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-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。实验表明,当SiO2/N-羟基酰亚胺复合物∶Co(OAc)2=5∶4时,于120℃,0.6 MPa氧压下反应16 h,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 employing the modified SiO2as seed and adding maleic anhydride(MA), solid carrier type SiO2/N-hydroxy imide composite catalyst was prepared successfully. The structure of the catalyst was characterized by FT-IR, SEM, XRD and XPS. Applying the catalyst in the oxidation of cinnamic alcohol, various parameters were screened. Experiments showed when SiO2/N- hydroxy imide composite∶Co(OAc)2= 5∶4, it allow approximately 56% conversion of cinnamic alcohol occurs in 120 ℃ for 16 h under 0.6 MPa pressures of oxygen, the oxidation product cinnamic aldehyde reached 53.2%.The mechanism for the 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 employing the modified SiO2as seed and adding maleic anhydride(MA), solid carrier type SiO2/N-hydroxy imide composite catalyst was prepared successfully. The structure of the catalyst was characterized by FT-IR, SEM, XRD and XPS. Applying the catalyst in the oxidation of cinnamic alcohol, various parameters were screened. Experiments showed when SiO2/N- hydroxy imide composite∶Co(OAc)2= 5∶4, it allow approximately 56% conversion of cinnamic alcohol occurs in 120 ℃ for 16 h under 0.6 MPa pressures of oxygen, the oxidation product cinnamic aldehyde reached 53.2%.The mechanism for the catalytic aerobic oxidation of cinnamic alcohol by SiO2/N-hydroxy imide composite was discussed.
引文
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[2]陈华林,刘白玲,罗荣.脂肪醛AAT在铬鞣软革及无铬鞣软革中的应用[J].西部皮革,2006,28(12):23-25.
[3]贝少华,刘燕,范浩军,等.高级碳链脂肪醛鞣剂的应用研究[C].2005年全国皮革化学品学术交流会论文集,2005:190-193.
[4]范浩军,范朝云.新型醛酸鞣剂的研制[J].中国皮革,1998,27(2):11-13.
[5]朱正鑫,李魏,张宗才,等.乙二醛、丙烯酸及胶原水解物制备铬鞣助剂[J].皮革科学与工程,2012,22(6):19-25.
[6]Hudicky M.Oxidations in Organic Chemistry[M].Washington,DC:American Chemical Society,1990.
[7]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.
[8]Guan B T,Xing D,Shi Z J,et al.Highly selective aerobic oxidation of alcohol catalyzed by a gold(I)complex with an anionic ligand[J].J.Am.Chem.Soc.,2005,127(51):18004-18005.
[9]苗成霞.TEMPO催化醇的氧化反应[D].南开大学,2010.
[10]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.
[11]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.
[12]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].复旦大学:物理化学,2012.
[13]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):1594-1600.
[14]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.
[15]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.
[16]Csjernyik G,Ell A H,Báckvall 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.
[17]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.
[18]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.
[19]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.
[20]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.
[21]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.
[22]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.
[23]Akiyama M,Shimizu K,Aiba S,et al.Synthesis of N-Hydroxymaleimide and N-Hydroxyitaconimide and their Related Derivatives[J].J Chem Soc,Perkin Trans1,1980,2122-2125.
[24]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].浙江大学理学院,2013.
[25]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.
[26]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.