Catalyst system, use thereof, and olefin polymerization method

Abstract

The present invention relates to the field of olefin polymerization catalyst technology, and in particular, to a catalyst system, use thereof, and an olefin polymerization method. The catalyst system comprises: (1) a solid catalyst component, comprising titanium, magnesium, a halogen, and an internal electron donor, wherein the internal electron donor is a non-plasticizer compound; (2) an alkylaluminum compound, serving as a co-catalyst; and (3) an external electron donor, wherein the external electron donor is a silane compound of formula (I). The catalyst system can improve the polymerization activity and hydrogen regulation sensitivity of Z-N catalysts, and is particularly suitable for the polymerization of CH2=CHR olefins.

Description

Catalyst systems and their applications, olefin polymerization methods

[0001] Cross-references to related applications

[0002] This application claims the benefit of Chinese Patent Application No. 202411640239.5, filed on November 15, 2024, and Chinese Patent Application No. 202411640295.9, filed on November 15, 2024, the contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to the field of olefin polymerization catalyst technology, and more particularly to a catalyst system and its application, and an olefin polymerization method. Background Technology

[0004] The polypropylene industry has a history of nearly seventy years since Professor Natta of the Polytechnic Institute of Milan, Italy, first synthesized crystalline polypropylene using a titanium tetrachloride-triethylaluminum catalyst in 1954. To date, 95% of polypropylene in the industry is still produced using the Ziegler-Natta propylene polymerization catalyst, which has high polymerization activity and produces polypropylene with good stereoregularity.

[0005] Ziegler-Natta propylene polymerization catalysts typically consist of three parts: (1) a solid catalyst component consisting of magnesium chloride, titanium tetrachloride, and an internal electron donor, i.e., the "main catalyst"; (2) an activator alkyl aluminum, currently mainly triethylaluminum in polypropylene industrial plants; and (3) an external electron donor (also known as a modifier), currently mainly silane compounds in polypropylene industrial plants.

[0006] The primary role of external electron donors, silane compounds, is to enhance the stereoregulation of catalysts. Silane compounds can selectively poison atactic active sites during polymerization, coordinating with internal electron donors in the main catalyst to influence the structure and performance of the active sites. This transforms atactic active sites into mesotactic active sites, and mesotactic active sites into hyperisotactic active sites. Furthermore, because external electron donors are added during polymerization, the type, amount, and method of addition are flexible and easy to manage, making them ideal for adjusting the final properties of the product. Currently, commonly used silane electron donors in polypropylene industrial plants include cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisobutyldimethoxysilane, and diisopropyldimethoxysilane. Generally, while silane external electron donors enhance the stereoregulation of catalysts, they also reduce the polymerization activity and hydrogen sensitivity to some extent.

[0007] Because external electron donors are added during the polymerization process, the types, amounts, and methods of addition are flexible and easy to operate, making them ideal for adjusting the final properties of the product. External electron donor technology has also been a research hotspot in the polypropylene industry and academia. For example, aminosilane compounds are a newly discovered class of external electron donors in recent years, exhibiting excellent hydrogen sensitivity and high stereoselectivity. Improving the hydrogen sensitivity of catalysts through external electron donors is of great significance. In polypropylene industrial plants (especially gas-phase plants), using catalysts with high hydrogen sensitivity can significantly reduce the amount of hydrogen added during polymerization, thereby reducing the reactor's operating pressure and lowering the requirements for the plant's heat exchange capacity.

[0008] Currently, most polypropylene industrial plants in China use fourth-generation Ziegler-Natta catalysts, which are phthalate catalysts. However, phthalate compounds, as plasticizers, pose increasing concerns about their potential harm to human health. With the enactment of the REACH regulation, developed countries such as the EU, the US, and Japan have strictly restricted the use of plasticizers in plastic products. my country has also successively formulated relevant national standards, such as the "Hygienic Standard for the Use of Additives in Food Containers and Packaging Materials," to limit the amount of phthalate compounds used. Therefore, in recent years, the development of fifth-generation Ziegler-Natta catalysts, i.e., non-phthalate ZN catalysts, has become a hot topic in the polypropylene industry and academia. The development of external electron donors for these catalysts has also become a research focus in the polypropylene industry and academia. Summary of the Invention

[0009] To address the aforementioned problems, this invention provides a catalyst system and its application, as well as an olefin polymerization method. The catalyst system contains silane compounds with specific structures as external electron donors, and when combined with non-plasticizer internal electron donors, it can improve the polymerization activity and hydrogen sensitivity of ZN catalysts compared to existing silane external electron donors, making it particularly suitable for CH2=CHR olefin polymerization.

[0010] The first aspect of the present invention provides a catalyst system comprising:

[0011] (1) The catalyst solid component contains titanium, magnesium, halogen and internal electron donor; the internal electron donor is a non-plasticizer compound;

[0012] (2) Alkyl aluminum compounds as co-catalysts;

[0013] (3) External electron donor, wherein the external electron donor is a silane compound represented by formula (I);

[0014] In equation (I), Ra and R a’ Each is independently selected from H, C1-20 straight-chain alkyl, C3-20 branched alkyl, C3-20 cycloalkyl, C6-20 aryl, C7-20 alkylaryl, and C7-20 aryl, R b R c They may be the same or different, each independently selected from C1-20 straight-chain alkyl, C3-20 branched alkyl, C3-20 cycloalkyl, C6-20 aryl, C7-20 alkylaryl, and C7-20 aryl, optionally R a R a’ R b R c The elements are connected to form saturated or unsaturated rings, where p is an integer from 1 to 4, q and m are each an independent integer from 0 to 3, n is an integer from 1 to 4, and m + n + q = 4.

[0015] A second aspect of the present invention provides an application of the catalyst system described in the first aspect of the present invention in olefin polymerization.

[0016] A third aspect of the present invention provides a method for olefin polymerization, comprising: contacting an olefin with a catalyst system described in the first aspect of the present invention and carrying out a polymerization reaction.

[0017] The beneficial effects of this invention are:

[0018] The external electron donor composition or catalyst system provided by the present invention comprises a silane compound with a specific structure as an external electron donor and a non-plasticizer compound as an internal electron donor. Compared with the catalysts with existing silane external electron donors, it can improve the polymerization activity and hydrogen regulation sensitivity of ZN catalysts, and is particularly suitable for application in CH2=CHR olefin polymerization. Detailed Implementation

[0019] The first aspect of the present invention provides a catalyst system comprising:

[0020] (1) The catalyst solid component contains titanium, magnesium, halogen and internal electron donor; the internal electron donor is a non-plasticizer compound;

[0021] (2) Alkyl aluminum compounds as co-catalysts;

[0022] (3) An external electron donor, wherein the external electron donor comprises a silane compound represented by formula (I);

[0023] In equation (I), R a and R a’Each is independently selected from H, C1-20 straight-chain alkyl, C3-20 branched alkyl, C3-20 cycloalkyl, C6-20 aryl, C7-20 alkylaryl, and C7-20 aryl, R b R c They may be the same or different, each independently selected from C1-20 straight-chain alkyl, C3-20 branched alkyl, C3-20 cycloalkyl, C6-20 aryl, C7-20 alkylaryl, and C7-20 aryl, optionally R a R a’ R b R c The elements are connected to form saturated or unsaturated rings, where p is an integer from 1 to 4, q and m are each an independent integer from 0 to 3, n is an integer from 1 to 4, and m + n + q = 4.

[0024] The external electron donor composition or catalyst system provided by the present invention comprises a silane compound with a specific structure as an external electron donor and a non-plasticizer compound as an internal electron donor. Compared with catalysts containing classic silane external electron donors, it can improve the polymerization activity and hydrogen regulation sensitivity of ZN catalysts, and is particularly suitable for application in CH2=CHR olefin polymerization.

[0025] In this invention, p is (OR b The number of repeating units.

[0026] In a specific embodiment of the present invention, in formula (I), R a R a’ R b R c Each is independently selected from C1-10 straight-chain alkyl, C3-10 branched alkyl, C3-10 cycloalkyl, C6-10 aryl and C7-10 aryl.

[0027] In a specific embodiment of the present invention, in formula (I), R a R a’ R b R c Each is independently selected from C1-6 straight-chain alkyl, C3-6 branched alkyl, C3-6 cycloalkyl, C6-9 aryl and C7-9 aryl.

[0028] In a specific embodiment of the present invention, in formula (I), R a R a’ R b R c They may be the same or different, each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, cyclopentyl, phenyl, and benzyl.

[0029] As a specific embodiment of the present invention, in formula (I), R b R c Whether the same or different, they are each independently selected from C1-4 straight-chain alkyl groups and C3-4 branched alkyl groups.

[0030] As a specific embodiment of the present invention, R b R c They may be the same or different, and are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0031] As a specific embodiment of the present invention, in formula (I), each R a and R a’ At least one of them is selected from C3-6 branched alkyl, C3-6 cycloalkyl, C6-9 aryl and C7-9 aryl.

[0032] As a specific embodiment of the present invention, in formula (I), each R a and R a’ At least one of them is selected from isopropyl, isobutyl, tert-butyl, isopentyl, cyclopentyl, phenyl and benzyl.

[0033] In a specific embodiment of the present invention, p is an integer from 1 to 2.

[0034] In a specific embodiment of the present invention, m is an integer from 1 to 3.

[0035] In a specific embodiment of the present invention, q is an integer from 0 to 3.

[0036] In a specific embodiment of the present invention, n is an integer from 1 to 2.

[0037] As a specific embodiment of the present invention, the silane compound described in formula (I) is selected from (2-methoxy)ethoxytriisopropylsilane, (2-ethoxy)ethoxytriisopropylsilane, 2-(2-methoxyethoxy)ethoxytriisopropylsilane, 2-(2-ethoxyethoxy)ethoxytriisopropylsilane, (2-methoxy)ethoxytert-butyldimethylsilane, (2-ethoxy)ethoxytert-butyldimethylsilane, bis(2-(2-methoxyethoxy))ethoxytert-butyldimethylsilane, bis(2-(2-ethoxyethoxy))ethoxytert-butyldimethylsilane, (2,2-Diethoxy)ethoxy-tert-butyldimethylsilane, bis(2-methoxy)ethoxydimethylsilane, bis(2-ethoxy)ethoxydimethylsilane, bis(2-(2-methoxyethoxy))ethoxydimethylsilane, bis(2-(2-ethoxyethoxy))ethoxydimethylsilane, bis(2-methoxy)ethoxydiisopropylsilane, bis(2-ethoxy)ethoxydiisopropylsilane, bis(2-(2-methoxyethoxy))ethoxydiisopropylsilane, bis(2-(2-ethoxyethoxy))ethoxydiisopropylsilane, bis(2-methoxy) ethoxydicyclopentylsilane, bis(2-ethoxy)ethoxydicyclopentylsilane, bis(2-(2-methoxyethoxy))ethoxydicyclopentylsilane, bis(2-(2-ethoxyethoxy))ethoxydicyclopentylsilane, bis(2-methoxy)ethoxydiphenylsilane, bis(2-ethoxy)ethoxydiphenylsilane, bis(2-(2-methoxyethoxy))ethoxydiphenylsilane, bis(2-(2-ethoxyethoxy))ethoxydiphenylsilane, bis(2-methoxy)ethoxycyclohexylmethylsilane, bis(2-ethoxy)ethoxycyclohexylmethylsilane, At least one of the following: bis(2-(2-methoxyethoxy))ethoxycyclohexylmethylsilane, bis(2-(2-ethoxyethoxy))ethoxycyclohexylmethylsilane, tris(2-methoxy)ethoxysilane, tris(2-ethoxy)ethoxysilane, tris(2-methoxyethoxy))ethoxysilane, tris(2-ethoxyethoxy))ethoxysilane, tetra(2-methoxy)ethoxysilane, tetra(2-ethoxy)ethoxysilane, tetra(2-ethoxy)ethoxysilane, and tetra(2-(2-ethoxyethoxy))ethoxysilane;Preferably selected from (2-methoxy)ethoxytriisopropylsilane, (2-ethoxy)ethoxytriisopropylsilane, 2-(2-methoxyethoxy)ethoxytriisopropylsilane, 2-(2-ethoxyethoxy)ethoxytriisopropylsilane, (2-methoxy)ethoxytert-butyldimethylsilane, (2-ethoxy)ethoxytert-butyldimethylsilane, di(2-(2-ethoxyethoxy))ethoxytert-butyldimethylsilane, (2,2-diethoxy)ethoxytert-butyldimethylsilane, di(2-methoxy)ethoxydimethylsilane, di(2-ethoxy)ethoxydimethylsilane, di(2-ethoxy)ethoxydimethylsilane, di(2-(2-methoxyethoxy))ethoxydimethylsilane, di(2-methoxy)ethoxydiisopropylsilane, di(2-ethoxy)ethoxydiisopropylsilane, di(2-(2-methoxyethoxy))ethoxy At least one of the following: diisopropylsilane, di(2-(2-ethoxyethoxy))ethoxydiisopropylsilane, di(2-methoxy)ethoxydicyclopentylsilane, di(2-ethoxy)ethoxydicyclopentylsilane, di(2-(2-ethoxyethoxy))ethoxydicyclopentylsilane, di(2-methoxy)ethoxydiphenylsilane, di(2-ethoxy)ethoxydiphenylsilane, di(2-methoxy)ethoxycyclohexylmethylsilane, di(2-ethoxy)ethoxycyclohexylmethylsilane, di(2-ethoxy)ethoxycyclohexylmethylsilane, tris(2-ethoxy)ethoxysilane, tetra(2-methoxy)ethoxysilane, tetra(2-ethoxy)ethoxysilane, tetra(2-ethoxy)ethoxysilane, and tetra(2-(2-ethoxyethoxy))ethoxysilane.

