Bridged nitrogen heterocyclic ring metallocene compound as well as preparation method and application thereof

Abstract

The invention provides a bridged nitrogen heterocyclic ring metallocene compound which has a structure as shown in a formula (I) defined in the description, wherein R1 is a substituted or unsubstituted alkyl group of C1 to C30, a substituted or unsubstituted cycloalkyl group of C3 to C30, a substituted or unsubstituted aryl group of C6 to C30, and a substituted or unsubstituted aromatic heterocyclic group of C6 to C30; R2 and R3 are respectively and independently alkyl groups or phenyl groups of C1 to C10; R4 is a substituted or unsubstituted alkyl group of C1 to C10, and a substituted or unsubstituted aryl group of C6 to C20; X is halogen, substituted or unsubstituted alkyl; and M is fourth subgroup transition metal titanium, zirconium or hafnium. Compared with the prior art, the metallocene compound provided by the invention has the advantages that the structure is convenient to modify, the catalytic activity is high, the temperature resistance is good, relatively high catalytic activity can be kept under a high-temperature condition, and a polymer product with high molecular weight and high comonomer insertion rate can be obtained when the metallocene compound is used for catalyzing a copolymerization reaction of ethylene and alpha-olefin.

Description

technical field [0001] The invention belongs to the technical field of olefin polymerization catalysts, and in particular relates to a bridged nitrogen-containing heterocyclic metallocene compound, its preparation method and application. Background technique [0002] As an important class of polymer materials, polyolefin has become an indispensable part of human life, and the market demand for polyolefin materials is also increasing. In recent years, new processes such as high-efficiency catalysis, metallocene process, copolymerization process, and bimodal process have been continuously innovated, and the application of various modification, compounding, and alloying technologies has broadened the application fields of polyolefin resins, making many engineering resins Polyolefin resins have also begun to be widely used in the field of application. The huge demand has promoted the rapid development of the polyolefin industry, and the progress of the polyolefin industry techn...

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Problems solved by technology

[0003] A variety of new semi-sandwiches were reported in articles published by Sumitomo Corporation of Japan (Organometallics., 2009, 28, 3785-3792; Organometallics., 2009, 28, 6915-6926; Organometallics., 2010, 43, 2299-2306.) Type PHENICS catalyst, this type of catalyst has excellent high temperature resistance, and it can be used as the main catalyst to catalyze the copolymerization reaction of ethylene and 1-hexene to obtain a high insertion rate copolymer product; the patents WO2019132523A1 and WO2019038605A1 applied by South Korea SK Company were issued in Japan Partial modification based on the PHENICS catalyst applied for protection by Sumitomo Company, which studied the effect of the modification group on the copolymerization of ethylene and 1-hexene catalyzed by the modified PHENICS catalyst, and obtained a series of high comonomer insertion rates under high temperature polymerization conditions polymer products; although these disclosed catalysts can ensure a high comonomer insertion rate under high temperature polymerization conditions, the molecular weight of the resulting polymer is generally low, and the main research in the literature reports is only the copolymerization of ethylene and 1-hexene reaction

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