CN111234068A - Catalyst system for olefin polymerization and use thereof - Google Patents

Catalyst system for olefin polymerization and use thereof Download PDF

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CN111234068A
CN111234068A CN201811443801.XA CN201811443801A CN111234068A CN 111234068 A CN111234068 A CN 111234068A CN 201811443801 A CN201811443801 A CN 201811443801A CN 111234068 A CN111234068 A CN 111234068A
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alkyl
aryl
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aralkyl
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CN111234068B (en
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林洁
黄庭
赵惠
郭子芳
周俊领
夏先知
张晓帆
孙竹芳
赵瑾
张军辉
付梅艳
严立安
岑为
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene

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Abstract

The invention relates to a catalyst system for olefin polymerization and application thereof. The catalyst system comprises 1) a solid catalyst component comprising magnesium, titanium, a halogen and an internal electron donor; 2) an alkyl aluminum compound; and 3) an external electron donor; wherein the outer partThe catalyst system disclosed by the invention not only can improve the polymerization activity and hydrogen regulation sensitivity of the catalyst propylene, but also can keep higher stereospecificity, and in the polymerization of ethylene propylene and propylene- α -olefin, the polymerization activity can be improved under the condition of keeping the content of a comonomer unchanged.

Description

Catalyst system for olefin polymerization and use thereof
Technical Field
The invention belongs to the field of olefin polymerization catalysts, and particularly relates to a catalyst system for olefin polymerization and application thereof.
Background
It is well known that the activity, stereospecificity, hydrogen response and copolymerization properties of polyolefin catalysts are important technical parameters in order to meet the needs of industrial production and to produce products with excellent properties. Catalysts with excellent combination properties have been the object of efforts of polyolefin resin production enterprises and research and development institutions.
The Ziegler-Natta catalyst mainly comprises magnesium/titanium/internal electron donor, and the catalyst is often used together with alkyl aluminum and external electron donor to form a complete catalyst system. The external electron donor has the obvious characteristics of rich varieties, flexible and controllable addition, large influence on various performances of the catalyst and the like, so that the regulation of the overall performance of the catalyst by selecting a proper external electron donor is an important direction for the research and development of the catalyst.
The cyclotri-veratrum hydrocarbon and the derivative thereof have unique C3 symmetrical structure and rigid electron-rich cavity, are mainly applied to the aspects of molecular recognition and supramolecular assembly, and are not applied to the field of olefin polymerization. The inventor introduces the cyclotri-veratrum hydrocarbon and the derivative thereof into a Ziegler-Natta type polyolefin catalyst system, and finds that the cyclotri-veratrum hydrocarbon and the derivative thereof are matched with a solid catalyst component containing a diether internal electron donor and/or an alcohol ester internal electron donor for use, and have excellent performance.
Disclosure of Invention
The invention provides a catalyst system for olefin polymerization and application thereof. By introducing an external electron donor with special properties, namely cyclotri-veratryl hydrocarbon and derivatives thereof into the Ziegler-Natta type polyolefin catalyst, the activity, hydrogen regulation sensitivity and copolymerization activity of the catalyst can be improved simultaneously.
In order to achieve the above object, the present invention provides a catalyst system for olefin polymerization, comprising:
1) a solid catalyst component comprising magnesium, titanium, a halogen and an internal electron donor;
2) an alkyl aluminum compound; and
3) an external electron donor;
wherein the external electron donor comprises a compound shown as a formula A, the internal electron donor comprises a diether compound and/or an alcohol ester compound,
Figure BDA0001885307340000021
in the formula A, the reaction solution is prepared,
M1to M12Identical or different, each independently selected from hydrogen, hydroxy, halogen, cyano, nitro, amino, mono-C1-C10Alkylamino radical, bis-C1-C10Alkylamino, aldehyde, carboxyl, RaC(O)-、RaO-、C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C8Cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl, 4-12 membered heterocycloalkyl and C5-C20Heteroaryl, when two groups adjacent to each other on the phenyl ring are each selected from RaC(O)-、RaO-、C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C8Cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl, 4-12 membered heterocycloalkyl and C5-C20In the case of heteroaryl, two adjacent groups may optionally form a ring with each other, the ring being selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring and combinations thereof, wherein R isaIs selected from C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C8Cycloalkyl radical, C6-C10Aryl radical, C7-C20Aralkyl, 4-12 membered heterocycloalkyl and C5-C20A heteroaryl group;
R1to R6The same or different, each is independently selected from hydrogen and C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C8Cycloalkyl radical, C6-C10Aryl radical, C7-C20Aralkyl, 4-12 membered heterocycloalkyl and C5-C20Heteroaryl radical；
Any of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocycloalkyl, and heteroaryl groups may be optionally substituted with one or more substituents selected from the group consisting of hydroxy, halo, cyano, nitro, amino, mono-C1-C10Alkylamino radical, bis-C1-C10Alkylamino groups, aldehyde groups, carboxyl groups and heteroatoms.
According to a second aspect of the present invention there is provided a prepolymerised catalyst composition for the polymerisation of olefins, said composition comprising a prepolymer obtainable by polymerisation of olefins using a catalyst system as hereinbefore described;
wherein the pre-polymerization multiple of the prepolymer is 0.1 to 1000g of olefin polymer per g of the solid catalyst component.
According to a third aspect of the present invention, there is provided a process for the polymerization of olefins having the general formula CH, wherein olefins are polymerized in the presence of said catalyst system and/or said prepolymerized catalyst composition2Wherein R is hydrogen or C1-C6An alkyl group; the olefin is preferably ethylene, propylene and/or 1-butene. The olefin polymerization may be homopolymerization of a single olefin or copolymerization of a plurality of olefins.