[0038] As a specific embodiment of the present invention, the external electron donor compound further includes a silane compound represented by formula (II).

[0039] (R d ) x Si(OR e ) y (II)

[0040] In equation (II), R d R e They may be the same or different, each independently selected from C1-20 straight-chain alkyl, C3-20 branched alkyl, C3-20 cycloalkyl, C6-20 aryl, C7-20 alkylaryl and C7-20 aralkyl, optionally connected to form saturated or unsaturated rings, x is an integer from 0 to 3, y is an integer from 1 to 4, and x+y=4.

[0041] In this invention, when the external electron donor compound includes both the silane compound shown in formula (I) and the silane compound shown in formula (II), the polymerization activity and hydrogen sensitivity of the catalyst system can be further improved.

[0042] As a specific embodiment of the present invention, in formula (II), R d R e Each is independently selected from C1-10 straight-chain alkyl, C3-10 branched alkyl, C3-10 cycloalkyl and C6-10 aryl.

[0043] As a specific embodiment of the present invention, in formula (II), R d R e Each is independently selected from C1-6 straight-chain alkyl, C3-6 branched alkyl, C3-6 cycloalkyl and C6-9 aryl.

[0044] As a specific embodiment of the present invention, in formula (II), R d R e Each is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, cyclopentyl, and phenyl.

[0045] As a specific embodiment of the present invention, in formula (II), x is an integer from 1 to 3.

[0046] As a specific embodiment of the present invention, in formula (II), y is an integer from 1 to 2.

[0047] As a specific embodiment of the present invention, the silane compound represented by formula (II) is selected from at least one of dimethoxydicyclopentylsilane, dimethoxydiisopropylsilane, dimethoxydiisobutylsilane, dimethoxymethylcyclohexylsilane, tetraethoxysilane, and isobutyltriethoxysilane; preferably selected from at least one of dimethoxydicyclopentylsilane, dimethoxydiisopropylsilane, dimethoxydiisobutylsilane, and dimethoxymethylcyclohexylsilane.

[0048] As a specific embodiment of the present invention, the molar ratio of the silane compound shown in formula (I) to the silane compound shown in formula (II) is 0.01-100:1, for example, it can be 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 4:1, 6:1, 8:1, 10:1, 12:1. 14:1, 16:1, 18:1, 20:1, 22:1, 24:1, 26:1, 28:1, 30:1, 32:1, 34:1, 36:1, 38:1, 40:1, 42:1, 44:1, 46:1, 48:1, 50:1, 52:1, 54:1, 56:1, 58:1, 60:1, 62:1, 64:1, 66:1, 68:1, 70:1, 72:1, 74:1, 76:1, 78:1, 80:1, 82:1, 84:1, 86:1, 88:1, 90:1, 92:1, 94:1, 96:1, 98:1, 100:1, and the range of any two values.

[0049] In this invention, when the molar ratio of the silane compound shown in formula (I) to the silane compound shown in formula (II) meets the above-mentioned range, the polymerization activity and hydrogen sensitivity of the catalyst system can be further improved.

[0050] As a specific embodiment of the present invention, the molar ratio of the silane compound shown in formula (I) to the silane compound shown in formula (II) is 0.05-20:1.

[0051] As a specific embodiment of the present invention, the non-plasticizer compound is selected from at least one of 1,3-diether compounds, diol ester compounds, cyanosuccinate compounds, succinate compounds, and diphenol ester compounds.

[0052] As a specific embodiment of the present invention, the 1,3-diether compound is selected from the diether compounds shown in formula (III).

[0053] In equation (III), R g R f They may be the same or different, each independently selected from C1-20 straight-chain alkyl, C3-20 branched alkyl, C3-20 cycloalkyl, C6-20 aryl, C7-20 alkylaryl, and C7-20 aryl, optionally R g R f Connect them to form a ring.

[0054] As a specific embodiment of the present invention, in formula (III), R g R f Each is independently selected from C1-10 straight-chain alkyl, C3-10 branched alkyl, C3-10 cycloalkyl, and C6-10 aryl.

[0055] As a specific embodiment of the present invention, in formula (III), R g R f Each is independently selected from C1-6 straight-chain alkyl, C3-6 branched alkyl, and C3-6 cycloalkyl.

[0056] As a specific embodiment of the present invention, in formula (III), R g R f Each is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, and cyclopentyl.

[0057] As a specific embodiment of the present invention, the diether compound represented by formula (III) is selected from at least one of 2,2-diisobutyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-isopentyl-2-isopropyl-1,3-dimethoxypropane and 9,9-bis(methoxymethyl)fluorene, preferably 2-isopentyl-2-isopropyl-1,3-dimethoxypropane and / or 9,9-bis(methoxymethyl)fluorene.

[0058] As a specific embodiment of the present invention, the diol ester compound is selected from the diol ester compounds shown in formula (IV).

[0059] Among them, R m R n R h R k and R j They may be the same or different, and are each independently selected from H, C1-10 straight-chain alkyl, C3-10 branched alkyl, C3-10 cycloalkyl or C6-10 aryl.

[0060] As a specific embodiment of the present invention, in formula (IV), R m R n R h R k and R j Each is independently selected from H, C1-6 straight-chain alkyl, C3-6 branched alkyl, more preferably from H, methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.

[0061] As a specific embodiment of the present invention, the diol ester compound represented by formula (IV) is selected from at least one of 2,4-pentanediol dibenzoate, 2,4-pentanediol di(4-methyl)benzoate, 2,4-pentanediol di(4-ethyl)benzoate, 2,4-pentanediol di(4-n-propyl)benzoate, 2,4-pentanediol di(4-n-butyl)benzoate, 3,5-heptanediol dibenzoate, 3,5-heptanediol di(4-methyl)benzoate, 3,5-heptanediol di(4-ethyl)benzoate, 3,5-heptanediol di(4-n-propyl)benzoate, and 3,5-heptanediol di(4-n-butyl)benzoate, preferably selected from at least one of 2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, and 3,5-heptanediol di(4-n-butyl)benzoate.

[0062] As a specific embodiment of the present invention, the cyanosuccinate compound is selected from diethyl 2-cyano-2,3-diisopropylsuccinate and / or di-n-butyl 2-cyano-2,3-diisopropylsuccinate.

[0063] As a specific embodiment of the present invention, the succinate compound is selected from diethyl 2,3-diisopropylsuccinate and / or di-n-butyl 2,3-diisopropylsuccinate.

[0064] As a specific embodiment of the present invention, the diphenol ester compound is at least one selected from 3-tert-butyl-5-methyl-1,2-catechol dibenzoate, 4-tert-butyl-1,2-catechol dibenzoate, and 3,5-di-tert-butyl-1,2-catechol dibenzoate.

[0065] As a specific embodiment of the present invention, the non-plasticizer compound is selected from at least one of the following: a combination of 1,3-diether compounds and diol ester compounds; a combination of 1,3-diether compounds and cyanosuccinate compounds; a combination of 1,3-diether compounds and succinate compounds; and a combination of 1,3-diether compounds and diphenol ester compounds.

[0066] As a specific embodiment of the present invention, the internal electron donor includes 1,3-diether compounds and diol ester compounds.

[0067] In a specific embodiment of the present invention, the mass ratio of the 1,3-diether compound to the diol ester compound is 0.01-100:1, for example, it can be 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 1 2:1, 14:1, 16:1, 18:1, 20:1, 22:1, 24:1, 26:1, 28:1, 30:1, 32:1, 34:1, 36:1, 38:1, 40:1, 42:1, 44:1, 46:1, 48:1, 50:1, 52:1, 54:1, 56:1, 58:1, 60:1, 62:1, 64:1, 66:1, 68:1, 70:1, 72:1, 74:1, 76:1, 78:1, 80:1, 82:1, 84:1, 86:1, 88:1, 90:1, 92:1, 94:1, 96:1, 98:1, 100:1, and the range of any two values.

[0068] In a preferred embodiment of the present invention, the mass ratio of the 1,3-diether compound to the diol ester compound is 0.1-10:1.

[0069] As a specific embodiment of the present invention, the internal electron donor includes 1,3-diether compounds and cyanosuccinate.

[0070] In a specific embodiment of the present invention, the mass ratio of the 1,3-diether compound to the cyanosuccinate is 0.01-100:1, for example, it can be 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 1 2:1, 14:1, 16:1, 18:1, 20:1, 22:1, 24:1, 26:1, 28:1, 30:1, 32:1, 34:1, 36:1, 38:1, 40:1, 42:1, 44:1, 46:1, 48:1, 50:1, 52:1, 54:1, 56:1, 58:1, 60:1, 62:1, 64:1, 66:1, 68:1, 70:1, 72:1, 74:1, 76:1, 78:1, 80:1, 82:1, 84:1, 86:1, 88:1, 90:1, 92:1, 94:1, 96:1, 98:1, 100:1, and the range of any two values.

[0071] In a preferred embodiment of the present invention, the mass ratio of the 1,3-diether compound to the cyanosuccinate is 0.1-10:1.

[0072] As a specific embodiment of the present invention, the internal electron donor includes 1,3-diether compounds and succinate compounds.

[0073] In a specific embodiment of the present invention, the mass ratio of the 1,3-diether compound to the succinate compound is 0.01-100:1, for example, it can be 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1. 12:1, 14:1, 16:1, 18:1, 20:1, 22:1, 24:1, 26:1, 28:1, 30:1, 32:1, 34:1, 36:1, 38:1, 40:1, 42:1, 44:1, 46:1, 48:1, 50:1, 52:1, 54:1, 56:1, 58:1, 60:1, 62:1, 64:1, 66:1, 68:1, 70:1, 72:1, 74:1, 76:1, 78:1, 80:1, 82:1, 84:1, 86:1, 88:1, 90:1, 92:1, 94:1, 96:1, 98:1, 100:1, and the range of any two values.

[0074] In a preferred embodiment of the present invention, the mass ratio of the 1,3-diether compound to the succinate compound is 0.1-10:1.

[0075] In a specific embodiment of the present invention, in the solid catalyst component, titanium is calculated as titanium atoms, magnesium as magnesium atoms, and halogens as halogen atoms. The content of titanium atoms is 1-8 wt% (for example, it can be 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, or any range of two values); the content of magnesium atoms is preferably 10-70 wt% (for example, it can be 10 wt%, 12 wt%, 14 wt%, 16 wt%, 18 wt%, 20 wt%, 22 wt%, 24 wt%, 26 wt%, 28 wt%, 30 wt%, 32 wt%, 34 wt%, 36 wt%, 38 wt%, 40 wt%, 42 wt%, 44 wt%, 46 wt%, 48 wt%, 50 wt%, 52 wt%, 54 wt%). 56wt%, 58wt%, 60wt%, 62wt%, 64wt%, 66wt%, 68wt%, 70wt%, and any two of these values); halogen content is 20-90wt% (e.g., 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, and any two of these values); internal electron donor content is 2-30wt% (e.g., 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt%, 22wt%, 24wt%, 26wt%, 28wt%, 30wt%, and any two of these values).

[0076] In this invention, when the content of each component in the solid component of the catalyst meets the above-mentioned range, the catalyst system can have higher polymerization activity.

[0077] In a preferred embodiment of the present invention, the solid component of the catalyst comprises titanium (based on titanium atoms), magnesium (based on magnesium atoms), and halogens (based on halogen atoms), with the titanium atom content being 1-6 wt%, the magnesium atom content being 12-40 wt%, the halogen atom content being 30-85%, and the internal electron donor content being 3-20 wt%.

[0078] In a specific embodiment of the present invention, the alkylaluminum compound is calculated as aluminum, the catalyst solid component is calculated as titanium, and the molar ratio of the alkylaluminum compound to the catalyst solid component is 5-5000:1, for example, it can be 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, 120:1, 140:1, 160:1, 180:1, 200:1, 250:1, 300:1, 350:1, 400:1, 450:1, 500:1, 550:1, 60 ...600:1, 700:1, 800:1, 900:1, 100:1, 120:1, 140:1, 160:1, 180:1, 200:1, 250:1, 300:1, 350:1, 400:1, 450:1, 500:1, 550:1, 600:1, 600:1, 700:1, 800:1, 9 0:1, 650:1, 700:1, 750:1, 800:1, 850:1, 900:1, 950:1, 1000:1, 1200:1, 1400:1, 1600:1, 1800:1, 2000:1, 2200:1, 2400:1, 2600:1, 2800:1, 3000:1, 3200:1, 3400:1, 3600:1, 3800:1, 4000:1, 4200:1, 4400:1, 4600:1, 5000:1, and any range of two values; preferably 20-1000:1; more preferably 50-500:1.

