剂用于肉桂醇的氧化反应,考察了各种因素对反应性能的影响。实验结果表明,当SiO2/N-羟基酰亚胺复合物:Co(OAc)2=5∶4时,于120℃,0.6MPa氧压下反应16h,56%的肉桂醇发生转化,氧化产物肉桂醛达53.2%。探讨了SiO2/N-羟基酰亚胺复合物/Co(OAc)2催化氧化肉桂醇的反应机理。
Nano-silica was surface modified with silane coupling agent KH570.Then using the modified SiO2 as seed and adding maleic anhydride(MA),solid carrier type SiO2/N-hydroxy imide composite catalyst was prepared.The structure of the catalyst was characterized by FTIR,SEM,XRD and XPS.Applying the catalyst in oxidation of cinnamic alcohol,various parameters were investigated.SiO2/N-hydroxy imide composite:Co(OAc)2 =5∶4allowed approximately 56%conversion of cinnamic alcohol at 120℃for 16 hunder 0.6MPa pressures of oxygen,and the yield of oxidation product cinnamic aldehyde reached 53.2%.The mechanism of catalytic aerobic oxidation of cinnamic alcohol by SiO2/N-hydroxy imide composite was discussed.
Nano-silica was surface modified with silane coupling agent KH570.Then using the modified SiO2 as seed and adding maleic anhydride(MA),solid carrier type SiO2/N-hydroxy imide composite catalyst was prepared.The structure of the catalyst was characterized by FTIR,SEM,XRD and XPS.Applying the catalyst in oxidation of cinnamic alcohol,various parameters were investigated.SiO2/N-hydroxy imide composite:Co(OAc)2 =5∶4allowed approximately 56%conversion of cinnamic alcohol at 120℃for 16 hunder 0.6MPa pressures of oxygen,and the yield of oxidation product cinnamic aldehyde reached 53.2%.The mechanism of catalytic aerobic oxidation of cinnamic alcohol by SiO2/N-hydroxy imide composite was discussed.
引文
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[2]赵晶晶,郑庚修,田忠贞,等.N,N′-二甲基乙二胺与TEMPO协同催化氧化醇[J].济南大学学报:自然科学版,2014,28(2):147-150.
[3]Guan B T,Xing D,Shi Z J,et al.Highly selective aerobic oxidation of alcohol catalyzed by agold(I)complex with an anionic ligand[J].J.Am.Chem.Soc.,2005,127(51):18004-18005.
[4]苗成霞.TEMPO催化醇的氧化反应[D].天津:南开大学,2010.
[5]孔德轮,高保娇,章艳.硅胶固载聚4-乙烯吡啶-Cu(Ⅱ)配合物催化分子氧氧化乙苯的性能研究[J].分子催化,2007,21(6):579-584.
[6]Zhang Hua,Fu Luoling,Zhong Hongmin.Silica gelsupported TEMPO with adsorbed NOx for selective oxidation of alcohols under mild conditions[J].Chinese J.Catal.,2013,34(10):1848-1854.
[7]倪吉.氧化物负载纳米金用于绿色催化选择还原与氧化反应研究[D].上海复旦大学,2012.
[8]马恒昌,王锋,曹伟,等.羊毛-Pd(0)催化剂的制备、表征及其在水相中对醇的催化氧化反应[J].催化学报,2012,33(9):1594-1600.
[9]马文娇,黄琼,陈英文,等.堇青石负载Fe-Mn-O混合氧化物催化氧化甲苯的性能研究[J].现代化工,2012,32(3):26-29.
[10]Edegger K,Mang H,Kroutil W,et al.Biocatalytic oxidation of sec-alcohols via hydrogen transfer[J].J.Mol.Catal.A:Chem.,2006,251:66-70.
[11]Csjernyik G,Ell A H,Bckvall J E,et al.Efficient ruthenium-catalyzed aerobic oxidation of alcohols using a biomimetic coupled catalytic system[J].J.Org.Chem.,2002,67(5):1657-1662.
[12]唐青华,周贤太,纪红兵.双核金属卟啉仿酶催化剂的合成及催化氧化进展[J].化工进展,2009,28(2):234-242.
[13]毋伟,陈建峰,屈一新.硅烷偶联剂的种类与结构对二氧化硅表面聚合物接枝改性的影响[J].硅酸盐学报,2004,32(5):570-575.
[14]Liu P,Tian J,Liu W M,et al.Preparation and characterization of polystyrene grafted nano-sized silica[J].Mat.Res.Innovat.,2003,7:105-109.
[15]Yoshinaga K,Tani Y,Tanaka Y.Surface modification of fine colloidal silica with copolymer silane-coupling agents composed of maleic anhydride[J].Colloid Polym.Sci.,2002,280(1):85-89.
[16]Yoshinaga K,Shimada J,Nishida H,et al.Effects of secondary polymer covalently attached to monodisperse,poly(maleic anhydride-styrene)-modified colloidal silica on dispersibility in organic solvent[J].J.Colloid Interface Sci.,1999,214(2):180-188.
[17]钱晓静,刘孝恒,陆路德,等.辛醇改性纳米二氧化硅表面的研究[J].无机化学学报,2004,3(20):335-338.
[18]Akiyama M,Shimizu K,Aiba S,et al.Synthesis of N-hydroxymaleimide and N-hydroxyitaconimide and their related derivatives[J].J.Chem.Soc.,Perkin Trans.1,1980:2122-2125.
[19]陈可先.N-羟基亚胺类有机催化剂的设计及其催化氧化机理研究[D].杭州浙江大学理学院,2013.
[20]Yoshino Y,Hayashi Y,Iwahama T,et al.Catalytic oxidation of alkylbenzenes with molecular oxygen under normal pressure and temperature by N-hydroxyphthalimide combined with Co(OAc)2[J].J.Org.Chem.,1997,62(20):6810-6813.
[21]Xu H,Tang R,Gong N,et al.Aerobic oxidation reactions catalyzed by N-hydroxyphthalimide and its analogues[J].Prog.Chem.,2007,19:1736-1745.