The invention adopts the cyclotri veratrum hydrocarbon and the derivative thereof shown in the formula A as an external electron donor, adopts the alkyl aluminum as a cocatalyst, and is matched with a solid catalyst component containing an internal electron donor of a diether compound and/or an alcohol ester compound for use, and the catalyst system can simultaneously improve the polymerization activity, the hydrogen regulation sensitivity and the copolymerization activity of the catalyst.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In a first aspect, the present invention provides a catalyst system for the polymerization of olefins, the catalyst system comprising:
1) a solid catalyst component comprising magnesium, titanium, a halogen and an internal electron donor;
2) an alkyl aluminum compound; and
3) an external electron donor;
wherein the external electron donor comprises a compound shown as a formula A, the internal electron donor comprises a diether compound and/or an alcohol ester compound,
Figure BDA0001885307340000031
in the formula A, the reaction solution is prepared,
M1to M12Identical or different, each independently selected from hydrogen, hydroxy, halogen, cyano, nitro, amino, mono-C1-C10Alkylamino radical, bis-C1-C10Alkylamino, aldehyde, carboxyl, RaC(O)-、RaO-、C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C8Cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl, 4-12 membered heterocycloalkyl and C5-C20Heteroaryl, when two groups adjacent to each other on the phenyl ring are each selected from RaC(O)-、RaO-、C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C8Cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl, 4-12 membered heterocycloalkyl and C5-C20In the case of heteroaryl, two adjacent groups may optionally form a ring with each other, the ring being selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring, and combinations thereof,
wherein R isaIs selected from C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C8Cycloalkyl radical, C6-C10Aryl radical, C7-C20Aralkyl, 4-12 membered heterocycloalkyl and C5-C20A heteroaryl group;
R1to R6The same or different, each is independently selected from hydrogen and C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C8Cycloalkyl radical, C6-C10Aryl radical, C7-C20Aralkyl, 4-12 membered heterocycloalkyl and C5-C20(ii) a heteroaryl group, wherein,
any of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocycloalkyl, and heteroaryl groups may be optionally substituted with one or more substituents selected from the group consisting of hydroxy, halo, cyano, nitro, amino, mono-C1-C10Alkylamino radical, bis-C1-C10Alkylamino groups, aldehyde groups, carboxyl groups and heteroatoms.
According to some embodiments of the catalyst system provided herein, M1To M12Identical or different, each independently selected from hydrogen, hydroxy, halogen, cyano, nitro, amino, mono-C1-C6Alkylamino radical, bis-C1-C6Alkylamino, aldehyde, carboxyl, RaC(O)-、RaO-、C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C6Cycloalkyl radical, C6-C10Aryl radical, C7-C10Aralkyl, 4-6 membered heterocycloalkyl and C5-C10Heteroaryl, wherein RaIs selected from C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C6Cycloalkyl radical, C6-C10Aryl radical, C7-C10Aralkyl, 4-6 membered heterocycloalkyl and C5-C10A heteroaryl group.
According to some embodiments of the catalyst system provided herein, M1To M12Selected from hydrogen, hydroxy, amino, halogen, aldehyde group, C1-C6Alkoxy and halogen substituted C1-C6An alkoxy group. Preferably, M1To M12Is differentWhen it is hydrogen.
According to some embodiments of the catalyst system provided herein, M1、M4、M5、M8、M9And M12Each independently selected from hydrogen and C1-C6An alkyl group.
According to some embodiments of the catalyst system provided herein, M2、M3、M6、M7、M10And M11Selected from hydroxyl, amino, halogen, aldehyde group, C1-C6Alkoxy and halogen substituted C1-C6An alkoxy group.
According to some embodiments of the catalyst system of the present invention, M1、M5And M9The same is true.
According to some embodiments of the catalyst system of the present invention, M2、M6And M10The same is true.
According to some embodiments of the catalyst system of the present invention, M3、M7And M11The same is true.
According to some embodiments of the catalyst system of the present invention, M4、M8And M12The same is true.
According to some embodiments of the catalyst system provided herein, RaIs selected from C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C6Cycloalkyl radical, C6-C10Aryl and C7-C10Aralkyl, wherein any of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and aralkyl groups may be optionally substituted with one or more substituents selected from the group consisting of hydroxy, halo, cyano, nitro, amino, mono-C1-C6Alkylamino radical, bis-C1-C6Alkylamino groups, aldehyde groups (-CHO), and carboxyl groups.
According to some embodiments of the catalyst system provided herein, R in formula A1To R6Each independently selected from hydrogen and C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C6Cycloalkyl radical, C6-C10Aryl radical, C7-C10Aralkyl, 4-6 membered heterocycloalkyl and C5-C10Heteroaryl, any of said alkyl, alkenyl, alkynyl, cycloalkyl, aryl and aralkyl groups may be optionally substituted with one or more substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C1-C6Alkylamino radical, bis-C1-C6Alkylamino groups, aldehyde groups, carboxyl groups (-COOH), and heteroatoms.
According to some embodiments of the catalyst system of the present invention, R in formula A1To R6Are the same or different and are each independently selected from hydrogen and C1-C6Alkyl radical, C1-C6Alkyl groups may be optionally substituted with one or more substituents selected from hydroxy (-OH), halogen, cyano (-CN), nitro (-NO)2) Amino (-NH-)2) mono-C1-C6Alkylamino radical, bis-C1-C6Alkylamino groups, aldehyde groups (-CHO), carboxyl groups (-COOH) and heteroatoms.
According to some embodiments of the catalyst system of the present invention, R1To R6Independently selected from hydrogen and C1-C6An alkyl group.
According to some embodiments of the catalyst system of the present invention, R1、R3And R5The same is true.
According to some embodiments of the catalyst system of the present invention, R2、R4And R6The same is true.
According to some embodiments of the catalyst system of the present invention, R1To R6Are all the same.
According to some embodiments of the catalyst system of the present invention, the compound of formula a has the structure shown as formula a1, a2, or A3.
Figure BDA0001885307340000051
According to an embodiment of the catalyst system of the present invention, the cyclotri veratryl hydrocarbon or derivative thereof represented by formula a is selected from at least one of the following compounds:
a compound A: m2＝M3＝M6＝M7＝M10＝M11＝OCH3，M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H；
Compound B: m2＝M3＝M6＝M7＝M10＝M11＝OCH2CH3，M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H；
Compound C: m2＝M3＝M6＝M7＝M10＝M11＝OCH2CH2CH3，M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H；
Compound D: m2＝M3＝M6＝M7＝M10＝M11＝OCH(CH3)2，M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H；
Compound E: m2＝M3＝M6＝M7＝M10＝M11＝OCH2CH2CH2CH3，M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H；
Compound F: m2＝M6＝M10＝OCH3；M3＝M7＝M11＝OCH2CH3，M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H；
Compound G: m2＝M6＝M10＝OCH3；M3＝M7＝M11＝OCH2CH2CH3，M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H；
Compound H: m2＝M6＝M10＝OCH3；M3＝M7＝M11＝OCH2CH2CH2CH3，M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H；
A compound I: m2＝M3＝M6＝M7＝M10＝M11＝OH，M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H；
Compound J: m2＝M6＝M10＝OCH3；M3＝M7＝M11＝OH，M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H；
Compound K: m2＝M6＝M10＝OCH3；M3＝M7＝M11＝NH2，M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H；
A compound L: m2＝M6＝M10＝OCH3；M3＝M7＝M11＝Cl，M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H；
Compound M: m2＝M6＝M10＝OCH3；M3＝M7＝M11＝Br，M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H；
Compound N: m2＝M6＝M10＝OCH3；M3＝M7＝M11＝I，M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H；
Compound O: m2＝M6＝M10＝OCH3；M3＝M7＝M11＝CHO，M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H；
Compound P: m2＝M6＝M10＝OCH3；M3＝M7＝M11＝OCH2CH2CH2Br，M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H；
Compound Q: m2＝M3＝M6＝M7＝M10＝M11＝OCH2CH2Cl；M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H；
A compound R: m2＝M6＝M10＝OH；M3＝M7＝M11＝OCH2CH3，M1＝M4＝M5＝M8＝M9＝M12＝H，R1＝R2＝R3＝R4＝R5＝R6＝H。
The structural formulae of the above compounds A to R are shown below:
Figure BDA0001885307340000071
Figure BDA0001885307340000081
according to some embodiments of the invention, the diether compound is a1, 3-diether compound represented by formula B,
Figure BDA0001885307340000082
in the formula B, RⅠ、RⅡ、RⅢ、RⅣ、RⅤAnd RⅥThe same or different, each independently selected from hydrogen, halogen, C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl and C7-C20An alkaryl group; rⅦAnd RⅧAre the same or different and are each independently selected from C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl and C7-C20An alkaryl group, wherein any of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl and alkaryl groups may be optionally substituted with one or more substituents selected from hydroxy, halo, cyano, nitro, amino, mono-C1-C10Alkylamino radical, bis-C1-C10Alkylamino groups, aldehyde groups, carboxyl groups, and heteroatoms; or, RⅠ、RⅡ、RⅢ、RⅣ、RⅤAnd RⅥTwo or more of which are bonded to each other to form a saturated or unsaturated monocyclic or polycyclic ring, such as a fluorene ring.