[0079] In a specific embodiment of the present invention, the molar ratio of the alkylaluminum compound to the external electron donor is 0.1-500:1, for example, it can be 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1, or 90:1. The ratios are 95:1, 100:1, 120:1, 140:1, 160:1, 180:1, 200:1, 220:1, 240:1, 260:1, 280:1, 300:1, 320:1, 340:1, 360:1, 380:1, 400:1, 420:1, 440:1, 460:1, 480:1, 500:1, and any range of two values, preferably 1-300:1, more preferably 3-100:1.

[0080] In a specific embodiment of the present invention, the magnesium in the catalyst solid component is derived from a magnesium compound, which includes at least one of the magnesium compound represented by formula (Va), a hydrate of the magnesium compound represented by formula (Vb), and an alcohol adduct of the magnesium compound represented by formula (Vc).

[0081] MgR1R2 (Va),

[0082] MgR1R2·qH2O (Vb),

[0083] MgR1R2·pR0OH (Vc),

[0084] Wherein, R1 and R2 may be the same or different, and each is independently selected from halogen, C1-5 straight-chain alkyl, C3-5 branched alkyl, C1-5 straight-chain alkoxy, and C3-5 branched alkoxy; R0 is selected from C1-18 hydrocarbon groups, preferably from C1-5 alkyl, and more preferably from methyl, ethyl, n-propyl, and isopropyl; 0.1≤q≤6, preferably 2≤q≤3.5; 0.1≤p≤6, preferably 2≤p≤3.5.

[0085] In a specific embodiment of the present invention, R1 and R2 are each independently selected from halogens; preferably, the halogens are selected from chlorine, bromine and iodine.

[0086] As a specific embodiment of the present invention, the magnesium compound is selected from at least one of dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium, diisobutoxy magnesium, dipentoxy magnesium, dihexyloxy magnesium, di(2-methyl)hexyloxy magnesium, methoxy magnesium chloride, methoxy magnesium bromide, methoxy magnesium iodide, ethoxy magnesium chloride, ethoxy magnesium bromide, ethoxy magnesium iodide, propoxy magnesium chloride, propoxy magnesium bromide, propoxy magnesium iodide, butoxy magnesium chloride, butoxy magnesium bromide, butoxy magnesium iodide, magnesium dichloride, magnesium dibromide, magnesium diiodide, alcohol adducts of magnesium dichloride, alcohol adducts of magnesium dibromide, and alcohol adducts of magnesium diiodide; preferably, the magnesium compound is diethoxy magnesium or magnesium dichloride.

[0087] In a specific embodiment of the present invention, the titanium in the catalyst solid component is derived from a titanium compound, and the titanium compound is selected from the titanium compound shown in formula (VI).

[0088] TiX m (OR3) 4-m (VI)

[0089] In formula (VII), X is a halogen, preferably chlorine, bromine or iodine, R3 is selected from C1-20 hydrocarbon groups, and m is an integer from 1 to 4; preferably, R3 is selected from C1-5 alkyl groups.

[0090] As a specific embodiment of the present invention, the titanium compound represented by formula (VI) is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloromonoethoxy; preferably titanium tetrachloride.

[0091] In this invention, the alkylaluminum compound can be any alkylaluminum compound commonly used in the field of olefin polymerization that can be used as a co-catalyst for Ziegler-Natta type catalysts. As a specific embodiment of this invention, the alkylaluminum compound is selected from the alkylaluminum compounds shown in formula (VII).

[0092] AlR' n' X' 3-n' (VII),

[0093] In formula (VII), R' is selected from hydrogen, C1-C 20 Alkyl and C6-C 20 The aryl group, X' is a halogen, and n' is an integer from 1 to 3.

[0094] As a specific embodiment of the present invention, the alkyl aluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydrogen, diisobutylaluminum hydrogen, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, and diethylaluminum chloride.

[0095] The catalyst solid component of the present invention can be prepared by contacting and reacting a magnesium compound, a titanium compound, and an internal electron donor under certain conditions. The amounts of the titanium compound, magnesium compound, and internal electron donor used to prepare the catalyst solid component are not particularly limited, and can be conventional substances and amounts used in the art.

[0096] As a specific embodiment of the present invention, the method for preparing the olefin polymerization catalyst component of the present invention by reacting a titanium compound, a magnesium compound, and an internal electron donor can be carried out by conventional methods for preparing olefin catalyst components in the art. For example, the olefin polymerization catalyst component of the present invention can be prepared by the following method.

[0097] Method 1: The catalyst component is prepared according to the following steps in accordance with CN102453150B: (1) An alkoxy magnesium compound or an alkoxy magnesium halide compound is reacted with a titanium compound and an electron donor compound (i.e., an internal electron donor) in the presence of an inert diluent; (2) The solid obtained in step (1) is washed with an inert solvent to obtain the catalyst solid component.

[0098] In Method 1, the alkoxymagnesium compound can be dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropoxymagnesium, dibutoxymagnesium, diisobutoxymagnesium, dipentoxymagnesium, dihexyloxymagnesium, di(2-methyl)hexyloxymagnesium, or a mixture thereof, preferably diethoxymagnesium or a mixture thereof. The preparation of this alkoxymagnesium compound can be carried out by methods known in the art, such as preparing it by reacting metallic magnesium with a fatty alcohol in the presence of a small amount of iodine.

[0099] In Method 1, the alkoxy magnesium halide compound can be methoxy magnesium chloride, ethoxy magnesium chloride, propoxy magnesium chloride, butoxy magnesium chloride, etc., with ethoxy magnesium chloride being preferred. The preparation method of this alkoxy magnesium halide compound can be any method known in the art, such as preparing ethoxy magnesium chloride by mixing the Grignard reagent butyl magnesium chloride with tetraethoxytitanium and tetraethoxysilane.

[0100] In step (1) of Method 1, the inert diluent is selected from at least one of C6-C10 alkanes or aromatics. Specific examples of the inert diluent may be one or a mixture of hexane, heptane, octane, decane, benzene, toluene, and xylene; toluene is preferred. There is no particular limitation on the order of contact; for example, the components can be contacted in the presence of the inert diluent, or the components can be pre-diluted with an inert solvent to allow them to contact. There is also no particular limitation on the number of contacts; there may be one contact or multiple contacts.

[0101] The catalyst solid component obtained through the above contact reaction can be washed with an inert solvent, such as a hydrocarbon compound. The inert solvent can be one or a mixture of hexane, heptane, octane, decane, benzene, toluene, and xylene, preferably hexane.

[0102] In this invention, there are no particular limitations on the washing method, but decantation, filtration, etc., are preferred. The amount of inert solvent used, the washing time, and the number of washing cycles are not particularly limited; typically, 1 to 1000 moles of solvent are used relative to 1 mole of magnesium compound, preferably 10 to 500 moles, and the washing time is typically 1 to 24 hours, preferably 1 to 6 hours. Furthermore, from the perspective of washing uniformity and efficiency, stirring is preferred during the washing operation. It should be noted that the obtained catalyst solid component can be stored in a dry state or in an inert solvent.

[0103] The amounts of each component used in Method 1, calculated per mole of magnesium, are as follows: The amount of titanium compound used is 0.5-100 moles, for example, 0.5 mol, 1 mol, 1.5 mol, 2 mol, 3 mol, 4 mol, 5 mol, 10 mol, 15 mol, 20 mol, 25 mol, 30 mol, 35 mol, 40 mol, 45 mol, 50 mol, 55 mol, 60 mol, 65 mol, 70 mol, 75 mol, 80 mol, 85 mol, 90 mol, 95 mol, 100 mol, and any range of two values, preferably 1-50 mol; the amount of inert diluent used is typically 0.5-100 mol, for example, 0.5 mol, 1 mol, 5 mol, 10 mol, 15 mol, 20 mol, 25 mol, 30 mol, 35 mol, 40 mol, 45 mol, 50 mol, 55 mol, 60 mol, 65 mol, 70 mol, 75 mol, 80 mol, 85 mol, 90 mol. The amounts are 95 mol, 100 mol, and any combination of two values, preferably 1-50 mol; the total amount of internal electron donors is typically 0.005-10 mol, for example, 0.005 mol, 0.01 mol, 0.05 mol, 0.01 mol, 0.15 mol, 0.2 mol, 0.25 mol, 0.3 mol, 0.35 mol, 0.4 mol, 0.45 mol, 0.5 mol, 0.55 mol, 0.6 mol, 0 The values ​​are 0.65 mol, 0.7 mol, 0.75 mol, 0.8 mol, 0.85 mol, 0.9 mol, 1 mol, 1.5 mol, 2 mol, 2.5 mol, 3 mol, 3.5 mol, 4 mol, 4.5 mol, 5 mol, 5.5 mol, 6 mol, 6.5 mol, 7 mol, 7.5 mol, 8 mol, 8.5 mol, 9 mol, 9.5 mol, 10 mol, and any range of two values, preferably 0.01-1 mol.

[0104] In Method 1, the contact temperature of each component is typically -40 to 200°C, for example, it can be -40°C, -30°C, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, or any combination of two values, preferably -20 to 150°C; the contact time is typically 1 minute to 20 hours, for example, it can be 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 5 hours, 60 minutes ... minutes, 80 minutes, 90 minutes, 100 minutes, 100 minutes, 100 minutes, 100 minutes, 100 minutes, 100 minutes The time is 0 minutes, 60 minutes, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours, 12.5 hours, 13 hours, 13.5 hours, 14 hours, 14.5 hours, 15 hours, 15.5 hours, 16 hours, 17.5 hours, 18 hours, 18.5 hours, 19 hours, 19.5 hours, 20 hours, and any range of two values, preferably 5 minutes to 8 hours.

[0105] Method 2, referring to the method of patent CN85100997A, involves dissolving magnesium dihalide in a solvent system composed of an organic epoxy compound, an organic phosphorus compound, and an inert diluent to form a homogeneous solution, which is then mixed with a titanium compound. In the presence of a precipitation aid, a solid is precipitated. The solid is then contacted with an internal electron donor to allow it to be attached to the solid to obtain the catalyst solid component.

[0106] The precipitation aid used in Method 2 can be at least one of organic anhydrides, organic acids, ethers, and ketones. Specific examples of the organic anhydrides can be at least one of acetic anhydride, phthalic anhydride, succinic anhydride, and maleic anhydride. Specific examples of the organic acids can be at least one of acetic acid, propionic acid, butyric acid, acrylic acid, and methacrylic acid. Specific examples of the ethers can be at least one of methyl ether, diethyl ether, propyl ether, butyl ether, and pentyl ether. The ketones can be at least one of acetone, methyl ethyl ketone, and benzophenone.

[0107] The organic epoxy compound used in Method 2 can be at least one selected from ethylene oxide, propylene oxide, butane oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, and diglycidyl ether, with epichlorohydrin being preferred.

[0108] The organophosphorus compound used in Method 2 can be a hydrocarbon ester or halohydrophosphoric acid or phosphorous acid. The organophosphorus compound can be: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, or phenyl phosphite, preferably tributyl orthophosphate.

[0109] The inert diluent used in Method 2 can be at least one of hexane, heptane, octane, decane, benzene, toluene, and xylene.

[0110] In Method 2, the amounts of each component used, calculated per mole of magnesium halide, are as follows: the organic epoxy compound can be 0.2-10 moles, for example, 0.2 mol, 0.3 mol, 0.4 mol, 0.5 mol, 0.6 mol, 0.7 mol, 0.8 mol, 0.9 mol, 1 mol, 2 mol, 3 mol, 4 mol, 5 mol, 6 mol, 7 mol, 8 mol, 9 mol, 10 mol, or any combination of two values, preferably 0.5-4 mol; the organophosphorus compound can be 0.1-3 moles, for example, 0.1 mol, 0.2 mol, 0.3 mol, 0.4 mol, 0.5 mol, 0.6 mol, 0.7 mol, 0.8 mol, 0.9 mol, 1 mol, 1.1 mol, 1.2 mol. The titanium compound can be in the range of 0.3-1.5 mol, 1.3 mol, 1.4 mol, 1.5 mol, 1.6 mol, 1.7 mol, 1.8 mol, 1.9 mol, 2 mol, 2.1 mol, 2.2 mol, 2.3 mol, 2.4 mol, 2.5 mol, 2.6 mol, 2.7 mol, 2.8 mol, 2.9 mol, 3 mol, and any two of these values, preferably 0.3-1.5 mol; the titanium compound can be in the range of 0.5-20 mol, for example, 0.5 mol, 1 mol, 1.5 mol, 2 mol, 2.5 mol, 3 mol, 3.5 mol, 4 mol, 4.5 mol, 5 mol, 5.5 mol, 6 mol, 6.5 mol, 7 mol, 7.5 mol, 8 mol, 8.5 mol, 9 mol, 9.5 mol. The concentrations of the precipitating component can be 10 mol, 10.5 mol, 11 mol, 11.5 mol, 12 mol, 12.5 mol, 13 mol, 13.5 mol, 14 mol, 14.5 mol, 15 mol, 15.5 mol, 16 mol, 16.5 mol, 17 mol, 17.5 mol, 18 mol, 18.5 mol, 19 mol, 19.5 mol, 20 mol, and any range of two values, preferably 5-15 mol; the concentration of the precipitating component can be 0.01-0.3 mol, for example, 0.01 mol, 0.02 mol, 0.03 mol, 0.04 mol, 0.05 mol, 0.06 mol, 0.07 mol, 0.08 mol, 0.09 mol, 0.1 mol, 0.12 mol, 0. The amounts of internal electron donors can be 14 mol, 0.16 mol, 0.18 mol, 0.2 mol, 0.22 mol, 0.24 mol, 0.26 mol, 0.28 mol, 0.3 mol, and any range of two values, preferably 0.02-0.08 mol; the total amount of internal electron donors can be 0-10 mol, for example, 0 mol, 0.01 mol, 0.02 mol, 0.03 mol, 0.04 mol, 0.05 mol, 0.06 mol, 0.07 mol, 0.08 mol, 0.09 mol, 0.1 mol, 0.15 mol, 0.2 mol, 0.25 mol, 0.3 mol, 0.35 mol, 0.4 mol, 0.45 mol, 0.5 mol, 0.55 mol, 0.6 mol, 0.The range of moles is 65 mol, 0.7 mol, 0.75 mol, 0.8 mol, 0.85 mol, 0.9 mol, 0.95 mol, 1 mol, 1.5 mol, 2 mol, 2.5 mol, 3 mol, 3.5 mol, 4 mol, 4.5 mol, 5 mol, 5.5 mol, 6 mol, 6.5 mol, 7 mol, 7.5 mol, 8 mol, 8.5 mol, 9 mol, 9.5 mol, 10 mol, and any two of these values, preferably 0.02-0.3 mol.

