新型树枝状PNP铬催化剂的合成及催化性能

doi:10.7503/cjcu20160687

摘要/Abstract

摘要：

以1.0代聚酰胺-胺(PAMAM)为配体骨架, 氯代二苯基膦为原料, 通过取代反应合成了1种含有较大空间位阻的新型树枝状PNP配体, 再以CrCl₃(THF)₃为络合试剂, 通过络合反应合成树枝状PNP铬催化剂. 采用傅里叶变换红外光谱(FTIR)、紫外-可见分光光度计(UV-Vis)、核磁共振波谱(NMR)、电喷雾电离质谱(ESI-MS)和元素分析等手段证实合成的新型树枝状PNP配体及其铬催化剂的结构与理论设计的结构一致. 以甲基铝氧烷(MAO)为助催化剂, 对乙烯齐聚反应进行了研究, 考察了溶剂种类、反应温度、反应压力及Al/Cr摩尔比对该催化剂活性和选择性的影响. 结果表明, 以甲苯为溶剂, MAO为助催化剂, 当反应温度为25 ℃, 反应压力为0.9 MPa, Al/Cr摩尔比为500时, 该催化剂的活性高达2.15×10⁵ g/(mol Cr·h), 催化剂对乙烯三聚、四聚反应的选择性共达到36.76%.

关键词: 1.0代聚酰胺-胺, 树枝状PNP配体, 树枝状PNP铬催化剂, 乙烯齐聚

Abstract:

A novel dendritic PNP ligand was synthesized using 1.0G dendritic polyammidoamine(PAMAM) and chlorodiphenylphosphine as the raw materials through substitution reaction, and the dendritic PNP chromium(Ⅲ) catalyst was synthesized from the reaction with chromium(Ⅲ) chloride tetrahydrofuran complex as material. The structure of novel dendritic PNP ligand and PNP chromium(Ⅲ) catalyst were characterized by Fourier transform infrared(FTIR), ultraviolet-visible(UV-Vis), nuclear magnetic resonance(NMR), electrospray ionization-mass spectroscopy(ESI-MS) and elemental analysis. The results indicate that the structure of novel dendritic PNP ligand and PNP chromium(Ⅲ) catalyst are consistent with theoretical structure. The dendritic PNP chromium(Ⅲ) catalyst was used as a precatalyst in the oligomerization of ethylene with the co-catalyst methylaluminoxane(MAO). The effects of solvent, reaction temperature, reaction pressure and the molar ratio of Al/Cr on the catalytic activities and selectivity in the oligomerization were investigated. With MAO as co-catalyst and toluene as solvent, the selectivity of novel dendritic PNP chromium(Ⅲ) catalyst on ethylene trimer and tetramer reached up to 36.76% and the catalytic activity was 2.15×10⁵ g/(mol Cr·h) at reaction temperature of 25 ℃, reaction pressure of 0.9 MPa and Al/Cr molar ratio of 500.

Key words: 1.0G Polyammidoamine, Novel dendritic PNP ligand, Dendritic PNP chromium catalyst, Ethylene trimerization and tetramerization

TrendMD:

王俊, 高瑞, 于彦龙, 张娜, 李翠勤, 施伟光. 新型树枝状PNP铬催化剂的合成及催化性能. 高等学校化学学报, 2017, 38(7): 1257.

WANG Jun, GAO Rui, YU Yanlong, ZHANG Na, LI Cuiqin, SHI Weiguang. Synthesis and Ethylene Oligomerization Behavior of Novel Dendritic PNP Chromium Catalyst^†. Chem. J. Chinese Universities, 2017, 38(7): 1257.