According to a preferred embodiment of the invention, the diether compound is selected from the group consisting of 2- (2-ethylhexyl) 1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2- (1-naphthyl) -1, 3-dimethoxypropane, 2- (2-fluorophenyl) -1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (p-chlorophenyl) -1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-sec-butyl-1, 3-dimethoxypropane, 2-di-sec-butyl-1, 3-dimethoxypropane, 2, 2-di-tert-butyl-1, 3-dimethoxypropane, 2-dineopentyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-isopropyl-2-phenyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-benzyl-1, 3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-sec-butyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 1-bis (methoxymethyl) -cyclopentadiene, 1-bis (methoxymethyl) -2,3,4, 5-tetramethylcyclopentadiene, 1-bis (methoxymethyl) -2,3,4, 5-tetraphenylcyclopentadiene, 1-bis (methoxymethyl) -2,3,4, 5-tetrafluorocyclopentadiene, 1, 1-bis (methoxymethyl) -3, 4-dicyclopentylcyclopentadiene, 1, 1-bis (methoxymethyl) indene, 1, 1-bis (methoxymethyl) -2, 3-dimethoxyindene, 1, 1-bis (methoxymethyl) -2,3,6, 7-tetrafluoroindene, 1, 1-bis (methoxymethyl) -4,5,6, 7-tetrafluoroindene, 1, 1-bis (methoxymethyl) -4, 7-dimethylindene, 1, 1-bis (methoxymethyl) -3, 6-dimethylindene, 1, 1-bis (methoxymethyl) -4-phenylindene, 1, 1-bis (methoxymethyl) -4-phenyl-2-methylindene, 1-bis (methoxymethyl) -4-phenylindene, 2-methylindene, 2-dimethylindene, 1, 1-bis (methoxymethyl) -4-phenylindene, 1,1, 1-bis (methoxymethyl) -4-tetracyclohexylindene, 1-bis (methoxymethyl) -7- (3,3, 3-trifluoropropyl) phenylindene, 1-bis (methoxymethyl) -7-cyclopentylindene, 1-bis (methoxymethyl) -7-isopropylindene, 1-bis (methoxymethyl) -7-cyclohexylindene, 1-bis (methoxymethyl) -7-tert-butylindene, 1-bis (methoxymethyl) -7-tert-butyl-2-methylindene, 1-bis (methoxymethyl) -7-phenylindene, 1-bis (methoxymethyl) -2-phenylindene, 1-bis (methoxymethyl) -7-phenylindene, 1-bis (methoxymethyl) -2-phenylindene, 9, 9-bis (methoxymethyl) fluorene, 9-bis (methoxymethyl) -2, 7-dicyclopentylfluorene, 9-bis (methoxymethyl) -1, 8-dichlorofluorene, 9-bis (methoxymethyl) -1, 8-difluorofluorene, 9-bis (methoxymethyl) -1,2,3, 4-tetrahydrofluorene, 9-bis (methoxymethyl) -4-tert-butylfluorene, 1-bis- (methoxymethyl) -2, 5-cyclohexadiene, 1-bis- (methoxymethyl) -benzonaphthalene, 7-bis- (methoxymethyl) -2, 5-norbornadiene, 9-bis- (methoxymethyl) -1, 4-methanodihydronaphthalene, 9-bis- (methoxymethyl) -1, 4-methanodihydroanthracene, 4-bis- (methoxymethyl) -1-phenyl-1, 4-dihydronaphthalene, 4-bis- (methoxymethyl) -1-phenyl-3, 4-dihydronaphthalene, 5-bis- (methoxymethyl) -1,3, 6-cycloheptatriene, and 1-methoxymethyl-1- (1' -methoxyethyl) -2,3,4, 5-tetramethylcyclopentadiene.
According to some embodiments of the invention, the alcohol ester compound is a glycol ester compound represented by formula C,
Figure BDA0001885307340000101
in the formula C, R1And R2Are the same or different and are each independently selected from C1-C20Alkyl radical, C2-C20Alkenyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl group, C7-C20Aralkyl and C10-C20A condensed ring aryl group, preferably each independently selected from C1-C10Alkyl radical, C2-C10Alkenyl radical, C3-C10Cycloalkyl radical, C6-C10Aryl radical, C7-C10Alkylaryl group, C7-C10Aralkyl and C10-C15A fused ring aryl group, said alkyl, alkenyl, cycloalkyl, aryl, alkaryl, aralkyl and fused ring aryl groups being optionally substituted with one or moreSubstituted with a plurality of substituents, said substituent(s) being selected from hydroxy, halogen, cyano, nitro, amino, mono-C1-C6Alkylamino radical, bis-C1-C6Alkylamino groups, aldehyde groups, carboxyl groups, and heteroatoms; m is a divalent linking group, preferably selected from C1-C20Alkylene radical, C3-C20Cycloalkylene and C6-C20Arylene radical, said alkylene, cycloalkylene and/or arylene radical being substituted by C1-C20Alkyl is substituted and the substituents are optionally bonded to one or more rings, the carbon or/and hydrogen atoms in M are optionally substituted by nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atoms.