[0111] Method 3: The catalyst component is prepared according to the preparation method in CN1091748A. The magnesium chloride ethanolate melt is dispersed in a dispersion system of white oil and silicone oil by high-speed stirring to form an emulsion. This emulsion is then rapidly cooled and solidified in a cooling liquid to form magnesium chloride ethanolate microspheres. The cooling liquid is an inert hydrocarbon solvent with a low boiling point, such as petroleum ether, pentane, hexane, or heptane. The obtained magnesium chloride ethanolate microspheres are washed and dried to form a spherical carrier. The molar ratio of alcohol to magnesium chloride is 2–3:1, for example, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, or any combination of two values, preferably 2–2.5:1. The carrier particle size is 10–300 micrometers, for example, it can be 10 micrometers, 20 micrometers, 30 micrometers, 40 micrometers, 50 micrometers, 60 micrometers, 70 micrometers, 80 micrometers, 90 micrometers, 100 micrometers, 110 micrometers, 120 micrometers, 130 micrometers, 140 micrometers, 150 micrometers, 160 micrometers, 170 micrometers, 180 micrometers, 190 micrometers, 200 micrometers, 210 micrometers, 220 micrometers, 230 micrometers, 240 micrometers, 250 micrometers, 260 micrometers, 270 micrometers, 280 micrometers, 290 micrometers, 300 micrometers, or any combination of two values, preferably 30–150 micrometers.

[0112] The above spherical support was treated with an excess of titanium tetrachloride at low temperature, and the temperature was gradually increased. An electron donor was added during the treatment process. After treatment, the support was washed multiple times with an inert solvent and dried to obtain a solid powdered spherical catalyst. The molar ratio of titanium tetrachloride to magnesium chloride is 20-200:1, for example, it can be 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1, 90:1, 95:1, 100:1, 110:1, 120:1, 130:1, 140:1, 150:1, 160:1, 170:1, 180:1, 190:1, 200:1, or any range of two values, preferably 30-60:1; the initial treatment temperature is -30 to 0℃, for example, it can be -30℃, -25℃, - The range of temperatures is 20℃, -15℃, -10℃, -5℃, 0℃, and any two of these values, with -25℃ to -20℃ being preferred. The final processing temperature is 80℃ to 136℃, for example, 80℃, 82℃, 84℃, 86℃, 88℃, 90℃, 92℃, 94℃, 96℃, 98℃, 100℃, 102℃, 104℃, 106℃, 108℃, 110℃, 112℃, 114℃, 116℃, 118℃, 120℃, 122℃, 124℃, 126℃, 128℃, 130℃, 132℃, 134℃, 136℃, and any two of these values, with 100℃ to 130℃ being preferred.

[0113] The resulting spherical catalyst has the following characteristics: titanium content (by weight) of 1–6% (e.g., 1%, 2%, 3%, 4%, 5%, 6%, or any combination of two values); ester content (by weight) of 3.0–20.0% (e.g., 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, or any combination of two values); and chlorine content (by weight) of 30–80% (e.g., 30%, 35%, 40%). 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, and any two of these values), magnesium content (by weight) 12-35% (e.g., 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 35%, and any two of these values), inert solvent content (by weight) 1-10% (e.g., 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, and any two of these values).

[0114] Method 4: The catalyst was prepared according to the method disclosed in CN1506384A. First, a magnesium compound and an organic alcohol compound were mixed with an inert solvent at a molar ratio of 2-5, and the mixture was heated to 120-150°C to form a homogeneous solution. Phthalic anhydride, a silicon-containing compound, or other auxiliaries that facilitate the precipitation of good particles were selectively added. Then, the alcohol compound and titanium compound were reacted at a titanium / magnesium molar ratio of 20-50 for 2-10 hours at a reaction temperature of -15 to -40°C. In the presence of the precipitation aid, the temperature was raised to 90-110°C. An internal electron donor was added at a magnesium / ester molar ratio of 2-10, and the reaction was carried out at 100-130°C for 1-3 hours. The solid particles were separated by filtration. Then (this process can be selectively repeated 2-3 times), the solid particles and titanium compound were reacted at 100-130°C for 1.5-3 hours at a titanium / magnesium molar ratio of 20-50. The solid particles were separated by filtration. Finally, the solid particles were washed with an inert solvent at 50-80°C and dried to obtain the catalyst component.

[0115] In any of the four methods for preparing the olefin polymerization catalyst components of the present invention, the internal electron donor may be used alone or in combination of two or more.

[0116] In any of the four methods for preparing the olefin polymerization catalyst components of the present invention, the internal electron donor can also be added before or during the contact between the magnesium compound and the titanium compound. For example, in Method 1, the internal electron donor is first added to a suspension of alkoxymagnesium or alkoxy magnesium halide in an inert diluent, and then mixed with the titanium compound to prepare the olefin polymerization catalyst; in Method 2, the internal electron donor is added to the magnesium halide solution before the magnesium halide solution contacts the titanium compound.

[0117] In the preparation of the above-mentioned olefin polymerization catalyst components, the molar ratio of the internal electron donor to magnesium atoms is typically 0.01–3:1, for example, 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1. The range of values ​​is 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, and any two values, preferably 0.02 to 0.3:1.

[0118] A second aspect of the present invention provides an application of the catalyst system described in the first aspect of the present invention in olefin polymerization.

[0119] As a specific embodiment of the present invention, the general structural formula of the olefin is CH2=CHR, wherein R is selected from hydrogen, C1-C12 alkyl and C6-C12 aryl, preferably selected from hydrogen and C1-C6 alkyl.

[0120] As a specific embodiment of the present invention, the olefin is selected from at least one of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene.

[0121] A third aspect of the present invention provides a method for olefin polymerization, comprising: contacting an olefin with a catalyst system described in the first aspect of the present invention and carrying out a polymerization reaction.

[0122] According to the polymerization method for preparing polyolefins of the present invention, the polymerization conditions can be conventional conditions in the art. The amount of catalyst used can be the amount of various catalysts in the prior art.

[0123] As a specific embodiment of the present invention, the general structural formula of the olefin is CH2=CHR, wherein R is selected from hydrogen, C1-C12 alkyl and C6-C12 aryl, preferably selected from hydrogen and C1-C6 alkyl.

[0124] As a specific embodiment of the present invention, the olefin is selected from at least one of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene.

[0125] According to the present invention, the components in the catalyst system, namely the solid catalyst component, the organoaluminum compound as a co-catalyst, and the silane compound as an external electron donor, can be contacted before contacting the olefin monomer, which is referred to in the industry as "pre-contact" or "pre-complexation"; or the above three components can be added to the olefin monomer separately before the polymerization reaction, that is, without "pre-contact".

[0126] As a specific embodiment of the present invention, the catalyst system is pre-contacted with each component before it comes into contact with the olefin.

[0127] As a specific embodiment of the present invention, the pre-contact conditions include: a temperature of -20°C to 80°C, for example, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, and any range of any two values, preferably 10°C to 50°C; and a time of 0.1 min to 30 min, for example, 0.1 min, 0.5 min, 1 min, 1.5 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, 15 min, 16 min, 17 min, 18 min, 19 min, 20 min, 21 min, 22 min, 23 min, 24 min, 25 min, 26 min, 27 min, 28 min, 29 min, 30 min, and any range of any two values, preferably 1 min to 10 min.

[0128] As a specific embodiment of the present invention, the conditions of the polymerization reaction include: a temperature of 60°C to 90°C, for example, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, or any range of two values; and a time of 30 min to 240 min, for example, 30 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 120 min, 140 min, 160 min, 180 min, 200 min, 220 min, 240 min, or any range of two values.

[0129] The catalyst system is first polymerized to a certain extent in the presence of a small amount of olefin monomers to obtain a prepolymerized catalyst. The prepolymerized catalyst is then further reacted with olefin monomers to obtain an olefin polymer. This process, referred to as "prepolymerization," helps to improve the polymerization activity of the catalyst and the bulk density of the polymer. According to the olefin polymerization method provided by the present invention, a "prepolymerization" process may or may not be used; the "prepolymerization" process is preferred.

[0130] As a specific embodiment of the present invention, the olefin polymerization method further includes: before carrying out the polymerization reaction, subjecting the olefin to a prepolymerization reaction with the above-mentioned catalyst system.

[0131] As a specific embodiment of the present invention, the conditions for the prepolymerization reaction include: 1-1000 g olefin monomer / gcat, for example, 1 g olefin monomer / gcat, 5 g olefin monomer / gcat, 10 g olefin monomer / gcat, 20 g olefin monomer / gcat, 40 g olefin monomer / gcat, 60 g olefin monomer / gcat, 80 g olefin monomer / gcat, 100 g olefin monomer / gcat, 120 g olefin monomer / gcat, 140 g olefin monomer / gcat, 160 g olefin monomer / gcat. 180g olefin monomer / gcat, 200g olefin monomer / gcat, 250g olefin monomer / gcat, 300g olefin monomer / gcat, 350g olefin monomer / gcat, 400g olefin monomer / gcat, 450g olefin monomer / gcat, 500g olefin monomer / gcat, 550g olefin monomer / gcat, 600g olefin monomer / gcat, 650g olefin monomer / gcat, 700g olefin monomer / gcat, 750g olefin monomer / gcat, 800g olefin monomer / gcat The values ​​are: t, 850 g olefin monomer / gcat, 900 g olefin monomer / gcat, 950 g olefin monomer / gcat, 1000 g olefin monomer / gcat, and any range of two values, preferably 1-500 g olefin monomer / gcat; temperature -20°C to 80°C, for example, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, and any range of two values, preferably 0°C to 50°C; time 30 min to 480 min, for example, 3 0 min, 40 min, 50 min, 60 min, 70 min, 80 min, 90 min, 100 min, 120 min, 140 min, 160 min, 180 min, 200 min, 220 min, 240 min, 260 min, 280 min, 300 min, 320 min, 340 min, 360 min, 380 min, 400 min, 420 min, 440 min, 460 min, 480 min, and any range of two values.

[0132] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0133] (one)

[0134] Test method:

[0135] 1. The purity of the external electron donor compound was determined by gas chromatography;

[0136] 2. Calculation of polymerization activity: Catalyst activity = (mass of prepared polyolefin) / (mass of solid catalyst component) kg / g;

[0137] 3. Bulk density determination: The prepared polymer powder is dropped freely from a height of 10 cm into a 100 mL container through a funnel. The weight of the polymer powder in the container is Mg. The bulk density of the polymer is M / 100 g / cm³. 3 .

[0138] 4. Polymer melt flow rate (MFR, i.e., melt index in Table 1): According to the method in GB / T3682-2000, the test temperature is 230℃ and the load is 2.16kg;

[0139] 5. Isotacticity index (II) of propylene polymer: determined by heptane extraction method: 2g of dry polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. After drying the residue to constant weight, the ratio of the polymer weight (g) to 2 (g) is the isotacticity.

[0140] Synthesis of external electron donor compounds

[0141] Preparation Example 1

[0142] Compound 1: (2-Methoxy)ethoxytriisopropylsilane

[0143] 100.0 g of triisopropylchlorosilane was added to 100 mL of dichloromethane. A mixture of 43.4 g of ethylene glycol monomethyl ether, 47.18 g of anhydrous pyridine, and 500 mL of dichloromethane was then added dropwise. Nitrogen gas was introduced into the reaction system to maintain a slight positive pressure. The temperature was kept below 5°C during the dropwise addition. After the addition was complete, the reaction was carried out at 25°C for 4 hours, then heated to reflux and reacted for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solvent was removed by rotary evaporation. 300 mL of n-hexane was added to the filtrate, and the mixture was stirred and filtered again. The solvent was removed by rotary evaporation to obtain the crude product, which was then distilled under reduced pressure to obtain 76.8 g of the final product, (2-methoxy)ethoxytriisopropylsilane, with a purity of 97.3% (GC).