图/表 8

参考文献 32

[1]	Wang J., Huo H. L., Li C. Q., Ma L. L., Shi W. G., Chen S., Chem. J. Chinese Universities,2015, 36(9), 1813—1818
	(王俊, 霍宏亮,李翠勤, 马立莉, 施伟光, 陈帅.高等学校化学学报, 2015, 36(9), 1813—1818)
[2]	Wang J., Yang G., Li C. Q., Shi W. G., Wang S. H., Chem. Pap., 2014, 68(11), 1532—1538
[3]	Malgas-Enus R., Mapolie S. F., Inorg. Chim.Acta,2014, 409(2), 96—105
[4]	Pijnenburga N. J. M., Tomás-Mendivila E., Mayland K. E., Kleijn H., Lutz M., Spek A. L., Kotena G., Gebbink R. J. K., Inorg. Chim.Acta,2014, 409(Part A), 163—173
[5]	Carter A., Cohen S. A., Cooley N. A., Murphy A., Scutt J., Wass D. F., Chem. Commun., 2002, 8(8), 858—859
[6]	McGuinness D. S., Chem. Rev., 2011, 111(3), 2321—2341
[7]	Agapie T., Coordin. Chem. Rev., 2011, 255(7), 861—880
[8]	Van Leeuwen P. W. N. M., Clément N. D., Tschan M. J. L., Coordin. Chem. Rev., 2011, 255(13), 1499—1517
[9]	Dixon J. T., Green M. J., Hess F. M., Morgan D. H., J. Organomet. Chem., 2004, 689(23), 3641—3668
[10]	Sydora O. L., Jones T. C., Small B. L., Nett A. J., Fischer A. A., Carney M. J., ACS Catal., 2012, 2(12), 2452—2455
[11]	Radcliffe J. E., Batsanov A. S., Smith D. M., Scott J. A., Dyer P. W., Hanton M. J., ACS Catal., 2015, 5(12), 7095—7098
[12]	Jiang T., Ning Y. N., Zhang B. J., Li J. Z., Wang G., Yi J. J., Huang Q., J. Mol. Catal. A: Chem., 2006, 259(1), 161—165
[13]	Sa S., Lee S. M., Kim S. Y., J. Mol. Cata. A: Chem., 2013, 378(11), 17—21
[14]	Bollmann A., Blann K., Dixon J. T., Hess F. M., Killian E., Maumela H., McGuinness D. S., Morgan D. H., Neveling A., Otto S., Overett M., Slawin A. M. Z., Wasserscheid P., Kuhlmann S., J. Am. Chem. Soc., 2004, 126(45), 14712—14713
[15]	Liu R., Xiao S. M., Zhong X. H., Cao Y. C., Liang S. B., Liu Z. Y., Ye X. F., Shen A., Zhu H. P., Chin. J. Org. Chem., 2015, 35(9), 1861—1888
	(刘睿, 肖树萌, 钟向宏, 曹育才, 梁胜彪, 刘振宇, 叶晓峰, 沈安, 朱红平.有机化学, 2015, 35(9), 1861—1888)
[16]	Shi W. G., Yang G., Wang S. H., Li C. Q., Wang J., Chem. Ind. & Eng. Pro., 2014, 33(7), 1763—1768
	(施伟光, 杨光, 王斯晗, 李翠勤, 王俊.化工进展, 2014, 33(7), 1763—1768)
[17]	Wang Q.A.,Fan H. F., Liao T. G., Technical Handbook of Organic Chemistry Laboratory, Chemical Industry Press, Beijing, 2012, 201—221
	(汪秋安, 范华芳, 廖头根.有机化学实验室技术手册,北京: 化学工业出版社, 2012, 201—221)
[18]	Zhang P., Study on the Synthesis and Catalysis of Dendritic Metal Complexes, Northeast Petroleum University, Daqing, 2011
	(张鹏. 树枝状金属配合物的合成及催化性能研究, 大庆: 东北石油大学, 2011)
[19]	Ning Y.C., Structural Identification of Organic Compounds and Organic Spectroscopy, Science Press, Beijing, 2000, 322—364
	(宁永成. 有机化合物结构鉴定与有机波谱学, 北京: 科学出版社, 2000, 322—364)
[20]	Wang J., Yang G., Li C. Q., Shi W. G., Chem. J. Chinese Universities,2014, 35(7), 1536—1540
	(王俊, 杨光, 李翠勤, 施伟光.高等学校化学学报, 2014, 35(7), 1536—1540)
[21]	Li L., Ren Z. G., Li N. Y., Zhang Y., Lang J. P., Inorg. Chim.Acta,2009, 362(11), 3910—3914
[22]	Shozi M. L., Friedrich H. B., South African Journal of Chemistry,2012, 659, 214—222
[23]	Suttil J. A., Wasserscheid P., McGuinness D. S., Gardiner M. G., Evans S. J., Catal. Sci. Technol., 2014, 4(8), 2574—2588
[24]	Wang S. H., Li J. Z., Wang G. Z., Zhang B. J., Qu J. B., Polym. Bull., 2012, 4, 122—126
	(王斯晗, 李建忠, 王桂芝, 张宝军, 曲家波. 高分子通报, 2012, 49, 122—126)
[25]	Mogorosi M. M., Mahamo T., Moss J. R., Mapolie S. F., Slootweg J. C., Lammertsma K., Smith G. S., J. Organomet. Chem., 2011, 696(23), 3585—3592
[26]	Yuan J. C., Yu F., Mei T. J., Wang X. H., Chem. Res. Chinese Universities,2011, 27(6), 1014—1018
[27]	Britovsek G. J. P., Bruce M., Gibson V. C., Kimberley B. S., Maddox P. J., Mastroianni S., McTavish S. J., Redshaw C., Solan G. A., Strömberg S., White A. J. P., Williams D. J., J. Am. Chem. Soc., 1999, 121(38), 8728—8740
[28]	Sun W. H., Song S. J., Li B. X., Redshaw C., Hao X., Li Y. S., Wang F. S., Dalton. Trans., 2012, 41(39), 11999—12010
[29]	Tang X. B., Zhang D. H., Jie S. Y., Sun W. H., Chen J. T., J. Organomet. Chem., 2005, 690(17), 3918—3928
[30]	McGuinness D. S., Rucklidge A. J., Tooze R. P., Slawin A. M. Z., Organometallics,2007, 26(10), 2561—2569
[31]	Walsh R., Morgan D. H., Bollmann A., Dixon J. T., Appl. Catal. A: Gen., 2006, 306(7), 184—191
[32]	Chen J. X., Huang Y. B., Li Z. S., Zhang Z. C., Wei C. X., Lan T. Y., Zhang W. J., J. Mol. Catal. A: Chem., 2006, 259(1/2), 133—141