According to some embodiments of the invention, the alcohol ester compound is a diol ester compound represented by formula D,
Figure BDA0001885307340000102
in the formula D, R1And R2Are the same or different and are each independently selected from C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl and C7-C20Alkylaryl, preferably selected from C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C10Cycloalkyl radical, C6-C10Aryl radical, C7-C10Aralkyl and C7-C10Alkylaryl, said alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl being optionally substituted by one or more substituents selected from halogen, C1-C6Alkyl and C1-C6One or more substituents in alkoxy; r3、R4、R5、R6And R1-R2nThe same or different, each is independently selected from hydrogen, halogen and C1-C20Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl group, C7-C20Aralkyl and C10-C20Condensed ring aryl, preferably selected from hydrogen, halogen, C1-C10Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C10Cycloalkyl radical, C6-C10Aryl radical, C7-C10Alkylaryl group, C7-C10Aralkyl and C10-C15A fused ring aryl, said alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkaryl, aralkyl and fused ring aryl optionally substituted with a substituent selected from halogen, C1-C6Alkyl and C1-C6One or more substituents in alkoxy; r3、R4、R5、R6And R1-R2nOptionally containing heteroatoms, which are one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus; or, R3、R4、R5、R6And R1-R2nTwo or more of which are bonded to each other to form a saturated or unsaturated monocyclic ring or a saturated or unsaturated polycyclic ring; wherein n is an integer of 0 to 10, preferably 1 to 8, more preferably 2 to 6, and when n is 0, the substituent is R3And R4The carbon atom and substituent of (A) is R5And R6Is bonded to the carbon atom(s) of (a).
Preferably, the alcohol ester compound is selected from the group consisting of 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 3, 5-heptanediol di-p-methylbenzoate, 3, 5-heptanediol di-o-methylbenzoate, 3, 5-heptanediol di-p-chlorobenzoate, 3, 5-heptanediol di-p-methoxybenzoate, 3, 5-heptanediol di-o-methoxybenzoate, 3, 5-heptanediol di-m-methoxybenzoate, 2-methyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, and mixtures thereof, 6-methyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 5-ethyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 4, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-propyl-3, 5-heptanediol dibenzoate, 4-methyl-4-propyl-3, 5-heptanediol dibenzoate, 6-methyl-2, 4-heptanediol di (p-chlorobenzoic acid) ester, 6-methyl-2, 4-heptanediol di (p-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-3, 5-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenz, 2,2,6, 6-tetramethyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-octanediol dibenzoate, 4-ethyl-3, 5-octanediol dibenzoate, 4-propyl-3, 5-octanediol dibenzoate, 4-butyl-3, 5-octanediol dibenzoate, 4-dimethyl-3, 5-octanediol dibenzoate, 4-methyl-4-ethyl-3, 5-octanediol dibenzoate, 2-methyl-6-ethyl-3, 5-octanediol dibenzoate, 5-methyl-4, 6-nonanediol dibenzoate, 5-ethyl-4, 6-nonanediol dibenzoate, 5-propyl-4, 6-nonanediol dibenzoate, 5-butyl-4, 6-nonanediol dibenzoate, 5-dimethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-ethyl-4, 6-nonanediol dibenzoate, 5-phenyl-4, 6-nonanediol dibenzoate, 4, 6-nonanediol dibenzoate and 4-butyl-3, 5-heptanediol dibenzoate, 1, 2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-phenylene dibenzoate, methyl-4, 6-nonanediol dibenzoate, 5-dimethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-ethyl-4, 6-, 3, 6-dimethyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene dibenzoate, 1, 2-naphthalene dibenzoate, 2, 3-naphthalene dibenzoate, 1, 8-naphthyl di-4-methylbenzoate, 1, 8-naphthyl di-3-methylbenzoate, 1, 8-naphthyl di-2-methylbenzoate, 1, 8-naphthyl di-4-ethylbenzoate, 1, 8-naphthyl di-4-n-propylbenzoate, 1, 8-naphthyl di-4-isopropylbenzoate, 1, 8-naphthyl di-4-n-butylbenzoate, 8-naphthyl ester, di-4-isobutylbenzoic acid-1, 8-naphthyl ester, di-4-tert-butylbenzoic acid-1, 8-naphthyl ester, di-4-phenylbenzoic acid-1, 8-naphthyl ester, di-4-fluorobenzoic acid-1, 8-naphthyl ester, di-3-fluorobenzoic acid-1, 8-naphthyl ester and di-2-fluorobenzoic acid-1, 8-naphthyl ester.
According to the present invention, in order to further improve the catalytic activity and stereospecificity of the catalyst system, the internal electron donor may further comprise an additional (other type) internal electron donor compound, preferably, the additional internal electron donor compound is at least one selected from the group consisting of a phenol ester compound, an aromatic carboxylate compound and a ketone compound.
According to an embodiment of the catalyst system of the present invention, the internal electron donor comprises a diether compound and an alcohol ester compound, wherein the molar ratio of the diether compound and the alcohol ester compound is 1 (0.02-50), preferably 1: (0.1-20).
According to an embodiment of the catalyst system of the present invention, the internal electron donor comprises a diether compound or an alcohol ester compound and a further internal electron donor compound, the molar ratio of the diether compound or the alcohol ester compound to the further internal electron donor compound being 1 (0.02-50), preferably 1: (0.1-20).
According to an embodiment of the catalyst system of the present invention, the structure of the aromatic carboxylic ester compound is represented by formula E:
Figure BDA0001885307340000121
in the formula E, R1And R2Same or different, independently C1-C8Alkyl radical, C5-C10Cycloalkyl radical, C6-C15Aryl radical, C7-C15Alkylaryl or C7-C15Aralkyl of (a), said C1-C8Alkyl radical, C3-C10Branched alkyl radical, C5-C10Cycloalkyl radical, C6-C15Aryl radical, C7-C15Alkylaryl or C7-C15The hydrogen on the arylalkyl carbon is optionally selected from alkanesAnd a halogen atom, preferably by a substituent selected from C1-C6Alkyl, fluorine atom, chlorine atom, bromine atom and iodine atom; r3-R6May be the same or different and is hydrogen, halogen, C1-C6Alkyl radical, C5-C10Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl or C7-C20Aralkyl radical, said C1-C8Alkyl radical, C5-C10Cycloalkyl radical, C6-C15Aryl radical, C7-C15Alkylaryl or C7-C15The hydrogen on the carbon in the aralkyl group of (a) is optionally substituted by a substituent selected from the group consisting of an alkane and a halogen atom, preferably by C1-C6Alkyl, fluorine atom, chlorine atom, bromine atom and iodine atom.
According to the present invention, the solid catalyst component comprises titanium, magnesium and an internal electron donor, which is a reaction product of a titanium compound, a magnesium compound and an internal electron donor. Since the present invention improves the performance of the olefin polymerization catalyst by changing the kinds of the internal electron donor and the external electron donor, the method of preparing the solid catalyst component by the above reaction in the present invention may be performed according to a method conventionally used in the art, for example, methods disclosed in CN1506384, CN1091748, CN85100997, CN102399326A, US4540679, etc., the disclosure of which is incorporated herein by reference.