[0144] Preparation Example 2

[0145] Compound 2: 2-(2-methoxyethoxy)ethoxytriisopropylsilane

[0146] The synthesis method differs from that in Preparation Example 1 in that ethylene glycol monomethyl ether is replaced with diethylene glycol monomethyl ether to prepare 2-(2-methoxyethoxy)ethoxytriisopropylsilane with a purity of 98.9% (GC).

[0147] Preparation Example 3

[0148] Compound 3: 2-(2-ethoxyethoxy)ethoxytriisopropylsilane

[0149] The synthesis method differs from that in Preparation Example 1 in that ethylene glycol monomethyl ether is replaced with diethylene glycol monoethyl ether to prepare 2-(2-ethoxyethoxy)ethoxytriisopropylsilane with a purity of 99.5% (GC).

[0150] Preparation Example 4

[0151] Compound 4: (2-Methoxy)ethoxytert-butyldimethylsilane

[0152] The synthesis method differs from that in Preparation Example 1 in that triisopropylchlorosilane is replaced with tert-butyldimethylchlorosilane to prepare (2-methoxy)ethoxytert-butyldimethylsilane with a purity of 99.3% (GC).

[0153] Preparation Example 5

[0154] Compound 5: (2-ethoxy)ethoxytert-butyldimethylsilane

[0155] The synthesis method differs from that in Preparation Example 1 in that triisopropylchlorosilane is replaced with tert-butyldimethylchlorosilane and ethylene glycol monomethyl ether is replaced with ethylene glycol monoethyl ether to prepare (2-ethoxy)ethoxytert-butyldimethylsilane with a purity of 99.7% (GC).

[0156] Preparation Example 6

[0157] Compound 6: Di(2-(2-ethoxyethoxy))ethoxytert-butyldimethylsilane

[0158] The synthesis method differs from that in Preparation Example 3 in that triisopropylchlorosilane is replaced with tert-butyldimethylchlorosilane to prepare di(2-(2-ethoxyethoxy))ethoxytert-butyldimethylsilane with a purity of 99.7% (GC).

[0159] Preparation Example 7

[0160] Compound 7: (2,2-diethoxy)ethoxytert-butyldimethylsilane

[0161] The synthesis method differs from that in Preparation Example 1 in that triisopropylchlorosilane is replaced with tert-butyldimethylchlorosilane and ethylene glycol monomethyl ether is replaced with 2,2-diethoxyethanol to prepare (2,2-diethoxy)ethoxytert-butyldimethylsilane with a purity of 98.4% (GC).

[0162] Preparation Example 8

[0163] Compound 8: Di(2-methoxy)ethoxydimethylsilane

[0164] The synthesis method differs from that in Preparation Example 1 in that triisopropylchlorosilane is replaced with dimethyldichlorosilane to prepare di(2-methoxy)ethoxydimethylsilane with a purity of 97.7% (GC).

[0165] Preparation Example 9

[0166] Compound 9: Di(2-ethoxy)ethoxydimethylsilane

[0167] The synthesis method differs from that in Preparation Example 5 in that tert-butyldimethylchlorosilane is replaced with dimethyldichlorosilane to prepare di(2-ethoxy)ethoxydimethylsilane with a purity of 97.4% (GC).

[0168] Preparation Example 10

[0169] Compound 10: Di(2-(2-methoxyethoxy))ethoxydimethylsilane

[0170] The synthesis method differs from that in Preparation Example 2 in that triisopropylchlorosilane is replaced with dimethyldichlorosilane to prepare bis(2-(2-methoxyethoxy))ethoxydimethylsilane with a purity of 98.4% (GC).

[0171] Preparation Example 11

[0172] Compound 11: Di(2-methoxy)ethoxydiisopropylsilane

[0173] The synthesis method differs from that in Preparation Example 1 in that triisopropylchlorosilane is replaced with diisopropyldichlorosilane to prepare di(2-methoxy)ethoxydiisopropylsilane with a purity of 99.9% (GC).

[0174] Preparation Example 12

[0175] Compound 12: Di(2-ethoxy)ethoxydiisopropylsilane

[0176] The synthesis method differs from that in Preparation Example 5 in that tert-butyldimethylchlorosilane is replaced with diisopropyldichlorosilane to prepare di(2-ethoxy)ethoxydiisopropylsilane with a purity of 99.5% (GC).

[0177] Preparation Example 13

[0178] Compound 13: Di(2-(2-methoxyethoxy))ethoxydiisopropylsilane

[0179] The synthesis method differs from that in Preparation Example 2 in that triisopropylchlorosilane is replaced with diisopropyldichlorosilane to prepare bis(2-(2-methoxyethoxy))ethoxydiisopropylsilane with a purity of 99.9% (GC).

[0180] Preparation Example 14

[0181] Compound 14: Di(2-(2-ethoxyethoxy))ethoxydiisopropylsilane

[0182] The synthesis method differs from that in Preparation Example 3 in that triisopropylchlorosilane is replaced with diisopropyldichlorosilane to prepare bis(2-(2-ethoxyethoxy))ethoxydiisopropylsilane with a purity of 99.8% (GC).

[0183] Preparation Example 15

[0184] Compound 15: Di(2-methoxy)ethoxydicyclopentylsilane

[0185] The synthesis method differs from that in Preparation Example 1 in that triisopropylchlorosilane is replaced with dicyclopentyldichlorosilane to prepare di(2-methoxy)ethoxydicyclopentylsilane with a purity of 99.9% (GC).

[0186] Preparation Example 16

[0187] Compound 16: Di(2-ethoxy)ethoxydicyclopentylsilane

[0188] The synthesis method differs from that in Preparation Example 5 in that tert-butyldimethylchlorosilane is replaced with dicyclopentyldichlorosilane to prepare di(2-ethoxy)ethoxydicyclopentylsilane with a purity of 99.9% (GC).

[0189] Preparation Example 17

[0190] Compound 17: Di(2-(2-ethoxyethoxy))ethoxydicyclopentylsilane

[0191] The synthesis method differs from that in Preparation Example 3 in that triisopropylchlorosilane is replaced with dicyclopentyldichlorosilane to prepare bis(2-(2-ethoxyethoxy))ethoxydicyclopentylsilane with a purity of 99.5% (GC).

[0192] Preparation Example 18

[0193] Compound 18: Di(2-methoxy)ethoxydiphenylsilane

[0194] The synthesis method differs from that in Preparation Example 1 in that triisopropylchlorosilane is replaced with diphenyldichlorosilane to prepare di(2-methoxy)ethoxydiphenylsilane with a purity of 99.8% (GC).

[0195] Preparation Example 19

[0196] Compound 19: Di(2-ethoxy)ethoxydiphenylsilane

[0197] The synthesis method differs from that in Preparation Example 5 in that tert-butyldimethylchlorosilane is replaced with diphenyldichlorosilane to prepare di(2-ethoxy)ethoxydiphenylsilane with a purity of 99.9% (GC).

[0198] Preparation Example 20

[0199] Compound 20: Di(2-methoxy)ethoxycyclohexylmethylsilane

[0200] The synthesis method differs from that in Preparation Example 1 in that triisopropylchlorosilane is replaced with cyclohexylmethyldichlorosilane to prepare di(2-methoxy)ethoxycyclohexylmethylsilane with a purity of 99.8% (GC).

[0201] Preparation Example 21

[0202] Compound 21: Di(2-ethoxy)ethoxycyclohexylmethylsilane

[0203] The synthesis method differs from that in Preparation Example 5 in that tert-butyldimethylchlorosilane is replaced with cyclohexylmethyldichlorosilane to prepare di(2-ethoxy)ethoxycyclohexylmethylsilane with a purity of 99.9% (GC).

[0204] Preparation Example 22

[0205] Compound 22: Di(2-(2-ethoxyethoxy))ethoxycyclohexylmethylsilane

[0206] The synthesis method differs from that in Preparation Example 3 in that triisopropylchlorosilane is replaced with cyclohexylmethyldichlorosilane to prepare di(2-(2-ethoxyethoxy))ethoxycyclohexylmethylsilane with a purity of 99.7% (GC).

[0207] Preparation Example 23

[0208] Compound 23: Tris(2-ethoxy)ethoxysilane

[0209] The synthesis method differs from that in Preparation Example 5 in that tert-butyldimethylchlorosilane is replaced with trichlorosilane to prepare tris(2-ethoxy)ethoxysilane with a purity of 95.7% (GC).

[0210] Preparation Example 24

[0211] Compound 24: Tetra(2-methoxy)ethoxysilane

[0212] The synthesis method differs from that in Preparation Example 1 in that triisopropylchlorosilane is replaced with silicon tetrachloride to prepare tetra(2-methoxy)ethoxysilane with a purity of 99.9% (GC).

[0213] Preparation Example 25

[0214] Compound 25: Tetra(2-ethoxy)ethoxysilane

[0215] The synthesis method differs from that in Preparation Example 5 in that tert-butyldimethylchlorosilane is replaced with silicon tetrachloride to prepare tetra(2-ethoxy)ethoxysilane with a purity of 99.7% (GC).

[0216] Preparation Example 26

[0217] Compound 26: Tetra(2-(2-methoxyethoxy))ethoxysilane

[0218] The synthesis method differs from that in Preparation Example 2 in that triisopropylchlorosilane is replaced with silicon tetrachloride to prepare tetra(2-(2-methoxyethoxy))ethoxysilane with a purity of 98.5% (GC).

[0219] Preparation Example 27

[0220] Compound 27: Tetra(2-(2-ethoxyethoxy))ethoxysilane

[0221] The synthesis method differs from that in Preparation Example 3 in that triisopropylchlorosilane is replaced with silicon tetrachloride to prepare tetra(2-(2-ethoxyethoxy))ethoxysilane with a purity of 97.3% (GC).

[0222] Preparation of solid components of catalyst

[0223] Preparation Example 28

[0224] (1) Preparation of magnesium alcohol solution:

[0225] In a reactor that has undergone repeated replacement with high-purity nitrogen, 20 g of anhydrous magnesium chloride, 80 mL of toluene, and 80 mL of isooctanol were added sequentially. The mixture was stirred at 300 rpm and at 110 °C for 3.0 hours. Then, 3.0 mL of tetrabutyl titanate was added, and the reaction was continued for 1.5 hours. Finally, 120 mL of toluene was added to obtain a stable and homogeneous magnesium alcohol solution.

[0226] (2) Preparation of solid catalyst components

[0227] 75 mL of the above magnesium alcohol solution and 0.5 g of 3,5-heptanediol dibenzoate were added dropwise to a reactor containing 60 mL of titanium tetrachloride and 40 mL of toluene, which had been fully purged with nitrogen. The mixture was stirred and kept in contact at -25°C for 1.5 hours. The temperature was then raised to 110°C over 3.5 hours and held for 1 hour. 108 mL of toluene and 12 mL of titanium tetrachloride were added, and the mixture was stirred for 1 hour. The mixture was then cooled and filtered. Another 12 mL of titanium tetrachloride and 108 mL of toluene were added, and the temperature was raised to 100°C. 3.0 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane (compound of formula (III)) was added, and the mixture was held for 1 hour. The temperature was then raised to 110°C, and 96 mL of toluene and 24 mL of titanium tetrachloride were added. The mixture was stirred for 1 hour, filtered, and the liquid was removed. This process was repeated twice. Another 108 mL of toluene and 12 mL of titanium tetrachloride were added, and the mixture was stirred for 1 hour. After filtration, the resulting solid was washed four times with 150 mL of hexane. The mixture was filtered, transferred, and dried to obtain the solid component C1 of the olefin polymerization catalyst. The titanium content was 2.0 wt% based on the total weight of the solid component C1.

[0228] Example A1

[0229] The catalyst in Example A1 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 1, and 2.5 mmol of triethylaluminum.

[0230] Example A2

[0231] The catalyst in Example A2 consisted of the above-mentioned 10 mg olefin polymerization catalyst solid component C1, 0.1 mmol external electron donor compound 2, and 2.5 mmol triethylaluminum.

[0232] Example A3

[0233] The catalyst in Example A3 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 3, and 2.5 mmol of triethylaluminum.

[0234] Example A4

[0235] The catalyst in Example A4 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 4, and 2.5 mmol of triethylaluminum.

[0236] Example A5

[0237] The catalyst in Example A5 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 5, and 2.5 mmol of triethylaluminum.

[0238] Example A6

[0239] The catalyst in Example A6 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 6, and 2.5 mmol of triethylaluminum.

[0240] Example A7

[0241] The catalyst in Example A7 consists of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 7, and 2.5 mmol of triethylaluminum.

[0242] Example A8

[0243] The catalyst in Example A8 consists of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 8, and 2.5 mmol of triethylaluminum.

[0244] Example A9

[0245] The catalyst in Example A9 consists of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 9, and 2.5 mmol of triethylaluminum.

