Ethylene Oligomerization and Friedel-Crafts Alkylation Tandem Action Catalyzed by Aryloxy Zirconium Catalysts†

doi:10.7503/cjcu20150312

Abstract

Abstract:

Linear α-olefins are currently produced predominantly by the oligomerization of ethylene. Among the most promising catalysts, zirconium catalysts are largely studied due to its mild reaction condition and well-distributed products. In this article, aryloxy zirconium catalysts, Zr(OAr)_nCl_4-_n·mArOH, were synthesized via modifying the aryl ring structure. The influence of Zr/Phenol molar ratio and the free phenol content on ethylene oligomerization was studied. Among these catalytic systems, Zr(OPh)₃Cl·mPhOH/TEA/EtAlCl₂ was proved to be highly active with the activity up to 6.8×10⁴ g/(mol Zr·h), while the product consisted of mainly α-olefins(C₄—C₂₄) without polymers. In addition, a suitable amount of free phenol was found to be responsible for stabilizing the active species. It was also found that increasing the ethylene pressure or altering the substituents on the benzene ring could result in the formation of a tandem catalytic system, in which the obtained α-olefins were then mostly converted into the corresponding Friedel-Crafts alkylated-toluene products.

Key words: Aryloxy zirconium catalyst, Ethylene oligomerization, Friedel-Crafts alkylated reaction, Tandem action, α-Olefin(Ed.: W.Z)

CLC Number:

O632.12

TrendMD:

QIN Yichao, YE Jian, JIANG Binbo, WANG Jingdai, YANG Yongrong. Ethylene Oligomerization and Friedel-Crafts Alkylation Tandem Action Catalyzed by Aryloxy Zirconium Catalysts^†[J]. Chem. J. Chinese Universities, 2015, 36(9): 1825.

Figures/Tables 10

Fig.1 Structures of complex Zr-1—Zr-5

Fig.2 Comparison of catalytic activities by Zr-1b, Zr-2—Zr-5a. Zr-1b; b. Zr-2; c. Zr-3;d. Zr-4; e. Zr-5.

Fig.3 Product distribution of Zr-1b on ordinary pressure(0.1 MPa)a. C4; b. C6; c. C8; d. C10; e. C12; f. C14;g. C16; h. C18; i. C20; j. C22; k. C24.

Table 1 Results of ethylene oligomerization with different amounts of phenol by Zr-1[n(Al)∶n(Zr)=30∶1]

Catalyst	n(Zr)∶n(PhOH)	10^-4 Activity/[g·(mol Zr·h)^-1]	K^a	LAO^b(%)
ZrCl₄	1∶0	2.51	0.43	80.81
Zr-1a	1∶2	5.33	0.61	80.05
Zr-1b	1∶4	6.83	0.57	83.36
Zr-1c	1∶6	6.75	0.59	84.36
Zr-1d	1∶8	6.48	0.60	84.42

Fig.4 Effects of oligomer distributions with different amounts of phenol by Zr-1a. C4; b. C6; c. C8; d. C10; e. C12; f. C14; g. C16; h. C18; i. C20; j. C22; k. C24; l. C26.

Table 2 Effects of free phenols on ethylene oligomerization

Catalyst	Phenol	n(Zr)∶n(Phenol)	10^-4Activity/ [g·(mol Zr·h)^-1]	Product
Zr-1b			6.83	α-Olefin
Zr-1e			30.10	Few Polymers
Zr-1e	PhOH	1∶1	4.19	α-Olefin
Zr-1e	^tBu₂PhOH	1∶1	3.72	α-Olefin

Table 3 Results of ethylene oligomerization with different pressures by complex Zr-1

Pressure/MPa	0.2	0.5	1.0	2.0
10^-5Activity/[g·(mol Zr·h)^-1]	72.40	1.59	1.38	2.29

Fig.5 Distributions of products on different pressuresa. C4; b. C6; c. C8; d. C10; e. C12; f. C14; g. C16; h. C18; i. L2; j. L4; k. L6; l. L8; m. L10;n. L12; o. L14; p. L16; q. M6; r. M8; s. M10; t. M12; u. M14; v. N12; w. N14; x. N16.

Fig.6 Tandem action of ethylene oligomerization and Friedel-Crafts alkylation

Fig.7 Distributions of normal pressure products by different catalystsa. C4; b. C6; c. C8; d. C10; e. C12; f. C14; g. C16; h. C18; i. C20; j. C22; k. L2;l. L4; m. L6; n. L8; o. L10; p. L12; q. L14; r. L16; s. M6; t. M8; u. M10; v. M12.

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