Ethylene oligomerization using hyperbranch-macromolecule-bridged salicylaldimine cobalt catalysts

doi:10.11949/j.issn.0438-1157.20161076

Abstract

Abstract:

Three novel hyperbranch-macromolecule-bridged salicylaldimine cobalt catalysts were synthesized by Schiff and complex reactions of 1.0G hyperbranched macromolecules, salicylaldehyde, and cobalt chloride hexahydrate, and were characterized by FT-IR, UV, MS and TG. The influences of solvent, co-catalyst, reaction temperature, reaction pressure, and Al/Co molar ratio on their catalytic performances in ethylene oligomerization were studied. The results showed that the hyperbranch-macromolecule-bridged salicylaldimine cobalt catalysts had excellent catalytic activities and selectivity for ethylene oligomerization of high carbon number olefins (C₁₀₊). The catalytic activity first increased and then decreased with the increase of reaction temperature and Al/Co molar ratio, however, it continuously increased with the increase of reaction pressure. The highest activity of 1.87×10⁵ g·(mol Co)^-1·h^-1 and 42.90% selectivity for high carbon number olefins were achieved under the condition of toluene as solvent, DEAC as co-catalyst, reaction temperature at 25℃, reaction pressure at 0.5 MPa, and Al/Co molar ratio at 500.

Key words: hyperbranched macromolecule, cobalt complex, catalyst, ethylene oligomerization, activation, reactivity

摘要：

以1.0代（1.0G）超支化大分子、水杨醛和CoCl₂·6H₂O为原料，依次经过希夫碱反应和络合反应合成了3种具有不同烷基链长度的新型超支化大分子桥联水杨醛亚胺钴催化剂。对目标产物的结构进行FT-IR、UV、MS及TG表征，考察了溶剂种类、助催化剂种类、反应温度、反应压力、Al/Co摩尔比等条件对超支化大分子桥联水杨醛亚胺钴催化剂催化乙烯低聚性能的影响。结果表明，超支化大分子桥联水杨醛亚胺钴催化剂催化乙烯低聚表现出良好的催化活性和高碳烯烃（C₁₀₊）的选择性。催化活性随反应温度和Al/Co摩尔比增加先增加后下降，随反应压力增加而增加。以甲苯为溶剂，在一氯二乙基铝（DEAC）活化下，当反应温度为25℃、反应压力为0.5 MPa、Al/Co摩尔比为500时，催化活性可达1.87×10⁵ g·（mol Co）^-1·h^-1，聚合产物中高碳烯烃的含量高达42.90%。

关键词: 超支化大分子, 钴配合物, 催化剂, 乙烯低聚, 活化, 活性

CLC Number:

O631

ZHANG Na, WANG Sihan, WANG Jiaming, LI Cuiqin, WANG Jun. Ethylene oligomerization using hyperbranch-macromolecule-bridged salicylaldimine cobalt catalysts[J]. CIESC Journal, 2017, 68(3): 903-909.

张娜, 王斯晗, 王嘉明, 李翠勤, 王俊. 超支化大分子桥联水杨醛亚胺钴催化剂催化乙烯低聚[J]. 化工学报, 2017, 68(3): 903-909.