[0246] Example A10

[0247] The catalyst in Example A10 consists of 10 mg of the solid component C1 of the above-mentioned olefin polymerization catalyst, 0.1 mmol of external electron donor compound 10, and 2.5 mmol of triethylaluminum.

[0248] Example A11

[0249] The catalyst in Example A11 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 11, and 2.5 mmol of triethylaluminum.

[0250] Example A12

[0251] The catalyst in Example A12 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 12, and 2.5 mmol of triethylaluminum.

[0252] Example A13

[0253] The catalyst in Example A13 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 13, and 2.5 mmol of triethylaluminum.

[0254] Example A14

[0255] The catalyst in Example A14 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 14, and 2.5 mmol of triethylaluminum.

[0256] Example A15

[0257] The catalyst in Example A15 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 15, and 2.5 mmol of triethylaluminum.

[0258] Example A16

[0259] The catalyst in Example A16 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 16, and 2.5 mmol of triethylaluminum.

[0260] Example A17

[0261] The catalyst in Example A17 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 17, and 2.5 mmol of triethylaluminum.

[0262] Example A18

[0263] The catalyst in Example A18 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 18, and 2.5 mmol of triethylaluminum.

[0264] Example A19

[0265] The catalyst in Example A19 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 19, and 2.5 mmol of triethylaluminum.

[0266] Example A20

[0267] The catalyst in Example A20 consists of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 20, and 2.5 mmol of triethylaluminum.

[0268] Example A21

[0269] The catalyst in Example A21 consists of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 21, and 2.5 mmol of triethylaluminum.

[0270] Example A22

[0271] The catalyst in Example A22 consists of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 22, and 2.5 mmol of triethylaluminum.

[0272] Example A23

[0273] The catalyst in Example A23 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 23, and 2.5 mmol of triethylaluminum.

[0274] Example A24

[0275] The catalyst in Example A24 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 24, and 2.5 mmol of triethylaluminum.

[0276] Example A25

[0277] The catalyst in Example A25 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 25, and 2.5 mmol of triethylaluminum.

[0278] Example A26

[0279] The catalyst in Example A26 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 26, and 2.5 mmol of triethylaluminum.

[0280] Example A27

[0281] The catalyst in Example A27 consisted of 10 mg of the solid component C1 of the olefin polymerization catalyst described above, 0.1 mmol of external electron donor compound 27, and 2.5 mmol of triethylaluminum.

[0282] Example A28

[0283] The catalyst in Example A28 consists of a mixture of 10 mg of the above-mentioned olefin polymerization catalyst solid component C1, 0.05 mmol of external electron donor compound 1 and 0.05 mmol of dimethoxymethylcyclohexylsilane, and 2.5 mmol of triethylaluminum.

[0284] Example A29

[0285] The catalyst in Example A29 consists of a mixture of 10 mg of the above-mentioned olefin polymerization catalyst solid component C1, 0.05 mmol of external electron donor compound 1 and 0.05 mmol of dimethoxydicyclopentylsilane, and 2.5 mmol of triethylaluminum.

[0286] Example A30

[0287] The catalyst in Example A30 consists of a mixture of 10 mg of the above-mentioned olefin polymerization catalyst solid component C1, 0.05 mmol of external electron donor compound 4 and 0.05 mmol of dimethoxymethylcyclohexylsilane, and 2.5 mmol of triethylaluminum.

[0288] Example A31

[0289] The catalyst in Example A31 consists of a mixture of 10 mg of the above-mentioned olefin polymerization catalyst solid component C1, 0.05 mmol of external electron donor compound 4 and 0.05 mmol of dimethoxydicyclopentylsilane, and 2.5 mmol of triethylaluminum.

[0290] Example A32

[0291] The catalyst in Example A32 consists of a mixture of 10 mg of the above-mentioned olefin polymerization catalyst solid component C1, 0.05 mmol of external electron donor compound 11 and 0.05 mmol of dimethoxymethylcyclohexylsilane, and 2.5 mmol of triethylaluminum.

[0292] Example A33

[0293] The catalyst in Example A33 consists of a mixture of 10 mg of the above-mentioned olefin polymerization catalyst solid component C1, 0.05 mmol of external electron donor compound 11 and 0.05 mmol of dimethoxydicyclopentylsilane, and 2.5 mmol of triethylaluminum.

[0294] Comparative Example DA1

[0295] The catalyst in Comparative Example DA1 consisted of 10 mg of the solid component C1 of the above-mentioned olefin polymerization catalyst, 0.1 mmol of the external electron donor dimethoxymethylcyclohexylsilane, and 2.5 mmol of triethylaluminum.

[0296] Comparative example DA2

[0297] The catalyst in Comparative Example DA2 consisted of the above-mentioned 10 mg olefin polymerization catalyst solid component C1, 0.1 mmol external electron donor dimethoxydicyclopentylsilane, and 2.5 mmol triethylaluminum.

[0298] propylene polymerization

[0299] Application Example 1

[0300] In a 5L autoclave, after sufficient purging with gaseous propylene, the catalysts (10mg) from Examples A1-A33 and Comparative Examples DA1-DA2, along with 10mL of anhydrous hexane, were added sequentially at room temperature (25℃). The autoclave was then closed, and a certain amount of hydrogen and 1.2kg of liquid propylene were introduced. The hydrogen addition was 4.5L, the polymerization temperature was 70℃, and the polymerization time was 1 hour before discharge. The polymerization results are shown in Table 1.

[0301] Table 1

[0302] As shown in Table 1, the polyolefin catalysts prepared using the silane compounds with the special structure described in this invention as external electron donors exhibit excellent hydrogen regulation performance, high polymerization activity, and stereoregulation ability. Compared with the classic external electron donor cyclohexylmethyldimethoxysilane, the stereoregulation ability of the catalysts is basically the same, while the hydrogen regulation sensitivity is improved to varying degrees; in nearly half of the examples, the catalyst activity is also improved. Therefore, the silane compounds with the special structure provided in this invention are very suitable for use as external electron donors in the solid component of Zn olefin polymerization catalysts, and can prepare high melt index polypropylene resins with high activity.

[0303] Preparation Example 29

[0304] (1) Preparation of alkoxymagnesium support:

[0305] In a 1L reactor equipped with a stirrer, reflux condenser, thermometer, and burette, after thorough purging with nitrogen, 550mL of ethanol, 10mL of isopropanol, and 0.68g of dissolved iodine were added. Stirring was initiated, and the temperature was increased until the reflux temperature of the reaction system was reached. Then, 32g of magnesium powder was added sequentially; the reaction continued until no more hydrogen gas was emitted. The mixture was then washed, filtered, and dried to obtain 147g of alkoxymagnesium support.

[0306] (2) Preparation of solid catalyst components

[0307] Take 10g of the prepared alkoxymagnesium support, 50mL of toluene, and 3.0g of a mixture of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane and 2,4-pentanediol dibenzoate (mass ratio 5:1) to prepare a suspension. In a 300mL reactor that has been repeatedly purged with high-purity nitrogen, add 10mL of toluene and 90mL of titanium tetrachloride, heat to 85℃, then add the prepared suspension to the reactor, continue heating to 115℃, maintain the temperature for 1.5 hours, and then filter the liquid thoroughly. Add a mixture of 60mL of toluene and 40mL of titanium tetrachloride, heat to 110℃, stir for 1 hour, and filter the liquid thoroughly. Repeat this process three times. The resulting solid is washed four times with 150mL of n-hexane at 55℃, and once with n-hexane at room temperature. Filter off the liquid and dry to obtain the solid component C2 of the olefin polymerization catalyst. Based on the total weight of the solid component C2, the titanium content is 3.7wt%.

[0308] Example B1

[0309] The catalyst in Example B1 consisted of the above-mentioned 10 mg olefin polymerization catalyst solid component C2, 0.1 mmol external electron donor compound 1, and 2.5 mmol triethylaluminum.

[0310] Example B2

[0311] The catalyst in Example B2 consists of the above-mentioned 10 mg olefin polymerization catalyst solid component C2, 0.1 mmol external electron donor compound 2, and 2.5 mmol triethylaluminum.

[0312] Example B3

[0313] The catalyst in Example B3 consisted of the above-mentioned 10 mg olefin polymerization catalyst solid component C2, 0.1 mmol external electron donor compound 4, and 2.5 mmol triethylaluminum.

[0314] Example B4

[0315] The catalyst in Example B4 consisted of the above-mentioned 10 mg olefin polymerization catalyst solid component C2, 0.1 mmol external electron donor compound 6, and 2.5 mmol triethylaluminum.

[0316] Example B5

[0317] The catalyst in Example B5 consisted of the above-mentioned 10 mg olefin polymerization catalyst solid component C2, 0.1 mmol external electron donor compound 7, and 2.5 mmol triethylaluminum.

[0318] Example B6

[0319] The catalyst in Example B6 consisted of the above-mentioned 10 mg olefin polymerization catalyst solid component C2, 0.1 mmol external electron donor compound 11, and 2.5 mmol triethylaluminum.

[0320] Example B7

[0321] The catalyst in Example B7 consisted of the above-mentioned 10 mg olefin polymerization catalyst solid component C2, 0.1 mmol external electron donor compound 15, and 2.5 mmol triethylaluminum.

[0322] Example B8

[0323] The catalyst in Example B8 consisted of the above-mentioned 10 mg olefin polymerization catalyst solid component C2, 0.1 mmol external electron donor compound 19, and 2.5 mmol triethylaluminum.

[0324] Example B9

[0325] The catalyst in Example B9 consisted of 10 mg of the above-mentioned olefin polymerization catalyst solid component C2, a mixture of 0.033 mmol of external electron donor compound 1 and 0.067 mmol of dimethoxymethylcyclohexylsilane, and 2.5 mmol of triethylaluminum.

[0326] Example B10

[0327] The catalyst in Example B10 consists of 10 mg of the above-mentioned olefin polymerization catalyst solid component C2, a mixture of 0.05 mmol of external electron donor compound 1 and 0.05 mmol of dimethoxymethylcyclohexylsilane, and 2.5 mmol of triethylaluminum.

[0328] Example B11

[0329] The catalyst in Example B11 consisted of 10 mg of the above-mentioned olefin polymerization catalyst solid component C2, a mixture of 0.067 mmol of external electron donor compound 1 and 0.033 mmol of dimethoxymethylcyclohexylsilane, and 2.5 mmol of triethylaluminum.

[0330] Example B12

[0331] The catalyst in Example B12 consisted of 10 mg of the above-mentioned olefin polymerization catalyst solid component C2, a mixture of 0.05 mmol of external electron donor compound 1 and 0.05 mmol of dimethoxydicyclopentylsilane, and 2.5 mmol of triethylaluminum.

[0332] Example B13

[0333] The catalyst in Example B13 consisted of 10 mg of the above-mentioned olefin polymerization catalyst solid component C2, a mixture of 0.05 mmol of external electron donor compound 4 and 0.05 mmol of dimethoxymethylcyclohexylsilane, and 2.5 mmol of triethylaluminum.

[0334] Example B14

[0335] The catalyst in Example B14 consisted of 10 mg of the above-mentioned olefin polymerization catalyst solid component C2, a mixture of 0.05 mmol of external electron donor compound 4 and 0.05 mmol of dimethoxydicyclopentylsilane, and 2.5 mmol of triethylaluminum.

[0336] Example B15

[0337] The catalyst in Example B15 consisted of 10 mg of the above-mentioned olefin polymerization catalyst solid component C2, a mixture of 0.05 mmol of external electron donor compound 11 and 0.05 mmol of dimethoxymethylcyclohexylsilane, and 2.5 mmol of triethylaluminum.

[0338] Example B16

[0339] The catalyst in Example B16 consisted of 10 mg of the above-mentioned olefin polymerization catalyst solid component C2, a mixture of 0.05 mmol of external electron donor compound 11 and 0.05 mmol of dimethoxydicyclopentylsilane, and 2.5 mmol of triethylaluminum.

[0340] Comparative example DB1

[0341] The catalyst in Comparative Example DB1 consisted of the above-mentioned 10 mg olefin polymerization catalyst solid component C2, 0.1 mmol external electron donor dimethoxycyclohexylmethylsilane, and 2.5 mmol triethylaluminum.

[0342] Comparative example DB2

[0343] The catalyst in Comparative Example DB1 consisted of the above-mentioned 10 mg olefin polymerization catalyst solid component C2, 0.1 mmol external electron donor dimethoxydicyclopentylsilane, and 2.5 mmol triethylaluminum.

[0344] propylene polymerization

[0345] Application Example 2

[0346] In a 5L autoclave, after sufficient purging with gaseous propylene, the catalysts (10mg) from Examples B1-B16 and Comparative Examples DB1-DB2, along with 10mL of anhydrous hexane, were added sequentially at room temperature (25℃). The autoclave was then closed, and a certain amount of hydrogen and 1.2kg of liquid propylene were introduced. The hydrogen addition was 4.5L, the polymerization temperature was 70℃, and the polymerization time was 1 hour before discharge. The polymerization results are shown in Table 2.