According to a specific embodiment of the present invention, a titanium compound or a mixture of a titanium compound and an inert solvent (such as hexane, heptane, octane, decane, toluene, etc.) pre-cooled to-15 ℃ to-40 ℃ is mixed with a magnesium compound, the temperature of the mixture is raised to 90 ℃ to 110 ℃ in stages and maintained for 0.1 to 2 hours, and an internal electron donor is added during the raising of the temperature. Then solid-liquid separation is carried out, the obtained solid phase is treated for at least 2 times by using the titanium compound again, and is washed by using a solvent, and finally, the solid catalyst component is obtained by vacuum drying.
According to the present invention, the magnesium compound may be various magnesium compounds conventionally used in the art for preparing olefin polymerization catalysts, and for example, the magnesium compound may be selected from at least one of magnesium dihalides, alkoxy magnesium, alkyl magnesium, hydrates of magnesium dihalides, alcoholates of magnesium dihalides, and derivatives in which one halogen atom in the molecule of magnesium dihalide is substituted with hydrocarbyloxy group or halohydrocarbyloxy group.
However, according to a preferred embodiment of the present invention, the magnesium compound is an alcoholate of a magnesium dihalide. More preferably, the alcoholate of magnesium dihalide has the form of a spherical magnesium alcoholate of formula (I),
MgX2·m(R’OH)·nE·qH2o formula (I)
In the formula (I), X is chlorine or bromine; r' is C1-C4Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl) of (a), m is 0.5 to 4.0; e is an ether or ester electron donor compound, n is 0-1.0, wherein the ether or ester can be an ether or ester which can be used as an electron donor and is known in the art, and can also be an internal electron donor and/or an external electron donor used in the invention; q is 0 to 0.8.
According to a further preferred embodiment of the present invention, in formula (I), X is chloro or bromo; r' is C1-C4M is 1.5 to 3.5; n and q are both 0, and more preferably, the magnesium compound is MgCl2·m(CH3CH2OH), m is 1.5-3.5.
According to the present invention, the preparation method of the magnesium dihalide alcoholate can be carried out according to the methods known in the art, for example, the preparation method can be referred to the method disclosed in CN1330086A, and preferably, the preparation method of the magnesium dihalide alcoholate comprises the following steps:
(1) mixing anhydrous magnesium dihalide with an alcohol compound (R' OH), optionally adding an ether or ester electron donor compound, and reacting at 90-140 ℃ to obtain an alcohol compound of magnesium halide;
(2) shearing the magnesium halide alcohol compound in a dispersion medium, and cooling in an inert medium after shearing to obtain the spherical magnesium halide alcohol compound.
The mixing ratio of the anhydrous magnesium dihalide and the alcohol compound may be determined according to the actual need of the alcohol compound supported on the anhydrous magnesium dihalide.
Wherein, the dispersion medium can adopt hydrocarbon inert solvent, such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil, etc. The inert medium may be selected from pentane, hexane, heptane, petroleum ether, raffinate oil, and the like.
Wherein the shearing means shearing the alcoholic product of the magnesium halide by external shearing force, for example, high-speed stirring method (e.g. CN1330086), spraying method (e.g. US6020279) and super-gravity rotating bed (e.g. CN1580136A) and emulsifier method (CN1463990A) and the like.
Preferably, in order to further improve the purity of the magnesium compound, the obtained alcohol hydrate of the spherical magnesium halide is also preferably subjected to washing and drying steps.
According to the present invention, the titanium compound may be various titanium compounds conventionally used in the art for preparing olefin polymerization catalysts. Preferably, the titanium compound has a structure represented by the formula (II),
Ti(OR”)4-kXkformula (II)
In the formula (II): r' is C1-C20Is preferably C1-C10Is preferably C1-C5Alkyl of (a), for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl; x is F, Cl or Br, preferably Cl; k is an integer of 0 to 4.
Preferably, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotris butoxytitanium, dichlorodibutoxytitanium, trichloro monobutoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloro-monoethoxytitanium and titanium trichloride; more preferably, the titanium compound is titanium tetrachloride.
According to a preferred embodiment of the present invention, the weight ratio of the titanium element, the magnesium element and the internal electron donor in the solid catalyst component is 1: (5-25): (2-15).
Preferably, the alkyl aluminum compound is of the general formula AlR3The compound shown in the specification, wherein R is C1-C20Alkyl or halo C1-C20Alkyl, preferably C1-C8Alkyl or halo C1-C8An alkyl group. More preferably, the aluminum alkyl compound is triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum dichloride, Al (n-C)6H13)3And Al (n-C)8H17)3One or more of (a). Most preferably, the alkyl aluminium compound is triethyl aluminium and/or triisobutyl aluminium.
According to an embodiment of the catalyst system of the present invention, in said catalyst system the molar ratio of the catalyst component, calculated as titanium element, to the aluminium of the alkylaluminium compound is 1: (5-5000), preferably 1: (20-2000).
According to an embodiment of the catalyst system of the invention, the molar ratio of the external electron donor to the aluminium of the alkylaluminium compound is 1: (0.1-500); preferably 1: (1-200).
According to a second aspect of the present invention there is provided a prepolymerised catalyst composition for the polymerisation of olefins, said composition comprising a prepolymer obtainable by polymerisation of olefins using a catalyst system as hereinbefore described;
wherein the pre-polymerization multiple of the prepolymer is 0.1 to 1000g of olefin polymer per g of the solid catalyst component.
According to the present invention, the "prepolymerized catalyst" means a catalyst which has been subjected to a polymerization step at a relatively low conversion, and in the present invention, the prepolymerization may be carried out using the same α -olefin as the olefin used for the polymerization, wherein the olefin to be subjected to the prepolymerization is preferably propylene, and specifically, it is particularly preferred that the prepolymerization is carried out using propylene or a mixture thereof with one or more α -olefins in a molar amount of up to 20%.
According to the invention, the prepolymerization conditions can be carried out at a temperature of-20 to 80 ℃, preferably 0 to 50 ℃, in liquid or gas phase. The pre-polymerization step may be carried out in-line as part of a continuous polymerization process or separately in a batch operation.
In the present invention, in order to prepare a polymer of 0.1 to 1000g of the olefin prepolymer per g of the solid catalyst component, preferably 0.2 to 500g of the olefin prepolymer per g of the solid catalyst component, more preferably 0.5 to 20g of the olefin prepolymer per g of the solid catalyst component, it is particularly preferred that the prepolymerization of the catalyst of the present invention with an olefin is carried out independently in a batch operation, and the polymerization pressure is preferably 0 to 5 MPa.
