CN110950986A - Catalyst component for olefin polymerization, catalyst and olefin polymerization method - Google Patents

Catalyst component for olefin polymerization, catalyst and olefin polymerization method Download PDF

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CN110950986A
CN110950986A CN201811123231.6A CN201811123231A CN110950986A CN 110950986 A CN110950986 A CN 110950986A CN 201811123231 A CN201811123231 A CN 201811123231A CN 110950986 A CN110950986 A CN 110950986A
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dione
benzo
dioxononane
naphtho
methyl
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CN110950986B (en
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王军
高明智
何世雄
刘文蕊
马吉星
刘海涛
马晶
蔡晓霞
胡建军
李昌秀
马长友
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Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention relates to a catalyst component for olefin polymerization, a catalyst and an olefin polymerization method. The catalyst component for olefin polymerization comprises magnesium, titanium, halogen and an internal electron donor, wherein the internal electron donor comprises a cyclic compound shown in a formula I. When the olefin polymerization catalyst component is used for propylene polymerization, the hydrogen regulation sensitivity of the catalyst is good, the isotactic index of the obtained polymer is adjustable, and the molecular weight distribution of the obtained polypropylene resin is wide.

Description

Catalyst component for olefin polymerization, catalyst and olefin polymerization method
Technical Field
The invention relates to a catalyst component for olefin polymerization, a catalyst and an olefin polymerization method.
Background
Olefin polymerization catalysts can be divided into three broad categories, namely, traditional Ziegler-Natta catalysts, metallocene catalysts, and non-metallocene catalysts. For the conventional Ziegler-Natta catalysts, polyolefin catalysts are continuously updated with the development of electron donor compounds in the catalysts. Development of the catalyst from the first TiCl3AlCl3/AlEt2Cl system and second generation of TiCl3/AlEt2Cl system, magnesium chloride of the third generation as a carrier, monoester or aromatic dibasic acid ester as an internal electron donor, and TiCl with silane as an external electron donor4·ED·MgCl2/AlR3The catalytic polymerization activity of the catalyst and the isotacticity of the obtained polypropylene are greatly improved by an ED system. In the prior art, a titanium catalyst system for propylene polymerization mostly uses magnesium, titanium, halogen and an electron donor as basic components, wherein the electron donor compound is one of the essential components in the catalyst component. At present, various electron donor compounds have been disclosed,such as mono-or polycarboxylic acid esters, anhydrides, ketone 12/monoethers or polyethers, alcohols, amines, etc., and derivatives thereof, among which aromatic dicarboxylic acid esters (e.g. di-n-butyl phthalate or diisobutyl phthalate, etc., see US4784983) are more commonly used. Due to the limited use of phthalate compounds in the EU, novel electron donor compounds such as 1, 3-diether compounds containing two ether groups [ e.g. 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane and 9, 9-bis (methoxymethyl) fluorene ] have been developed for environmental protection, see US4971937 and EP0728769]And dibasic aliphatic carboxylic acid ester compounds (e.g. succinate, malonate, glutarate, etc., see patents WO98/56830, WO98/56834, WO01/57099, WO01/63231 and WO00/55215), and glycol ester compounds (see patents CN1436766A, CN1453298A, etc.). In recent years, many novel internal electron donor compounds containing nitrogen atom structures, such as maleic amide internal electron donor compounds (CN102268109), hydrazide internal electron donor compounds (CN103539874), diamide internal electron donor compounds (US2017/0240667), carbamate internal electron donor compounds (WO2014/048861) and amide ester internal electron donor compounds of dow ring ball technology ltd (US2012322962), have emerged, but the overall effect of the obtained catalyst is not outstanding.
The present inventors have found and synthesized a novel organic compound having a cyclic structure, and have found that when the novel compound having a cyclic structure is added to prepare a catalyst for olefin polymerization, a catalyst having excellent overall properties can be obtained, and when the catalyst is used for propylene polymerization, a polymer having a high molecular weight distribution and a high melt index can be obtained.
Disclosure of Invention
It is a first object of the present invention to provide a novel catalyst component (which may also be referred to as a solid catalyst component) for the polymerization of olefins.
It is a second object of the present invention to provide a novel catalyst for olefin polymerization.
It is a third object of the present invention to provide a novel olefin polymerization process.