[0347] Table 2

[0348] As shown in Table 2, the polyolefin catalysts prepared using the silane compounds described in this invention as external electron donors exhibit high activity and excellent hydrogen regulation performance. Compared with classic external electron donors dimethoxycyclohexylmethylsilane and dimethoxydicyclopentylsilane, the polymerization activity of the catalysts is improved to varying degrees, and the hydrogen regulation sensitivity is also significantly enhanced. Therefore, the silane compounds with special structures provided in this invention are very suitable for use as external electron donors in the solid component of Zn olefin polymerization catalysts, enabling the preparation of polypropylene resins with high activity.

[0349] Preparation Example 30

[0350] Using the method of Preparation Example 29, the mixture of 3.0 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane and 2,4-pentanediol dibenzoate was replaced with 3.0 g of 9,9-bis(methoxymethyl)fluorene to obtain the olefin polymerization catalyst solid component C3. Based on the total weight of the olefin polymerization catalyst solid component C3, the titanium content was 4.8 wt%.

[0351] Preparation Example 31

[0352] Using the method of Preparation Example 29, the composition of 3.0 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane and 2,4-pentanediol dibenzoate was replaced with a composition of 3.0 g of 9,9-bis(methoxymethyl)fluorene and 2,4-pentanediol dibenzoate (mass ratio of the two is 1:5) to obtain the olefin polymerization catalyst solid component C4. Based on the total weight of the olefin polymerization catalyst solid component C4, the titanium content is 4.7 wt%.

[0353] Preparation Example 32

[0354] Using the method of Preparation Example 29, the composition of 3.0 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane and 2,4-pentanediol dibenzoate was replaced with 3.0 g of diethyl 2-cyano-2,3-diisopropylsuccinate to obtain the olefin polymerization catalyst solid component C5. Based on the total weight of the olefin polymerization catalyst solid component C5, the titanium content was 2.8 wt%.

[0355] Preparation Example 33

[0356] Using the method of Preparation Example 29, the composition of 3.0 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane and 2,4-pentanediol dibenzoate was replaced with a composition of 3.0 g of 2-cyano-2,3-diisopropylsuccinate and 2-isopentyl-2-isopropyl-1,3-dimethoxypropane (mass ratio 1:1) to obtain olefin polymerization catalyst solid component C6. Based on the total weight of olefin polymerization catalyst solid component C6, the titanium content was 3.1 wt%.

[0357] Preparation Example 34

[0358] Using the method of Preparation Example 29, the composition of 3.0 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane and 2,4-pentanediol dibenzoate was replaced with 3.0 g of 3-tert-butyl-5-methyl-1,2-catechol dibenzoate to obtain the olefin polymerization catalyst solid component C7. Based on the total weight of the olefin polymerization catalyst solid component C7, the titanium content was 4.2 wt%.

[0359] Preparation Example 35

[0360] Using the method of Preparation Example 29, the composition of 3.0 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane and 2,4-pentanediol dibenzoate was replaced with 3.0 g of diethyl 2,3-diisopropylsuccinate to obtain olefin polymerization catalyst solid component C8. Based on olefin polymerization catalyst solid component C8, the titanium content was 2.8 wt%.

[0361] Preparation Example 36

[0362] Using the method of Preparation Example 29, the composition of 3.0 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane and 2,4-pentanediol dibenzoate was replaced with a composition of 3.0 g of 2,3-diisopropylsuccinate diethyl ester and 2-isopentyl-2-isopropyl-1,3-dimethoxypropane (mass ratio 1:1) to obtain olefin polymerization catalyst solid component C9. Based on olefin polymerization catalyst solid component C9, the titanium content is 3.1 wt%.

[0363] Comparative Preparation Example 1

[0364] Using the method of Preparation Example 29, the composition of 3.0 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane and 2,4-pentanediol dibenzoate was replaced with 3.0 g of di-n-butyl phthalate to obtain olefin polymerization catalyst solid component DC1. Based on olefin polymerization catalyst solid component DC1, the titanium content was 2.1 wt%.

[0365] Comparative Preparation Example 2

[0366] Using the method of Preparation Example 29, the composition of 3.0 g of 2-isopentyl-2-isopropyl-1,3-dimethoxypropane and 2,4-pentanediol dibenzoate was replaced with 3.0 g of diisobutyl phthalate to obtain olefin polymerization catalyst solid component DC2. Based on olefin polymerization catalyst solid component DC2, the titanium content was 2.0 wt%.

[0367] Example E1

[0368] The catalyst in Example E1 consisted of 10 mg of olefin catalyst solid component C3, 1 mmol of external electron donor compound 1, and 2.5 mmol of triethylaluminum.

[0369] Comparative Example DE1

[0370] The catalyst in Comparative Example DE1 consisted of 10 mg of olefin catalyst solid component C3, 1 mmol of cyclohexylmethyldimethoxysilane (C-donor), and 2.5 mmol of triethylaluminum.

[0371] Comparative Example DE2

[0372] The catalyst in Comparative Example DE2 consisted of 10 mg of olefin catalyst solid component C3, 1 mmol of tetraethoxysilane (T-donor), and 2.5 mmol of triethylaluminum.

[0373] Example E2

[0374] The catalyst in Example E2 consisted of 10 mg of olefin catalyst solid component C4, 1 mmol of external electron donor compound 1, and 2.5 mmol of triethylaluminum.

[0375] Example E3

[0376] The catalyst in Example E3 consisted of 10 mg of olefin catalyst solid component C4, 1 mmol of external electron donor compound 4, and 2.5 mmol of triethylaluminum.

[0377] Comparative Example DE3

[0378] The catalyst in Comparative Example DE3 consisted of 10 mg of olefin catalyst solid component C4, 1 mmol of cyclohexylmethyldimethoxysilane (C-donor), and 2.5 mmol of triethylaluminum.

[0379] Comparative Example DE4

[0380] The catalyst in Comparative Example DE4 consisted of 10 mg of olefin catalyst solid component C4, 1 mmol of tetraethoxysilane (T-donor), and 2.5 mmol of triethylaluminum.

[0381] Example E4

[0382] The catalyst in Example E4 consisted of 10 mg of olefin catalyst solid component C5, 1 mmol of external electron donor compound 1, and 2.5 mmol of triethylaluminum.

[0383] Comparative Example DE5

[0384] The catalyst in Comparative Example DE5 consisted of 10 mg of olefin catalyst solid component C5, 1 mmol of cyclohexylmethyldimethoxysilane (C-donor), and 2.5 mmol of triethylaluminum.

[0385] Comparative Example DE6

[0386] The catalyst in Comparative Example DE6 consisted of 10 mg of olefin catalyst solid component C5, 1 mmol of tetraethoxysilane (T-donor), and 2.5 mmol of triethylaluminum.

[0387] Example E5

[0388] The catalyst in Example E5 consisted of 10 mg of olefin catalyst solid component C6, 1 mmol of external electron donor compound 1, and 2.5 mmol of triethylaluminum.

[0389] Comparative Example DE7

[0390] The catalyst in Comparative Example DE7 consisted of 10 mg of olefin catalyst solid component C6, 1 mmol of cyclohexylmethyldimethoxysilane (C-donor), and 2.5 mmol of triethylaluminum.

[0391] Comparative Example DE8

[0392] The catalyst in Comparative Example DE8 consisted of 10 mg of olefin catalyst solid component C6, 1 mmol of tetraethoxysilane (T-donor), and 2.5 mmol of triethylaluminum.

[0393] Example E6

[0394] The catalyst in Example E6 consisted of 10 mg of olefin catalyst solid component C7, 1 mmol of external electron donor compound 1, and 2.5 mmol of triethylaluminum.

[0395] Comparative Example DE9

[0396] The catalyst in Comparative Example DE9 consisted of 10 mg of olefin catalyst solid component C7, 1 mmol of cyclohexylmethyldimethoxysilane (C-donor), and 2.5 mmol of triethylaluminum.

[0397] Comparative Example DE10

[0398] The catalyst in Comparative Example DE10 consisted of 10 mg of olefin catalyst solid component C7, 1 mmol of tetraethoxysilane (T-donor), and 2.5 mmol of triethylaluminum.

[0399] Example E7

[0400] The catalyst in Example E7 consisted of 10 mg of olefin catalyst solid component C8, 1 mmol of external electron donor compound 1, and 2.5 mmol of triethylaluminum.

[0401] Comparative Example DE11

[0402] The catalyst in Comparative Example DE11 consisted of 10 mg of olefin catalyst solid component C8, 1 mmol of cyclohexylmethyldimethoxysilane (C-donor), and 2.5 mmol of triethylaluminum.

[0403] Example E8

[0404] The catalyst in Example E8 consisted of 10 mg of olefin catalyst solid component C9, 1 mmol of external electron donor compound 1, and 2.5 mmol of triethylaluminum.

[0405] Comparative Example DE12

[0406] The catalyst in Comparative Example DE12 consisted of 10 mg of olefin catalyst solid component C9, 1 mmol of cyclohexylmethyldimethoxysilane (C-donor), and 2.5 mmol of triethylaluminum.

[0407] Comparative Example DE13

[0408] The catalyst in Comparative Example DE13 consisted of 10 mg of olefin catalyst solid component DC1, 1 mmol of external electron donor compound 1, and 2.5 mmol of triethylaluminum.

[0409] Comparative Example DE14

[0410] The catalyst in Comparative Example DE14 consisted of 10 mg of olefin catalyst solid component DC2, 1 mmol of external electron donor compound 1, and 2.5 mmol of triethylaluminum.

[0411] Comparative Example DE15

[0412] The catalyst in Comparative Example DE15 consisted of 10 mg of olefin catalyst solid component DC1, 1 mmol of external electron donor compound 11, and 2.5 mmol of triethylaluminum.

[0413] Comparative Example DE16

[0414] The catalyst in Comparative Example DE16 consisted of 10 mg of olefin catalyst solid component DC2, 1 mmol of external electron donor compound 11, and 2.5 mmol of triethylaluminum.

[0415] Comparative Example DE17

[0416] The catalyst in Comparative Example DE17 consisted of 10 mg of olefin catalyst solid component DC1, 1 mmol of cyclohexylmethyldimethoxysilane (C-donor), and 2.5 mmol of triethylaluminum.

[0417] Comparative Example DE18

[0418] The catalyst in Comparative Example DE18 consisted of 10 mg of olefin catalyst solid component DC1, 1 mmol of tetraethoxysilane (T-donor), and 2.5 mmol of triethylaluminum.

[0419] propylene polymerization

[0420] Application Example 3

[0421] In a 5L autoclave, after sufficient purging with gaseous propylene, the catalysts (10mg) from Examples E1-E6 and Comparative Examples DE1-DE6, along with 10mL of anhydrous hexane, were added sequentially at room temperature (25℃). The autoclave was then closed, and a certain amount of hydrogen and 1.2kg of liquid propylene were introduced. The hydrogen addition was 4.5L, the polymerization temperature was 70℃, and the polymerization time was 1 hour before discharge. The polymerization results are shown in Table 3.

[0422] Table 3

[0423] As shown in Table 3, using the silane compounds described in this invention as external electron donors, and in combination with non-plasticizer internal electron donors, yields polyolefin catalysts with high activity and excellent hydrogen regulation performance. Compared with currently used external electron donors C-donor and T-donor, or catalysts using n-butyl phthalate and isobutyl phthalate as internal electron donors, the polymerization activity of the catalysts is improved to varying degrees, and the hydrogen regulation sensitivity is also significantly improved. Therefore, the silane compounds with special structures provided in this invention are very suitable for use as external electron donors in the solid component of Zn olefin polymerization catalysts, enabling the preparation of polypropylene resin with high activity.

Claims

1. A catalyst system characterized in that, include: (1) The catalyst solid component contains titanium, magnesium, halogens and internal electron donors; The internal electron donor is a non-plasticizer compound; (2) Alkyl aluminum compounds as co-catalysts; (3) an external electron donor including a silane-based compound represented by formula (I); In equation (I), R a and R a’ Each is independently selected from H, C1-20 straight-chain alkyl, C3-20 branched alkyl, C3-20 cycloalkyl, C6-20 aryl, C7-20 alkylaryl, and C7-20 aryl, R b R c They may be the same or different, each independently selected from C1-20 straight-chain alkyl, C3-20 branched alkyl, C3-20 cycloalkyl, C6-20 aryl, C7-20 alkylaryl, and C7-20 aryl, optionally R a R a’ R b R c The elements are connected to form saturated or unsaturated rings, where p is an integer from 1 to 4, q and m are each an independent integer from 0 to 3, n is an integer from 1 to 4, and m + n = 4.

2. The catalyst system of claim 1, wherein, In equation (I), R a R a’ R b R c Each is independently selected from C1-10 straight-chain alkyl, C3-10 branched alkyl, C3-10 cycloalkyl, C6-10 aryl, and C7-10 aryl; preferably, R a R a’ R b R c Each is independently selected from C1-6 straight-chain alkyl, C3-6 branched alkyl, C3-6 cycloalkyl, C6-9 aryl, and C7-9 aryl; more preferably, R a R a’ R b R c They may be the same or different, each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, cyclopentyl, phenyl, and benzyl; and / or In equation (I), p is an integer from 1 to 2, and / or m is an integer from 1 to 3, and / or q is an integer from 0 to 3, and n is an integer from 1 to 2.