References 31

[1]	曹胜先, 陈谦, 祖春兴. 线性α-烯烃的技术现状及应用前景[J]. 中外能源, 2012, 17(2):80-85. CAO S X, CHEN Q, ZU C X. Linear alpha olefin technology today and application prospects[J]. Sino-Global Energy, 2012, 17(2):80-85.
[2]	宋宪风, 毕四勇, 毛国梁, 等. 乙烯三聚和四聚催化剂的研究进展[J]. 石油化工, 2008, 37(8):858-861. SONG X F, BI S Y, MAO G L, et al. Advance in catalysts for trimerization and tetramerization of ethylene[J]. Petrochem. Techno., 2008, 37(8):858-861.
[3]	张君涛, 张国利, 梁生荣, 等. 乙烯齐聚制α-烯烃多相催化剂研究进展[J]. 化工进展, 2008, 27(1):157-163. ZHANG J T, ZHANG G L, LIANG S R, et al. Recent developments in heterogeneous catalyst of ethylene oligomerization to α-olefins[J]. Chem. Ind. & Eng. Pro., 2008, 27(1):157-163.
[4]	FINIELS A, FAJULA F, HULEA V. Nickel-based solid catalysts for ethylene oligomerization-a review[J]. Catal. Sci. Technol., 2014, 4(8):2412-2426.
[5]	CHEN L, HOU J, SUN W. Ethylene oligomerization by hydrazone Ni(Ⅱ) complexes/MAO[J]. Appl. Catal. A:Gen., 2003, 246(1):11-16.
[6]	BREUIL P A R, MAGNA L, OLIVIER-BOURBIGOU H. Role of homogeneous catalysis in oligomerization of olefins:focus on selected examples based on group 4 to group 10 transition metal complexes[J]. Catal. Lett., 2015, 145(1):173-192.
[7]	KEIM W. Oligomerization of ethylene to a-olefins:discovery and development of the shell higher olefin process (SHOP)[J]. Angew. Chem. Int. Edit., 2013, 52(48):12492-12496.
[8]	BOUDIER A, BREUIL P A R, MAGNA L, et al. Ethylene oligomerization using iron complexes:beyond the discovery of bis(imino)pyridine ligands[J]. Chem. Commun., 2014, 50(12):1398-1407.
[9]	AINOOSON M K, OJWACH S O, GUZEI I A, et al. Pyrazolyl iron, cobalt, nickel, and palladium complexes:synthesis, molecular structures, and evaluation as ethylene oligomerization catalysts[J]. J. Organomet. Chem., 2011, 696:1528-1535.
[10]	NYAMATO G S, OJWACH S O, AKERMAN M P. Unsymmetrical (pyrazolylmethyl)pyridine metal complexes as catalysts for ethylene oligomerization reactions:role of solvent and co-catalyst in product distribution[J]. J. Mol. Catal. A:Chem., 2014, 394:274-282.
[11]	ULBRICH A D H P S, CAMPEDELLI R R, MILANI J L S, et al. Nickel catalysts based on phenyl ether-pyrazol ligands:synthesis, XPS study, and use in ethylene oligomerization[J]. Appl. Catal. A:Gen., 2013, 453:280-286.
[12]	CHANDRAN D, LEE K M, CHANG H C, et al. Ni(Ⅱ) complexes with ligands derived from phenylpyridine, active for selective dimerization and trimerization of ethylene[J]. J. Organomet. Chem., 2012, 718:8-13.
[13]	PAVLOVA I S, PERVOVA I G, BELOV G P, et al. Ethylene oligomerization mediated by iron formazanates and organoaluminum compounds[J]. Petrol. Chem., 2013, 53(2):127-133.
[14]	YANG P J, YANG Y, ZHANG C, et al. Synthesis, structure, and catalytic ethylene oligomerization of nickel(Ⅱ) and cobalt(Ⅱ) complexes with symmetrical and unsymmetrical 2,9-diary-1,10-phenanthroline ligands[J].Inorg. Chim. Acta, 2009, 362:89-96.
[15]	OJWACH S O, GUZEI I A, BENADE L L, et al. (Prazol-1-ylmethyl)pyridine nickel complexes:ethylene oligomerization and unusual Friedel-Crafts alkylation catalysts[J]. Organometallics, 2009, 28:2127-2133.
[16]	NYAMATO G S, ALAM M G, OJWACH S O, et al. Nickel(Ⅱ) complexes bearing pyrazolylpyridines:synthesis, structures and ethylene oligomerization reactions[J]. Appl. Organomet. Chem., 2016, 30:89-94.
