Pd(DD)<sub>2</sub>/Hβ上苯酚氧化羰基化反应研究

摘要

采用微波辅助浸渍法,以Hβ分子筛为载体,合成了负载型席夫碱钯配合物催化剂Pd(DD)₂/Hβ(DD为对羟基苯甲醛缩对氨基苯甲酸配体)。采用¹H-NMR、XRD、FT-IR、ICP等方法对Pd(DD)₂/Hβ进行结构确认,将该配合物用于催化苯酚氧化羰基化制备碳酸二苯酯反应,考察了助催化剂Cu加入量、助催化剂铜钴锰复合氧化物加入量、反应温度、反应时间对DPC产率和选择性的影响。实验结果表明,在反应条件为:铜加入量0.04 g、铜钴锰复合氧化物加入量0.4 g、反应时间8 h、反应温度110℃时,碳酸二苯酯的收率及选择性分别为36.1%和82.2%。

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	程庆彦
	刘运东
	王延吉
	赵新强

关键词：席夫碱； Hβ；苯酚氧化羰基化；碳酸二苯酯；微波

Abstract：

A novel catalyst of Hβ supported schiff base Pd complex-Pd(DD)₂/Hβ was prepared by microwave assisted solvothermal method. Pd(DD)₂/Hβ were characterized by means of ¹H-NMR,XRD,FT-IR,and ICP. The catalytic performance of Pd(DD)₂/Hβ and the effects of Cu(OAc)₂ dosage, Cu-Co-Mn mixed oxide dosage,reaction time and reaction temperature on the catalytic performance of Pd(DD)₂ in the oxidative carbonylation of phenol to diphenyl carbonate were studied. The results showed that the yield and selectivity of DPC reached 36.1% and 82.2% respectively,under the reaction conditions of Cu(OAc)₂ dosage 0.04 g,Cu-Co-Mn mixed oxide dosage 0.4 g,reaction temperature 110℃, reaction time 8 h.

Keywords： schiff base； Hβ； oxidative carbonylation； diphenyl carbonate； microwave

Received 2015-07-15;

Fund:

国家自然科学基金(21106030)。

Corresponding Authors: 程庆彦,E-mail:chengqingyan@hebut.edu.cn。 Email: chengqingyan@hebut.edu.cn

About author: 程庆彦(1974-),女,博士,教授,现从事绿色催化反应工程与工艺方面的研究。

引用本文:

程庆彦, 刘运东, 王延吉, 赵新强.Pd(DD)₂/Hβ上苯酚氧化羰基化反应研究[J]. 化学工业与工程, 2015,32(5): 103-108

Cheng Qingyan, Liu Yundong, Wang Yanji, Zhao Xinqiang.Oxidative Carbonylation of Phenol to Diphenyl Carbonate over Mesoporous Hβ Molecular Sieve Supported Pd(DD)₂ Catalyst[J]. Chemcial Industry and Engineering, 2015,32(5): 103-108