3. The catalyst system of claim 1 or 2, wherein, In equation (I), R b R c Whether the same or different, each is independently selected from C1-4 straight-chain alkyl groups and C3-4 branched alkyl groups; preferably, R b R c They may be the same or different, each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; and / or In equation (I), each R a and R a’ At least one of them is selected from C3-6 branched alkyl, C3-6 cycloalkyl, C6-9 aryl, and C7-9 aryl; preferably, each R a and R a’ At least one of them is selected from isopropyl, isobutyl, tert-butyl, isopentyl, cyclopentyl, phenyl and benzyl.

4. The catalyst system according to any one of claims 1 to 3, wherein, The silane compound represented by formula (I) is selected from (2-methoxy)ethoxytriisopropylsilane, (2-ethoxy)ethoxytriisopropylsilane, 2-(2-methoxyethoxy)ethoxytriisopropylsilane, 2-(2-ethoxyethoxy)ethoxytriisopropylsilane, (2-methoxy)ethoxytert-butyldimethylsilane, (2-ethoxy)ethoxytert-butyldimethylsilane, bis(2-(2-methoxyethoxy))ethoxytert-butyldimethylsilane, bis(2-(2-ethoxyethoxy))ethoxytert-butyldimethylsilane, (2,2-diethoxy) )ethoxy-tert-butyldimethylsilane, bis(2-methoxy)ethoxydimethylsilane, bis(2-ethoxy)ethoxydimethylsilane, bis(2-(2-methoxyethoxy))ethoxydimethylsilane, bis(2-(2-ethoxyethoxy))ethoxydimethylsilane, bis(2-methoxy)ethoxydiisopropylsilane, bis(2-ethoxy)ethoxydiisopropylsilane, bis(2-(2-methoxyethoxy))ethoxydiisopropylsilane, bis(2-(2-ethoxyethoxy))ethoxydiisopropylsilane, bis(2-methoxy)ethoxydicyclopentane Silane, bis(2-ethoxy)ethoxydicyclopentylsilane, bis(2-(2-methoxyethoxy))ethoxydicyclopentylsilane, bis(2-(2-ethoxyethoxy))ethoxydicyclopentylsilane, bis(2-methoxy)ethoxydiphenylsilane, bis(2-ethoxy)ethoxydiphenylsilane, bis(2-(2-methoxyethoxy))ethoxydiphenylsilane, bis(2-(2-ethoxyethoxy))ethoxydiphenylsilane, bis(2-methoxy)ethoxycyclohexylmethylsilane, bis(2-eth ... At least one of -(2-methoxyethoxy))ethoxycyclohexylmethylsilane, bis(2-(2-ethoxyethoxy))ethoxycyclohexylmethylsilane, tris(2-methoxy)ethoxysilane, tris(2-ethoxy)ethoxysilane, tris(2-(2-methoxyethoxy))ethoxysilane, tris(2-(2-ethoxyethoxy))ethoxysilane, tetra(2-methoxy)ethoxysilane, tetra(2-ethoxy)ethoxysilane, tetra(2-ethoxy)ethoxysilane, and tetra(2-(2-ethoxyethoxy))ethoxysilane.

5. The catalyst system according to any one of claims 1 to 4, wherein, The external electron donor also includes silane compounds represented by formula (II). (R d ) x Si(OR e ) y (II) In equation (II), R d R e They may be the same or different, each independently selected from C1-20 straight-chain alkyl, C3-20 branched alkyl, C3-20 cycloalkyl, C6-20 aryl, C7-20 alkylaryl and C7-20 aralkyl, optionally connected to form saturated or unsaturated rings, x is an integer from 0 to 3, y is an integer from 1 to 4, and x+y=4.

6. The catalyst system of claim 5, wherein, In equation (II), R d R e Each of Rd and Re is independently selected from C1-10 straight-chain alkyl, C3-10 branched alkyl, C3-10 cycloalkyl, and C6-10 aryl; preferably, Rd and Re are each independently selected from C1-6 straight-chain alkyl, C3-6 branched alkyl, C3-6 cycloalkyl, and C6-9 aryl; more preferably, Rd and Re are each independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, cyclopentyl, and phenyl; and / or In equation (II), x is an integer from 1 to 3, and / or y is an integer from 1 to 2.

7. The catalyst system of claim 5 or 6, wherein, The silane compound represented by formula (II) is selected from at least one of dimethoxydicyclopentylsilane, dimethoxydiisopropylsilane, dimethoxydiisobutylsilane, dimethoxymethylcyclohexylsilane, tetraethoxysilane and isobutyltriethoxysilane.

8. The catalyst system according to any one of claims 5-7, wherein, The molar ratio of the silane compound shown in formula (I) to the silane compound shown in formula (II) is 0.01-100:1, preferably 0.05-20:

1.

9. The catalyst system according to any one of claims 1 to 8, wherein, The non-plasticizer compound is selected from at least one of 1,3-diether compounds, diol ester compounds, cyanosuccinate compounds, succinate compounds, and diphenol ester compounds; Preferably, the non-plasticizer compound is selected from at least one of the following: a combination of 1,3-diether compounds and diol ester compounds; a combination of 1,3-diether compounds and cyanosuccinate compounds; a combination of 1,3-diether compounds and succinate compounds; and a combination of 1,3-diether compounds and diphenol ester compounds. Preferably, the mass ratio of the 1,3-diether compound to the diol ester compound is 0.01-100:1, or the mass ratio of the 1,3-diether compound to the cyanosuccinate is 0.01-100:1, or the mass ratio of the 1,3-diether compound to the diol ester compound is 0.01-100:1, or the mass ratio of the 1,3-diether compound to the succinate is 0.01-100:1, or the mass ratio of the 1,3-diether compound to the diphenol ester is 0.01-100:1, or the mass ratio of any two compounds is 0.01-100:

1.

10. The catalyst system of claim 9, wherein, said 1,3-dicarbonyl compound is selected from the group consisting of dicarbonyl compounds of formula (II), In equation (III), R g R f They may be the same or different, each independently selected from C1-20 straight-chain alkyl, C3-20 branched alkyl, C3-20 cycloalkyl, C6-20 aryl, C7-20 alkylaryl, and C7-20 aryl, optionally R g R f Linked into a ring; preferably, selected from C1-10 straight-chain alkyl, C3-10 branched alkyl, C3-10 cycloalkyl, and C6-10 aryl; preferably, selected from C1-6 straight-chain alkyl, C3-6 branched alkyl, and C3-6 cycloalkyl; more preferably, R g R f Each is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, and cyclopentyl; Preferably, the diether compound represented by formula (III) is selected from at least one of 2,2-diisobutyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-isopentyl-2-isopropyl-1,3-dimethoxypropane, and 9,9-bis(methoxymethyl)fluorene, preferably 2-isopentyl-2-isopropyl-1,3-dimethoxypropane and / or 9,9-bis(methoxymethyl)fluorene; and / or The diol ester compound is selected from a diol ester compound represented by formula (IV); Among them, R m R n R h R k and R j They may be the same or different, each independently selected from H, C1-10 straight-chain alkyl, C3-10 branched alkyl, C3-10 cycloalkyl, and C6-10 aryl; preferably selected from C1-6 straight-chain alkyl and C3-6 branched alkyl, more preferably selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl; Preferably, the diol ester compound represented by formula (IV) is selected from at least one of 2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, and 3,5-heptanediol di(4-n-butyl)benzoate; and / or The cyanosuccinate compounds are selected from diethyl 2-cyano-2,3-diisopropylsuccinate and / or di-n-butyl 2-cyano-2,3-diisopropylsuccinate; and / or The succinate compound is diethyl 2,3-diisopropylsuccinate and / or di-n-butyl 2,3-diisopropylsuccinate; and / or The diphenol ester compound is at least one selected from 3-tert-butyl-5-methyl-1,2-catechol dibenzoate, 4-tert-butyl-1,2-catechol dibenzoate, and 3,5-di-tert-butyl-1,2-catechol dibenzoate.

11. The catalyst system according to any one of claims 1 to 10, wherein, In the solid component of the catalyst, titanium is calculated as titanium atoms, magnesium as magnesium atoms, and halogens as halogen atoms. The content of titanium atoms is 1-8 wt%, preferably 1-6 wt%; the content of magnesium atoms is preferably 10-70 wt%, preferably 12-40 wt%; the content of halogen atoms is 20-90 wt%, preferably 30-85%; and the content of internal electron donors is 2-30 wt%, preferably 3-20 wt%. Preferably, the alkylaluminum compound is based on aluminum, the catalyst solid component is based on titanium, and the molar ratio of the alkylaluminum compound to the catalyst solid component is 5-5000:1; preferably 20-1000:1; more preferably 50-500:1; and / or, the molar ratio of the alkylaluminum compound to the external electron donor is 0.1-500:1, preferably 1-300:1, more preferably 3-100:

1.

12. The catalyst system according to any one of claims 1 to 11, wherein, The magnesium in the catalyst solid component is derived from magnesium compounds, including at least one of the magnesium compound of formula (Va), a hydrate of the magnesium compound of formula (Vb), and an alcohol adduct of the magnesium compound of formula (Vc). MgR1R2 (Va), MgR1R2·qH2O (Vb), MgR1R2·pR0OH (Vc), Wherein, R1 and R2 may be the same or different, and are each independently selected from halogens, C1-5 straight-chain alkyl groups, C3-5 branched-chain alkyl groups, C1-5 straight-chain alkoxy groups, and C3-5 branched-chain alkoxy groups; R0 is selected from C1-18 hydrocarbon groups, preferably from C1-5 alkyl groups, and more preferably from methyl, ethyl, n-propyl, and isopropyl groups; 0.1≤q≤6, preferably 2≤q≤3.5; 0.1≤p≤6, preferably 2≤p≤3.5; Preferably, R1 and R2 are each independently selected from halogens; preferably, the halogens are selected from chlorine, bromine, and iodine; Preferably, the magnesium compound is selected from at least one of dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropoxymagnesium, dibutoxymagnesium, diisobutoxymagnesium, dipentoxymagnesium, dihexyloxymagnesium, di(2-methyl)hexyloxymagnesium, methoxymagnesium chloride, methoxymagnesium bromide, methoxymagnesium iodide, ethoxymagnesium chloride, ethoxymagnesium bromide, ethoxymagnesium iodide, propoxymagnesium chloride, propoxymagnesium bromide, propoxymagnesium iodide, butoxymagnesium chloride, butoxymagnesium bromide, butoxymagnesium iodide, magnesium dichloride, magnesium dibromide, magnesium diiodide, alcohol adducts of magnesium dichloride, alcohol adducts of magnesium dibromide, and alcohol adducts of magnesium diiodide; and / or The titanium in the solid component of the catalyst is derived from a titanium compound, which is selected from the titanium compounds shown in formula (VI). TiX m (OR3) 4-m (VI) In formula (VI), X is a halogen, preferably chlorine, bromine or iodine, R3 is selected from C1-20 hydrocarbon groups, and m is an integer from 1 to 4; preferably, R3 is selected from C1-5 alkyl groups; More preferably, the titanium compound represented by formula (VI) is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, and titanium trichloroethoxy; and / or The alkylaluminum compound is selected from the alkylaluminum compounds shown in formula (VII). AlR' n' X' 3-n' (VII), In formula (VII), R' is selected from the group consisting of hydrogen, C1-C 20 alkyl and C6-C 20 aryl, X' is halogen, and n' is an integer from 1 to 3. Preferably, the alkylaluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum hydrogen, diisobutylaluminum hydrogen, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride, and diethylaluminum chloride.

13. The application of the catalyst system according to any one of claims 1-12 in olefin polymerization, preferably, the olefin has the general structural formula CH2=CHR, wherein R is selected from hydrogen, C1-C12 alkyl and C6-C12 aryl, preferably selected from hydrogen and C1-C6 alkyl; preferably, the olefin is selected from at least one of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene.

14. A process for the polymerization of olefins, characterized in that, include: The olefin is contacted with the catalyst system according to any one of claims 1-12 and subjected to a polymerization reaction. Preferably, the olefin has the general structural formula CH2=CHR, wherein R is selected from hydrogen, C1-C12 alkyl and C6-C12 aryl, preferably selected from hydrogen and C1-C6 alkyl; preferably, the olefin is selected from at least one of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene. Preferably, the catalyst system is pre-contacted with each component before contacting with the olefin; preferably, the pre-contact conditions include: temperature -20°C to 80°C, more preferably 10°C to 50°C; time 0.1 min to 30 min, more preferably 1 min to 10 min. Preferably, the conditions for the polymerization reaction include: a temperature of 60°C to 90°C and a time of 30 min to 240 min.

15. The method of claim 14, wherein, The method further includes: prior to carrying out the polymerization reaction, subjecting the olefin to a prepolymerization reaction with the catalyst system according to any one of claims 1-12; Preferably, the conditions for the prepolymerization reaction include: 1-1000 g olefin monomer / gcat, more preferably 1-500 g olefin monomer / gcat, temperature -20°C to 80°C, more preferably 0°C to 50°C, and time 30 min to 480 min.

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