In a first aspect, the present invention provides a catalyst component for olefin polymerization, comprising magnesium, titanium, a halogen and an internal electron donor, wherein the internal electron donor comprises a cyclic compound represented by formula I,
Figure BDA0001811714040000021
wherein R is1And R2The same or different, are independently selected from hydrogen and C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C6-C30Aryl radical, C4-C30Heterocyclic group, halogen atom, hydroxyl group and C1-C30Alkoxy radical, said C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C6-C30Aryl radical, C4-C30Heterocyclyl and C1-C30The hydrogen on the carbon of the alkoxy group is optionally selected from halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group;
a is (CR)3R4)m-Gn-(CR5R6)pWherein G is selected from NR7、PR8O, S and SiR9R10，R3To R10The same or different, are independently selected from hydrogen and C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C3-C30And aliphatic cyclic hydrocarbon group of6-C30An aromatic group of1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C3-C30And aliphatic cyclic hydrocarbon group of6-C30The hydrogen on carbon of the aromatic radical being optionally selected from among halogen atomsSeed, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10Alkyl, m, n and p are independently selected from integers of 0-6 such as 0, 1, 2,3,4, 5, 6, or R3And R4Linked to form a ring, and/or R5And R6Connecting to form a ring;
ar is C6-C30Arylene radicals or C4-C30Heteroarylene radical, C6-C30Arylene group and/or C4-C30The heteroarylene group is optionally substituted by a halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group;
x and Y are the same or different and are selected from O, S and NR11，R11Selected from hydrogen and C1-C30An alkyl group.
According to a preferred embodiment of the invention, R1And R2The same or different, are independently selected from hydrogen and C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C6-C20Aryl radical, C4-C20Heterocyclic group, halogen atom, hydroxyl group and C1-C20Alkoxy, preferably selected from hydrogen, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C20Alkynyl, C6-C15Aryl radical, C4-C10Heterocyclic group, halogen atom, hydroxyl group and C1-C10Alkoxy, more preferably selected from hydrogen, C1-C8Alkyl radical, C2-C8Alkenyl radical, C6-C10Aryl radical, C2-C8Alkynyl, C4-C8Heterocyclic group, halogen atom, hydroxyl group and C1-C8An alkoxy group. According to some embodiments, R1And R2Selected from methyl, ethyl, n-butylPropyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, hydroxyalkyl, benzyl, phenyl, halophenyl, naphthyl, biphenyl, or a group containing a heterocyclic compound, and the like. The heterocyclic compound-containing group is preferably an azole-containing group, a pyridine-containing group, a pyrimidine-containing group, a quinoline-containing group, or the like.
According to a preferred embodiment of the invention, R3To R10The same or different, are independently selected from hydrogen and C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20And C is an aliphatic cyclic hydrocarbon6-C20Aromatic radicals, preferably selected from hydrogen, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C10And C is an aliphatic cyclic hydrocarbon6-C15An aromatic group.
According to a preferred embodiment of the invention, Ar is C6-C20Arylene radicals or C4-C20A heteroarylene group, preferably Ar is C6-C15Arylene radicals or C4-C15A heteroarylene group. In some embodiments, Ar is substituted or unsubstituted naphthylene. In some embodiments, Ar is selected from
Figure BDA0001811714040000031
Figure BDA0001811714040000041
Wherein each R is1Independently selected from hydrogen, halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group.
In the present invention, C1-C10Examples of alkyl groups include C1-C6Alkyl radicals, e.g. methyl, ethyl, n-propyl, isopropylN-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2-dimethylpropyl, 2-methylbutyl, n-hexyl, and the like.