[1] Murayama T,Hayashi T,Arai Y,et al. Direct synthesis of diphenyl carbonate by mediated electrocarbonylation of phenol at Pd²⁺-supported activated carbon anode[J]. Electrochimica Acta,2011,56: 2 929-2 933
[2] Zhou W,Zhao X,Wang Y,et al. Synthesis of diphenyl carbonate by transesterification over lead and zinc double oxide catalyst[J]. Applied Catalysis A: General,2004,260(1): 19-24
[3] Takagi M, Miyagi H, Yoneyama T, et al. Palladium-Lead catalyzed oxidative carbonylation of phenol[J]. Journal of Molecular Catalysis A: Chemical,1998,129(1): L1-L3
[4] Zhang Y,Xiang S,Wang G,et al. Preparation and application of cocout shell activated carbon immobilized palladium complexes[J]. Catalysis Science &Technology, 2014, 4: 1 055-1 063
[5] Lu W,Du Z,Yuan H,et al. Synthesis of diphenyl carbonate over the magnetic catalysts Pd/La_1-xPb_xMnO₃(x=0.2—0.7)[J]. Chinese Journal of Chemical Engineering, 2013, 21(1): 8-13
[6] 王松涛,高文涛,任庆云. Schiff base 类配位化合物的应用[J]. 广东化工, 2014, 41(6): 110-118 Wang Songtao, Gao Wentao, Ren Qingyun.The application of Schiff base complexes[J]. Guangdong Chemical Industry, 2014, 41(6): 110-118(in Chinese)
[7] 程庆彦,周杰,王延吉, 等. ZSM-5负载氨基酸席夫碱型异双核配合物催化剂的制备及其催化苯酚氧化羰基化反应性能[J]. 石油学报(石油加工), 2013, 30(2): 224-230 Cheng Qingyan, Zhou Jie, Wang Yanji,et al. Preparation of novel amino acid heterodinuclear Schiff base complex catalyst supported on ZSM-5 and its catalytic performance in oxidative carbonylation of phenol[J]. Acta Petrolei Sinica(Petroleum Processing Section), 2014, 30(2): 224-230(in Chinese)
[8] 程庆彦,李超毅,王延吉, 等. HMS介孔分子筛催化剂上苯酚氧化羰基化合成碳酸二苯酯[J]. 石油化工, 2011, 40(7): 712-716 Cheng Qingyan, Li Chaoyi, Wang Yanji, et al.Oxidative carbonylation of phenol to diphenyl over mesoporous HMS molecular sieve supported vatalyst[J]. Petrochemical Technology, 2011, 40(7): 712-716(in Chinese)
[9] 郭红霞. Pd-Co/铜钴锰氧化物催化苯酚氧化羰基化法合成碳酸二苯酯[J]. 天然气化工, 2012, 37(3): 18-22 Guo Hongxia. Synthesis of diphenyl carbonate by oxidative carbonylation of phenol over Pd-Co/Cu-Co-Mn composite oxide catalyst [J]. Natural Gas Chemical Industry, 2012, 37(3): 18-22(in Chinese)
[10] 贤景春,李瑞延,曹高娃, 等. Zn(Ⅱ)Ni(Ⅱ)与5-氯水杨醛缩乙二胺碱单、双核配合物的合成及其对O₂^-的催化歧化作用[J]. 无机化学学报, 2000, 16(5): 833-836. Xian Jingchun, Li Ruiyan, Cao Gaowa,et al. Synthesis of mononuclear and dinuclear Zn(Ⅱ)Ni(Ⅱ)complexes with 5-chlorosalicylaldehyde-ethylenediamine schiff base and their dismutation to O₂^- free radicl[J]. Chinese Journal of Inorganic Chemistry, 2000, 16(5): 833-836 (in Chinese)
[11] 杨俊召,任君,贾广信, 等. 改性Hβ沸石在甲醇汽油催化改性中的应用和表征[J]. 石油化工, 2011, 40(2): 146-150 Yang Junzhao, Ren Jun, Jia Guangxin,et al. Characterization of modified Hβ zeolite and its application to catalytic modification of methanol gasoline[J]. Petrochemical Technology, 2011, 40(2): 146-150(in Chinese)
[12] 宁永成. 有机波谱学谱图解析[M]. 北京:科学出版社,2010 Ning Yongcheng.Interpretation of organic spectra[M]. Beijing: Science Press, 2010(in Chinese)
[13] Meenakshi G, Ritsuko Na, Junichi S, et al. Effect of inorganic redox cocatalyst on Pd-catalyzed oxidative carbonylation of phenol for direct synthesis of diphenyl carbonate[J]. Catalysis Letters, 1998, 54(1/2): 29-31
[14] 郭红霞,吕敬德,李忠, 等. 羰基化法合成碳酸二苯酯催化剂的研究进展[J]. 上海化工, 2008, 33(3): 7-10 Guo Hongxia, Lv Jingde, Li Zhong, et al. Thermodynamic analysis for the synthesis of diphenyl carbonate by oxidative carbonylation of phenol with CO and O₂^-[J]. Shanghai Chemical Industry, 2008, 33(3): 7-10(in Chinese)