According to a third aspect of the present invention there is provided the use of a catalyst system as described above and/or a prepolymerised catalyst composition as described above in the polymerisation of olefins. According to the present invention, both the above catalyst system and the prepolymerized catalyst composition of the present invention can be used in the homopolymerization of olefins, preferably propylene, or in the copolymerization with other olefins. Thus, the present invention also provides a process for the polymerisation of olefins, which process comprises: the olefin is polymerized in the presence of the above-described catalyst system or the above-described prepolymerized catalyst composition.
According to the invention, the olefin has the general formula CH2Wherein R is hydrogen or C1-C12Alkyl or aryl of (a). Preferably, the olefin is selected from the group consisting of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene, more preferably, the olefin is propylene. According to the invention, the catalyst system can be directly added into a reactor for a polymerization process, or the catalyst system and olefin are prepolymerized to obtain a prepolymerized catalyst which is then added into the reactor for polymerization. According to the invention, the olefin polymerization can be carried out according to known polymerization methods, in liquid or gas phase, or in a combination of liquid and gas phase polymerization stages, orConventional techniques such as slurry processes, gas phase fluidized beds, etc. Preferred polymerisation conditions include a temperature of from 0 to 150 ℃ for a period of from 0.2 to 5 hours and a pressure of from 0.01 to 10MPa, more preferably a temperature of from 50 to 90 ℃ for a period of from 0.3 to 2 hours and a pressure of from 0.02 to 5 MPa. According to the invention, the polymerization can be carried out in the presence of a solvent. Wherein the concentration of the catalyst system in the solvent may be 0.1X 10 in terms of the titanium element in the solid catalyst component-5-5×10-5Mol/l, preferably 0.2X 10-5-2×10-5Mol/l.
In the present invention, the hydrocarbon group may be selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl and alkaryl groups.
In the present invention, alkyl means a straight or branched alkyl group, non-limiting examples of which include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, tetrahydrogeranyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl and n-eicosyl.
In the present invention, examples of the alkenyl group may include, but are not limited to: ethenyl, propenyl, butenyl, pentenyl, octenyl. In the present invention, examples of alkynyl groups may include, but are not limited to: ethynyl and propargyl. In the present invention, examples of the cycloalkyl group may include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloundecyl and cyclododecyl. In the present invention, examples of the halogen include, but are not limited to, fluorine, chlorine, bromine and iodine. In the present invention, examples of the aryl group may include, but are not limited to: phenyl, methylphenyl, ethylphenyl, 4-tert-butylphenyl, naphthyl. In the present invention, aralkyl means an alkyl group having an aryl substituent, and examples may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butyl and phenyl-isopropyl. In the present invention, the alkylaryl group means an aryl group having an alkyl substituent group with a carbon number of 7 to 20, and examples thereof may include, but are not limited to: methylphenyl, ethylphenyl. In the present invention, examples of alkoxy groups may include, but are not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy, and hexoxy. In the present invention, examples of the condensed ring aryl group may include, but are not limited to: naphthyl, anthryl, phenanthryl, pyrenyl. In the present invention, the hetero atom means an atom usually contained in a molecular structure other than a halogen atom, a carbon atom and a hydrogen atom, for example, O, N, S, P, Si and B, etc.
The present invention will be described in detail below by way of examples. However, the present invention is not limited to the following examples. In the following examples, the test methods involved are as follows:
1. polymerization activity of catalyst: the amount of polymer obtained in kg over time is divided by the amount of catalyst added in g.
2. Weight average molecular weight: the high temperature sol-gel chromatography is measured according to the standard GB/T36214.4-2018.
3. Polymer isotactic index: reference is made to the standard GB/T2412-.
4. Ethylene content: fourier Infrared Spectroscopy VERTEX 70.
Preparation example 1
This preparation example is intended to illustrate the preparation of a magnesium compound.
Mixing anhydrous magnesium chloride and ethanol according to a molar ratio of 1:2.6, heating to 120 ℃ for reaction to generate magnesium chloride alcoholate melt, stirring at a high speed in white oil and silicone oil serving as dispersion media, then putting into cooled hexane to form spherical magnesium chloride alcoholate particles, and washing and drying to obtain the spherical carrier.
Preparation example 2
This preparation example is intended to illustrate the preparation of the solid catalyst component.
Adding 100ml of titanium tetrachloride into a 300ml glass reaction bottle with a stirrer, which is fully replaced by high-purity nitrogen, cooling to-20 ℃, adding 8g of the spherical magnesium chloride alcoholate prepared in preparation example 1, slowly heating to 110 ℃, adding the internal electron donor shown in table 1 or table 2 in the heating process, keeping the temperature at 110 ℃ for 0.5h, filtering out liquid, adding titanium tetrachloride for two times, washing with hexane for five times, and drying in vacuum to obtain the titanium-containing solid catalyst component.
Examples and comparative examples
This example illustrates the catalyst system and its applications provided by the present invention.
Polymerization reaction A:
blowing the mixture in a 48-channel parallel pressure reactor (PPR, the reaction volume is 20ml) by adopting nitrogen at high temperature, and cooling the mixture to normal temperature; replacing the reactor with propylene at normal temperature, and filling propylene with a certain pressure and a certain amount of hydrogen; filling propylene gas to about 1MPa, and adding 5ml of liquid propylene; several 1ml glass bottles were placed on a shaking table and filled with triethylaluminium (calculated as aluminium): external electron donors in table 1: the solid catalyst component prepared in preparation example 2 (by titanium element) is sequentially added with triethyl aluminum, an external electron donor and a heptane solution of the solid catalyst component in a molar ratio of 500:25:1 to prepare a mixed solution; automatically extracting a certain amount of mixed liquid by using a needle head and injecting the mixed liquid into the reactor; the temperature was raised to 70 ℃ to react for 1 hour.
Discharging, weighing the polymer by using a weighing device carried by the PPR, and calculating to obtain the catalyst activity; the isotactic index and the weight-average molecular weight of the polymer were also measured, and the results are shown in Table 1.
Polymerization reaction B:
blowing the mixture in a 48-channel parallel pressure reactor (PPR, the reaction volume is 20ml) by adopting nitrogen at high temperature, and cooling the mixture to normal temperature; replacing the reactor with hydrogen at normal temperature; filling propylene gas to about 1MPa, and adding 5ml of liquid propylene; several 1ml glass bottles were placed on a shaking table and filled with triethylaluminium (calculated as aluminium): external electron donors in table 1: the solid catalyst component prepared in preparation example 2 (by titanium element) is sequentially added with triethyl aluminum, an external electron donor and a heptane solution of the solid catalyst component in a molar ratio of 250:10:1 to prepare a mixed solution; automatically extracting a certain amount of mixed liquid by using a needle head and injecting the mixed liquid into the reactor; the temperature was raised to 70 ℃ to react for 40 minutes. The reactor is emptied, the system is replaced by ethylene-propylene mixed gas, and the reaction is carried out for 20 minutes at 80 ℃ under the pressure control of 0.7 MPa.