According to a preferred embodiment of the invention, R11Selected from hydrogen and C1-C20Alkyl, preferably hydrogen and C1-C10Alkyl, more preferably hydrogen and C1-C6An alkyl group. Examples of cyclic compounds of formula I described herein include, but are not limited to, the following: 7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 3-methyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 3-ethyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 3-propyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecan-6, 10-dione, 3-butyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 2, 3-dimethyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 2-methyl-3-ethyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 2-methyl-3-propyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 2-methyl-3-butyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 2-methyl-3-ethyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 2, 3-diethyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 2-ethyl-3-propyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 2-ethyl-3-butyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 2, 4-dimethyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 2, 4-diethyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 2, 4-dipropyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 2, 4-dibutyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 2-methyl-4-ethyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 2-methyl-4-propyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 2-methyl-4-butyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 2-ethyl-4-propyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 2,3, 4-trimethyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 2, 4-diethyl-3-methyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 2, 4-dipropyl-3-methyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione,2, 4-dibutyl-3-methyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 2, 3-dimethyl-4-ethyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 2, 3-dimethyl-4-propyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecan-6, 10-dione, 2, 3-dimethyl-4-butyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 2-ethyl-3-methyl-4-propyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 2, 4-dimethyl-3-ethyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower ring-6, 10-dione, 2,3, 4-triethyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 2, 4-dipropyl-3-ethyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 2, 4-dibutyl-3-ethyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 2-methyl-3, 4-diethyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 2-methyl-3-ethyl-4-propyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 2-methyl-3-ethyl-4-butyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower ring-6, 10-dione, 2, 3-diethyl-4-propyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower-6, 10-dione, 7, 8-benzo [ g ]]-1, 5-Dioxononane-6, 9-dione, 3-methyl-7, 8-benzo [ g ]]-1, 5-Dioxononane-6, 9-dione, 3-Ethyl-7, 8-benzo [ g ]]-1, 5-Dioxononane-6, 9-dione, 3-propyl-7, 8-benzo [ g]-1, 5-Dioxononane-6, 9-dione, 3-butyl-7, 8-benzo [ g)]-1, 5-dioxononane-6, 9-dione, 3-isopropyl-3-isopentyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 3-methyl-3-isoamyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 3-ethyl-3-isoamyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 3-butyl-3-isoamyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxol-6, 10-dione, 3-pentyl-3-isopentyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxol-6, 10-dione, 3-cyclopentyl-3-isopentyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower ring-6, 10-dione, 3-cyclohexyl-3-isopentyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecan-6, 10-dione, 3-isopropyl-3-butyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 3-isopropyl-3-cyclopentyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecan-6, 10-dione, 3-isopropyl-3-cyclohexyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxodecyl-6, 10-dione, 3-isopropyl-3-isoamyl-7, 8-Benzo [ g ]]-1, 5-Dioxononane-6, 9-dione, 3-methyl-3-isopentyl-7, 8-benzo [ g ]]-1, 5-Dioxononane-6, 9-dione, 3-isopropyl-3-ethyl-7, 8-benzo [ g)]-1, 5-Dioxononane-6, 9-dione, 3-isopropyl-3-butyl-7, 8-benzo [ g)]-1, 5-Dioxononane-6, 9-dione, 3-isopropyl-3-cyclopentyl-7, 8-benzo [ g]-1, 5-Dioxononane-6, 9-dione, 3-isopropyl-3-cyclohexyl-7, 8-benzo [ g)]-1, 5-Dioxononane-6, 9-dione, 3-isopropyl-3-cyclopropyl-7, 8-benzo [ g)]-1, 5-Dioxononane-6, 9-dione, 3-isopentyl-3-cyclopentyl-7, 8-benzo [ g]-1, 5-Dioxononane-6, 9-dione, 3-isopentyl-3-cyclohexyl-7, 8-benzo [ g)]-1, 5-Dioxononane-6, 9-dione, 3-isopentyl-3-cyclopropyl-7, 8-benzo [ g ]]-1, 5-Dioxononane-6, 9-dione, 2, 3-dimethyl-7, 8-benzo [ g ]]-1, 5-Dioxononane-6, 9-dione, 2-methyl-3-ethyl-7, 8-benzo [ g)]-1, 5-Dioxononane-6, 9-dione, 2-methyl-3-propyl-7, 8-benzo [ g)]-1, 5-Dioxononane-6, 9-dione, 2-methyl-3-butyl-7, 8-benzo [ g)]-1, 5-Dioxononane-6, 9-dione, 2, 3-diethyl-7, 8-benzo [ g ]]-1, 5-Dioxononane-6, 9-dione, 2-ethyl-3-propyl-7, 8-benzo [ g)]-1, 5-Dioxononane-6, 9-dione, 2-ethyl-3-butyl-7, 8-benzo [ g)]-1, 5-Dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8-benzo [ g ]]-1, 5-Dioxononane-6, 9-dione, 2, 4-diethyl-7, 8-benzo [ g ]]-1, 5-Dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8-benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8-benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-diamyl-7, 8-benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2,3, 4-trimethyl-7, 8-benzo [ g ]]-1, 5-Dioxononane-6, 9-dione, 2, 4-diethyl-3-methyl-7, 8-benzo [ g ]]-1, 5-Dioxononane-6, 9-dione, 2, 4-dipropyl-3-methyl-7, 8-benzo [ g)]-1, 5-Dioxononane-6, 9-dione, 2, 4-dibutyl-3-methyl-7, 