Peak No.	Species of hydrogen proton	Types of peak	Number of protons	δ	J/Hz
1	—N—CH₂—CH₂—N—	t	4	2.19—2.28
2	—N—CH₂—CH₂—CO—	t	8	2.93—3.00	7.5
3	—CO—CH₂—	t	8	2.38—2.45	6.0
4	—CONH—	s	4	8.27
5	—CON—CH₂—	q	8	2.88—2.95
6	—CH₂—NP—	t	8	2.70—2.80	7.6
7,8,9	Ph—H	m	80	7.29—7.59

Peak No.	Species of hydrogen proton	Types of peak	Number of protons	δ	J/Hz
1	—N—CH₂—CH₂—N—	t	4	2.19—2.28
2	—N—CH₂—CH₂—CO—	t	8	2.93—3.00	7.5
3	—CO—CH₂—	t	8	2.38—2.45	6.0
4	—CONH—	s	4	8.27
5	—CON—CH₂—	q	8	2.88—2.95
6	—CH₂—NP—	t	8	2.70—2.80	7.6
7,8,9	Ph—H	m	80	7.29—7.59

Solvent	10^-5Activity/[g·(mol Cr·h)^-1]	Selectivity(%)
Solvent	10^-5Activity/[g·(mol Cr·h)^-1]	C₄	C₆	C₈	C₁₀₊
Hexane	1.41	92.86	7.12	0.01	0.01
Cyclohexane	1.55	84.55	9.65	3.85	1.95
Toluene	2.05	77.65	7.77	11.13	3.45

Solvent	10^-5Activity/[g·(mol Cr·h)^-1]	Selectivity(%)
Solvent	10^-5Activity/[g·(mol Cr·h)^-1]	C₄	C₆	C₈	C₁₀₊
Hexane	1.41	92.86	7.12	0.01	0.01
Cyclohexane	1.55	84.55	9.65	3.85	1.95
Toluene	2.05	77.65	7.77	11.13	3.45

Temperature/℃	10^-5Activity/[g·(mol Cr·h)^-1]	Selectivity(%)
Temperature/℃	10^-5Activity/[g·(mol Cr·h)^-1]	C₄	C₆	C₈	C₁₀₊
15	1.94	82.42	3.78	12.87	0.93
25	2.05	77.65	7.77	11.13	3.45
35	1.51	73.53	8.01	16.76	1.70
45	1.21	69.51	8.21	21.24	1.04
55	1.00	68.77	5.71	19.01	6.51