Discharging, weighing the polymer by using a weighing device carried by the PPR, and calculating to obtain the catalyst activity; the ethylene content of the polymer was also determined and the results are shown in Table 2.
As can be seen from Table 1, when the catalyst system provided by the invention is used for olefin polymerization, especially propylene polymerization, the isotactic index of the polymer is high, and the catalytic activity and the hydrogen regulation sensitivity are good. Compared with C-Donor as an external electron Donor and Cyclotriveratryl hydrocarbon and derivatives thereof as an external electron Donor, the diether compound or the glycol ester compound or the compound thereof is used as a catalyst of the internal electron Donor, and the polymer of the diether compound or the glycol ester compound or the compound thereof has the advantages of obviously improved activity of a polymerization system and improved hydrogen regulation sensitivity while keeping high isotactic index.
According to the characteristics of the catalyst provided by the invention, the catalyst system provided by the invention is particularly suitable for preparing polypropylene products with low ash content, high melt index and high isotactic index, and the weight average molecular weight of the products can be regulated and controlled in a wider range by adjusting the hydrogenation amount. When the catalyst system compounded by the internal electron donor is adopted, the activity of the catalyst system is higher than that when the catalyst system is singly used, and the isotactic index still meets the requirement, so that the high isotactic index of the polymer is kept, the ash content is reduced, and the catalyst system is used for preparing the high-purity polymer.
As can be seen from Table 2, when the catalyst system provided by the invention is used for olefin copolymerization, particularly ethylene-propylene copolymerization, compared with a catalyst system using C-Donor as an external electron Donor, the copolymer obtained by using the cyclotri-veratrum hydrocarbon and the derivative thereof as the external electron Donor has equivalent ethylene content and obviously high polymerization activity. According to the characteristics of the catalyst provided by the invention, the catalyst system provided by the invention is also suitable for a copolymerization system, and is beneficial to improving the copolymerization capacity.
TABLE 1
Figure BDA0001885307340000181
Note: the catalyst A has an internal electron donor of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane;
the internal electron donor of the catalyst B is a compound of 2, 4-pentanediol dibenzoate and 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane;
the internal electron donor of the catalyst C is 3-methyl-2, 4-pentanediol dibenzoate;
C-Donor: cyclohexylmethyldimethoxysilane.
TABLE 2
Figure BDA0001885307340000191
Note: the catalyst A has an internal electron donor of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane;
the internal electron donor of the catalyst B is a compound of 2, 4-pentanediol dibenzoate and 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane;
C-Donor: cyclohexyl methyl dimethoxy silane
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (10)

1. A catalyst system for olefin polymerization, comprising:
1) a solid catalyst component comprising magnesium, titanium, a halogen and an internal electron donor;
2) an alkyl aluminum compound; and
3) an external electron donor;
wherein the external electron donor comprises a compound shown as a formula A, the internal electron donor comprises a diether compound and/or an alcohol ester compound,
Figure FDA0001885307330000011
in the formula A, the reaction solution is prepared,
M1to M12Identical or different, each independently selected from hydrogen, hydroxy, halogen, cyano, nitro, amino, mono-C1-C10Alkylamino radical, bis-C1-C10Alkylamino, aldehyde, carboxyl, RaC(O)-、RaO-、C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C8Cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl, 4-12 membered heterocycloalkyl and C5-C20Heteroaryl, when two groups adjacent to each other on the phenyl ring are each selected from RaC(O)-、RaO-、C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C8Cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl, 4-12 membered heterocycloalkyl and C5-C20In the case of heteroaryl, two adjacent groups may optionally form a ring with each other, the ring being selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring, and combinations thereof,
wherein R isaIs selected from C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C8Cycloalkyl radical, C6-C10Aryl radical, C7-C20Aralkyl, 4-12 membered heterocycloalkyl and C5-C20A heteroaryl group;
R1to R6The same or different, each is independently selected from hydrogen and C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C8Cycloalkyl radical, C6-C10Aryl radical, C7-C20Aralkyl, 4-12 membered heterocycloalkyl and C5-C20A heteroaryl group;
any of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocycloalkyl, and heteroaryl groups may be optionally substituted with one or more substituents selected from the group consisting of hydroxy, halo, cyano, nitro, amino, mono-C1-C10Alkylamino radical, bis-C1-C10Alkylamino groups, aldehyde groups, carboxyl groups and heteroatoms.
2. The catalyst system of claim 1, wherein in formula A, M is1To M12Identical or different, each independently selected from hydrogen, hydroxy, halogen, cyano, nitro, amino, mono-C1-C6Alkylamino radical, bis-C1-C6Alkylamino, aldehyde, carboxyl, RaC(O)-、RaO-、C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C6Cycloalkyl radical, C6-C10Aryl radical, C7-C10Aralkyl, 4-6 membered heterocycloalkyl and C5-C10Heteroaryl, wherein RaIs selected from C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C6Cycloalkyl radical, C6-C10Aryl radical, C7-C10Aralkyl, 4-6 membered heterocycloalkyl and C5-C10A heteroaryl group;
preferably, M1To M12Selected from hydrogen, hydroxy, amino, halogen, aldehyde group, C1-C6Alkoxy and halogen substituted C1-C6An alkoxy group.
3. The catalyst system as claimed in claim 1 or 2, characterized in that in formula A, M1、M4、M5、M8、M9And M12Each independently selected from hydrogen and C1-C6An alkyl group; and/or M2、M3、M6、M7、M10And M11Selected from hydroxyl, amino, halogen, aldehyde group, C1-C6Alkoxy and halogen substituted C1-C6An alkoxy group.
4. A catalyst system according to any one of claims 1 to 3, wherein in formula A, R isaIs selected from C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C6Cycloalkyl radical, C6-C10Aryl and C7-C10Aralkyl, wherein any of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and aralkyl groups may be optionally substituted with one or more substituents selected from the group consisting of hydroxy, halo, cyano, nitro, amino, mono-C1-C6Alkylamino radical, bis-C1-C6Alkylamino, aldehyde and carboxyl groups; r1To R6Each independently selected from hydrogen and C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C6Cycloalkyl radical, C6-C10Aryl radical, C7-C10Aralkyl, 4-6 membered heterocycloalkyl and C5-C10Heteroaryl, any of said alkyl, alkenyl, alkynyl, cycloalkyl, aryl and aralkyl groups may be optionally substituted with one or more substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C1-C6Alkylamino radical, bis-C1-C6Alkylamino groups, aldehyde groups, carboxyl groups and heteroatoms.