8-benzo [ g)]-1, 5-Dioxononane-6, 9-dione, 2, 4-dimethyl-3-ethyl-7, 8-benzo [ g ]]-1, 5-Dioxononane-6, 9-dione, 2,3, 4-triethyl-7, 8-benzo [ g ]]-1, 5-Dioxononane-6, 9-dione, 2, 4-dipropyl-3-ethyl-7, 8-benzo [ g)]-1, 5-Dioxononane-6, 9-dione, 2, 4-dibutyl-3-ethyl-7, 8-benzo [ g ]]-1, 5-Dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (2' -methyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (2' -methyl) benzo [ g]-1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (2' -methyl) ketoneYl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (2' -methyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-diamyl-7, 8- (2' -methyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (3' -methyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (3' -methyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (3' -methyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (3' -methyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-diamyl-7, 8- (3' -methyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4' -methyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (4' -methyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (4' -methyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4' -methyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-diamyl-7, 8- (4' -methyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4' -Ethyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (4' -Ethyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (4' -Ethyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4' -ethyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-diamyl-7, 8- (4' -ethyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4' -propyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (4' -propyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (4' -propyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4' -propyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-diamyl-7, 8- (4' -propyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4' -butyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (4' -butyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (4' -butyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4' -butyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-diamyl-7, 8- (4' -butyl) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4' -chloro) benzo [ g]-1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8-, (4' -chloro) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (4' -chloro) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4' -chloro) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-diamyl-7, 8- (4' -chloro) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4' -methoxy) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (4' -methoxy) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (4' -methoxy) benzo [ g]-1, 5-Dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4' -methoxy) benzo [ g]-1, 5-Dioxononane-6, 9-dione and 2, 4-diamyl-7, 8- (4' -methoxy) benzo [ g]-1, 5-dioxononane-6, 9-dione.
According to an embodiment of the present invention, the cyclic compound represented by formula I may be prepared by a method comprising: reacting a compound represented by formula II with at least one compound selected from an acid halide compound represented by formula III, an acid anhydride compound represented by formula IV and an ester compound represented by formula V to produce the cyclic compound represented by formula I,
Figure BDA0001811714040000071
wherein R is1And R2The same or different, are independently selected from hydrogen and C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C6-C30Aryl radical, C4-C30Heterocyclic group, halogen atom, hydroxyl group and C1-C30Alkoxy radical, said C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C6-C30Aryl radical, C4-C30Heterocyclyl and C1-C30The hydrogen on the carbon of the alkoxy group is optionally selected from halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group;
a is (CR)3R4)m-Gn-(CR5R6)pWherein G is selected from NR7、PR8O, S and SiR9R10，R3To R10The same or different, are independently selected from hydrogen and C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C3-C30And aliphatic cyclic hydrocarbon group of6-C30An aromatic group of1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C3-C30And aliphatic cyclic hydrocarbon group of6-C30The hydrogen on carbon of the aromatic group being optionally selected from halogen atoms, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10Alkyl, m, n and p are independently selected from integers from 0 to 6, or R3And R4Linked to form a ring, and/or R5And R6Connecting to form a ring;
ar is C6-C30Arylene radicals or C4-C30Heteroarylene radical, C6-C30Arylene group and/or C4-C30The heteroarylene group is optionally substituted by a halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group;
x and Y are the same or different and are selected from O, S and NR11，R11Selected from hydrogen and C1-C30An alkyl group;
e is a halogen atom, preferably fluorine, chlorine, bromine and iodine;
r is C1-C20Alkyl, preferably C1-C10Alkyl, more preferably C1-C5An alkyl group.
According to some preferred embodiments, R1And R2The same or different, are independently selected from hydrogen and C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C6-C20Aryl radical, C4-C20Heterocyclic group, halogen atom, hydroxyl group and C1-C20Alkoxy, preferably selected from hydrogen, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C20Alkynyl, C6-C15Aryl radical, C4-C10Heterocyclic group, halogen atom, hydroxyl group and C1-C10Alkoxy, more preferably selected from hydrogen, C1-C8Alkyl radical, C2-C8Alkenyl radical, C6-C10Aryl radical, C2-C8Alkynyl, C4-C8Heterocyclic group, halogen atom, hydroxyl group and C1-C8An alkoxy group.