[17]	SONG D P, SHI X C, WANG Y X, et al. Ligand steric and electronic effects on β-ketiminato neutral nickel(Ⅱ) olefin polymerization catalysts[J]. Organometallics, 2012, 31(3):966-975.
[18]	LI C Q, WANG F F, LIN Z Y, et al. Novel nickel complexes with hyperbranched structure:synthesis, characterization and performance in ethylene oligomerization[J]. Inorg. Chim. Acta, 2016, 453:430-438.
[19]	BOULENS P, LUTZ M, JEANNEAU E, et al. Iminobisphosphines to (non-) symmetrical diphosphinoamine ligands:metal-induced synthesis of diphosphorus nickel complexes and application in ethylene oligomerisation reactions[J]. Eur. J. Inorg. Chem., 2014, 2014(23):3754-3762
[20]	KERMAGORET A, BRAUNSTEIN P. Mono-and dinuclear nickel complexes with phosphino-, phosphinito-, and phosphonitopyridine ligands:synthesis, structures, and catalytic oligomerization of ethylene[J]. Organometallics, 2008, 27(1):88-99.
[21]	BOULENS P, PELLIER E, JEANNEAU E, et al. Self-assembled organometallic nickel complexes as catalysts for selective dimerization of ethylene into 1-butene[J]. Organometallics, 2015, 34(7):1139-1142.
[22]	AINOOSON M K, GUZEI I A, SPENCER L C, et al. Pyrazolylimine iron and cobalt, and pyrazolylamine nickel complexes:synthesis and evaluation of nickel complexes as ethylene oligomerization catalysts[J]. Polyhedron, 2013, 53:295-303.
[23]	KULANGARA S V, HAVEMAN D, VIDJAYACOUMAR B, et al. Effect of cocatalysts and solvent on selective ethylene oligomerization[J]. Organometallics, 2015, 34(7):1203-1210.
[24]	THIELE D, SOUZA R F D. Biphasic ethylene oligomerization using bis(imino)pyridine cobalt complexes in methyl-butylimidazolium organochloroaluminate ionic liquids[J]. J. Mol. Catal A:Chem., 2011, 340(1/2):83-88.
[25]	SONG S J, XIAOT P F, REDSHAW C, et al. Iron(Ⅱ) and cobalt(Ⅱ) complexes bearing 8-(1-aryliminoethylidene) quinaldines:synthesis, characterization and ethylene dimerization behavior[J]. J. Organomet. Chem., 2011, 696(13):2594-2599.
[26]	NYAMATO G S, ALAM M G, OJWACH S O, et al. (Pyrazolyl)-(phosphinoyl)pyridine iron(Ⅱ), cobalt(Ⅱ) and nickel(Ⅱ) complexes:synthesis, characterization and ethylene oligomerization studies[J]. J. Organomet. Chem., 2015, 783:64-72.
[27]	WANG J, LI C Q, ZHANG S Y, et al. Synthesis and characterization of lower generation broom molecules[J]. Chinese Chem. Lett., 2008, 19(1):43-49.
[28]	ZHANG N, WANG S H, SONG L, et al. Iron(Ⅱ) complexes with hyperbranched salicylaldimine ligands:synthesis, characterization and ethylene oligomerization[J]. Inorg. Chim. Acta, 2016, 453:369-375.
[29]	WANG J, ZHANG N, LI C Q, et al. Synthesis and ethylene oligomerization of hyperbranched salicylal dimine nickel complexes[J]. Adv. Polym., Tech. DOI:10.1002/adv.21704.
[30]	WANG J, ZHANG N, LI C Q, et al. Nickel complexes based on hyperbranched salicylaldimine ligands:synthesis, characterization, and catalytic properties for ethyleneoligomerization[J]. J. Organomet. Chem., 2016, 822:104-111.
[31]	傅知盛, 蔡俊飞, 杨洪瑞, 等. 烷基铝在α-二亚胺镍催化体系中的应用[J]. 高分子材料科学与工程, 2012, 28(2):165-173. FU Z S, CAI J F, YANG H R, et al. Application of alkylaluminum in (α-diimine) nickel catalysts[J]. Polym. Mater. Sci. Eng., 2012, 28(2):165-173.