5. The catalyst system of any of claims 1-4, wherein the diether compound is a1, 3 diether compound of formula B and the alcohol ester compound is a glycol ester compound of formula C,
Figure FDA0001885307330000021
in the formula B, RⅠ、RⅡ、RⅢ、RⅣ、RⅤAnd RVI are identical or different and are each independently selected from hydrogen, halogen, C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl and C7-C20An alkaryl group; rⅦAnd RⅧAre the same or different and are each independently selected from C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl and C7-C20An alkaryl group, wherein any of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl and alkaryl groups may be optionally substituted with one or more substituents selected from hydroxy, halo, cyano, nitro, amino, mono-C1-C10Alkylamino radical, bis-C1-C10Alkylamino groups, aldehyde groups, carboxyl groups, and heteroatoms; or, RⅠ、RⅡ、RⅢ、RⅣ、RⅤAnd RⅥTwo or more of them are bonded to each other to form a saturated or unsaturated monocyclic or polycyclic ring such as a fluorene ring;
Figure FDA0001885307330000031
in the formula C, R1And R2Are the same or different and are each independently selected from C1-C20Alkyl radical, C2-C20Alkenyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl group, C7-C20Aralkyl and C10-C20A condensed ring aryl group, preferably each independently selected from C1-C10Alkyl radical, C2-C10Alkenyl radical, C3-C10Cycloalkyl radical, C6-C10Aryl radical, C7-C10Alkylaryl group, C7-C10Aralkyl and C10-C15A fused ring aryl, said alkyl, alkenyl, cycloalkyl, aryl, alkaryl, aralkyl and fused ring aryl being optionally substituted with one or more substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C1-C6Alkylamino radical, bis-C1-C6Alkylamino groups, aldehyde groups, carboxyl groups, and heteroatoms; m is a divalent linking group, preferably selected from C1-C20Alkylene radical, C3-C20Cycloalkylene and C6-C20Arylene radical, said alkylene, cycloalkylene and/or arylene radical being substituted by C1-C20Alkyl substituted and the substituents are optionally bonded to one or more rings, the carbon or/and hydrogen atoms in M are optionally substituted by nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atoms;
preferably, the alcohol ester compound is a diol ester compound represented by formula D,
Figure FDA0001885307330000032
in the formula D, R1And R2Are the same or different and are each independently selected from C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Aralkyl and C7-C20Alkylaryl, preferably selected from C1-C6Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C10Cycloalkyl radical, C6-C10Aryl radical, C7-C10Aralkyl and C7-C10Alkylaryl, said alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl being optionally substituted by one or more substituents selected from halogen, C1-C6Alkyl and C1-C6One or more substituents in alkoxy; r3、R4、R5、R6And R1-R2nThe same or different, each is independently selected from hydrogen, halogen and C1-C20Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl group, C7-C20Aralkyl and C10-C20Condensed ring aryl, preferably selected from hydrogen, halogen, C1-C10Alkyl radical, C2-C6Alkenyl radical, C2-C6Alkynyl, C3-C10Cycloalkyl radical, C6-C10Aryl radical, C7-C10Alkylaryl group, C7-C10Aralkyl and C10-C15A fused ring aryl, said alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkaryl, aralkyl and fused ring aryl optionally substituted with a substituent selected from halogen, C1-C6Alkyl and C1-C6One or more substituents in alkoxy; r3、R4、R5、R6And R1-R2nOptionally containing heteroatoms, which are one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus; or, R3、R4、R5、R6And R1-R2nTwo or more of which are bonded to each other to form a saturated or unsaturated monocyclic ring or a saturated or unsaturated polycyclic ring; wherein n is an integer of 0 to 10, preferably 1 to 8, more preferably 2 to 6, and when n is 0, the substituent is R3And R4The carbon atom and substituent of (A) is R5And R6Is bonded to the carbon atom(s) of (a).
6. Catalyst system according to any of claims 1-5, characterized in that the internal electron donor further comprises an additional internal electron donor compound, preferably the additional internal electron donor compound is selected from at least one of a phenol ester compound, an aromatic carboxylate compound and a ketone compound,
more preferably, the aromatic carboxylate compound has a structure represented by formula E:
Figure FDA0001885307330000041
in the formula E, R1And R2Same or different, independently C1-C8Alkyl radical, C5-C10Cycloalkyl radical, C6-C15Aryl radical, C7-C15Alkylaryl or C7-C15Aralkyl of (a), said C1-C8Alkyl radical, C3-C10Branched alkyl radical, C5-C10Cycloalkyl radical, C6-C15Aryl radical, C7-C15Alkylaryl or C7-C15The hydrogen on the arylalkyl carbon is optionally substituted by a substituent selected from the group consisting of alkanes and halogen atoms, preferably by a substituent selected from the group consisting of C1-C6Alkyl, fluorine atom, chlorine atom, bromine atom and iodine atom; r3-R6May be the same or different and is hydrogen, halogen, C1-C6Alkyl radical, C5-C10Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl or C7-C20Aralkyl radical, said C1-C8Alkyl radical, C5-C10Cycloalkyl radical, C6-C15Aryl radical, C7-C15Alkylaryl or C7-C15The hydrogen on the carbon in the aralkyl group of (a) is optionally substituted by a substituent selected from the group consisting of an alkane and a halogen atom, preferably by C1-C6Alkyl, fluorine atom, chlorine atom, bromine atom and iodine atom.
7. Catalyst system according to any of claims 1 to 6, characterized in that the internal electron donor comprises a diether compound and an alcohol ester compound, wherein the molar ratio of diether compound and alcohol ester compound is 1 (0.02-50), preferably 1: (0.1-20); or the internal electron donor comprises a diether compound or an alcohol ester compound and an additional internal electron donor compound, and the molar ratio of the diether compound or the alcohol ester compound to the additional internal electron donor compound is 1 (0.02-50), preferably 1: (0.1-20).
8. Catalyst system according to any one of claims 1 to 7, characterized in that the alkylaluminum compound is of the general formula AlR3The compound shown in the specification, wherein R is C1-C20Alkyl or halo C1-C20Alkyl, preferably C1-C8Alkyl or halo C1-C8An alkyl group; preferably, in said catalyst system, the molar ratio of the catalyst component, calculated as titanium element, to the aluminium of the alkylaluminium compound is 1: (5-5000), preferably 1: (20-2000); the molar ratio of the external electron donor to the aluminum in the alkyl aluminum compound is 1: (0.1-500); preferably 1: (1-200).
9. A prepolymerized catalyst composition for olefin polymerization comprising a prepolymer obtained by polymerizing an olefin using the catalyst system according to any one of claims 1 to 8; wherein the pre-polymerization multiple of the prepolymer is 0.1 to 1000g of olefin polymer per g of the solid catalyst component.
10. A process for the polymerization of olefins having the general formula CH in the presence of a catalyst system according to any of claims 1-8 or a prepolymerized catalyst composition according to claim 92Wherein R is hydrogen or C1-C6An alkyl group; the olefin is preferably ethylene, propylene and/or 1-butene.
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