According to some preferred embodiments, R3To R10The same or different, are independently selected from hydrogen and C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20And C is an aliphatic cyclic hydrocarbon6-C20Aromatic radicals, preferably selected from hydrogen, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C10And C is an aliphatic cyclic hydrocarbon6-C15An aromatic group.
According to some preferred embodiments, Ar is C6-C20Arylene radicals or C4-C20A heteroarylene group, preferably Ar is C6-C15Arylene radicals or C4-C15A heteroarylene group. In some embodiments, Ar is substituted or unsubstituted naphthylene. In some embodiments, Ar is selected from
Figure BDA0001811714040000081
Wherein each R is1Independently selected from hydrogen, halogen atoms、OH、OR、SR、C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group.
According to some preferred embodiments, R11Selected from hydrogen and C1-C20Alkyl, preferably hydrogen and C1-C10An alkyl group.
According to some preferred embodiments, the reaction is carried out in a solvent in the presence of an acid or base and optionally an inorganic salt.
According to some preferred embodiments, the acid is selected from inorganic or organic acids, preferably from hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, benzoic acid and oxalic acid.
According to some preferred embodiments, the base is selected from inorganic or organic bases, preferably from sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium bicarbonate, potassium carbonate, sodium carbonate, cesium carbonate, sodium methoxide, sodium ethoxide, potassium tert-butoxide, butyllithium, sodium amide, trimethylamine, triethylamine, diethylamine, ethylenediamine, diisopropylethylamine, pyridine, picoline, hexahydropyridine, piperidine, pyrimidine, quinoline, triethanolamine, tetrabutylammonium hydroxide, BDU (1, 8-diazabicyclo [5,4,0] undec-7-ene), DBN (1, 5-diazabicyclono-5-ene) and pyrazole.
According to some preferred embodiments, the solvent is selected from the group consisting of alcohols, ethers and hydrocarbon solvents, preferably from the group consisting of methanol, ethanol, propanol, butanol, ethylene glycol, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, acetonitrile, propionitrile, butyronitrile, benzene, toluene, xylene, hexane, heptane, octane, petroleum ether, white oil, silicone oil, paraffin, methylene chloride, chloroform, ethylene oxide, propylene oxide, butylene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether, more preferably from the group consisting of diethyl ether, tetrahydrofuran, 1, 4-dioxane, acetonitrile, DMF and acetone.
According to some preferred embodiments, the inorganic salt is selected from the group consisting of sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, cesium carbonate, sodium bicarbonate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, and cesium sulfate.
According to some preferred embodiments of the present invention, the catalyst component comprises a titanium compound, a magnesium compound and an internal electron donor compound or a reaction product of a titanium compound, a magnesium compound and an internal electron donor compound.
According to some embodiments of the present invention, the internal electron donor further comprises an additional internal electron donor compound selected from ketones, ethers, amines, esters (aromatic or aliphatic diesters), and alcohol ester compounds.
Different methods can be chosen for the preparation of the solid catalyst component of the invention, and several methods for the preparation of the catalyst component are listed below without being limited thereto.
The method comprises the following steps: the magnesium halide is dissolved in a homogeneous solution of an organic epoxy compound and an organic phosphorus compound, and an inert diluent may also be added. The homogeneous solution is mixed with titanium tetrahalide or its derivative, and when a precipitation assistant is present in the reaction system, a solid is precipitated. The compound with the structure I is carried on a solid and then treated by titanium tetrahalide or inert diluent to obtain the solid catalyst containing titanium, magnesium, halogen, electron donor and other components.
The method 2 comprises the following steps: suspending the alkoxy magnesium or alkoxy magnesium chloride or magnesium chloride alcoholate spherical carrier in an inert solvent to form a suspension, and mixing and contacting the suspension solution with titanium tetrahalide or derivatives thereof to obtain a solid. And then contacting the compound with the structure I with a solid to obtain the solid catalyst containing titanium, magnesium, halogen, electron donor and other components.
The method 3 comprises the following steps: fully mixing and stirring magnesium halide or an organic magnesium compound, an alcohol compound and a titanate or titanium halide compound in an inert solvent, heating and cooling to obtain a spherical carrier or adding the spherical carrier into the inert solvent to obtain a uniform alcohol compound solution. Mixing the carrier or the uniform solution with titanium tetrahalide or derivatives thereof, maintaining at a low temperature for a period of time, heating, adding the compound with the structure I, treating with titanium tetrahalide or an inert diluent, treating with the compound, and finally filtering, washing and drying to obtain the solid catalyst containing titanium, magnesium, halogen, electron donor and other components.
The method for preparing the catalyst component also includes such methods as forming an emulsion of a magnesium compound, the electron donor compound of the formula I and the like in a diluent, adding a titanium compound to fix the emulsion to obtain a spherical solid, and then treating the spherical solid to obtain the solid catalyst.
The magnesium compound may be selected from one of magnesium dihalide, hydrate or alcoholate of magnesium dihalide and derivatives of magnesium dihalide in which one halogen atom in the molecular formula is replaced by hydrocarbyloxy or halohydrocarbyloxy, or mixtures thereof, preferably from the group consisting of magnesium dihalide or alcoholate, such as magnesium dichloride, magnesium dibromide, magnesium diiodide and alcoholate thereof. The magnesium compound may be dissolved in a solvent system containing an organic epoxy compound and an organic phosphorus compound, or may be dissolved in a 1, 3-diol ester compound. Wherein the organic epoxy compound comprises at least one of an oxide, a glycidyl ether and an internal ether of aliphatic olefin with 2-8 carbon atoms, diene or halogenated aliphatic olefin or diene. Specific compounds are as follows: ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran.
The titanium compound may be of the general formula TiXm(OR1)4-mA compound of (1), wherein R1The metal halide is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, m is 1 to 4, and is preferably at least one selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, and trichloromonoethoxytitanium, and is preferably titanium tetrachloride. The organophosphorus compound may be selected from hydrocarbyl or halohydrocarbyl esters of orthophosphoric acid or phosphorous acid, preferably at least one selected from trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite and trityl phosphiteOne kind of the medicine.
In a second aspect, the present invention provides a catalyst for olefin polymerization, comprising:
A) a catalyst component as provided in the first aspect of the invention;
B) an alkyl aluminum compound; and
C) optionally, an external electron donor component.
According to an embodiment of the invention, the alkylaluminum compound is of the general formula AlRI nX3-nA compound of (1), wherein RIIs hydrogen, alkyl with 1-20 carbon atoms, X is halogen, and n is a number which is more than 1 and less than or equal to 3; specifically, the aluminum chloride can be selected from triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydrochloride, diisobutylaluminum monohydrochloride, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride, and preferably triethylaluminum and triisobutylaluminum are selected.
For the application of olefin polymers with high stereoregularity, an external electron donor compound is added, for example, the general formula RII kSi(ORIII)4-kIn the formula, k is more than or equal to 0 and less than or equal to 3, RIIAnd RIIIIs the same or different alkyl, cycloalkyl, aryl, haloalkyl, RIIAnd may be a halogen or hydrogen atom. For example: trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, methyl-tert-butyldimethoxysilane, preferably cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane.
Wherein the ratio of the component A), the component B) and the component C) is 1 (5-1000) to 0-500 in terms of the molar ratio of titanium to aluminum to silicon; preferably 1 (25-100) to (25-100).
In a third aspect, the present invention provides a process for the polymerisation of olefins as described in the first aspect of the present inventionThe catalyst component provided or the catalyst as provided in the second aspect of the present invention, wherein the olefin has the general formula CH2Wherein R is hydrogen or C1～C6Alkyl groups of (a); the olefin is preferably ethylene, propylene and/or 1-butene.
The olefin polymerization reaction of the present invention is carried out according to a known polymerization method, and may be carried out in a liquid phase or a gas phase, or may be carried out in an operation combining liquid phase and gas phase polymerization stages. The homopolymerization of propylene and/or the copolymerization of other olefins of propylene is carried out by conventional techniques such as slurry process, bulk process, gas-phase fluidized bed, bulk-gas phase process, etc., wherein the olefin is selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene. The following reaction conditions are preferably employed: the polymerization temperature is 0-150 ℃, preferably 60-90 ℃.
The catalyst of the invention can be added directly to the reactor for use in the polymerization process or the catalyst can be prepolymerized before being added to the first polymerization reactor. In the present invention, "prepolymerized catalyst" means a catalyst which has undergone a polymerization step at a relatively low degree of conversion. According to the invention, the pre-polymerization catalyst comprises a pre-polymer obtained by pre-polymerizing the solid catalyst component and olefin, and the pre-polymerization multiple is 0.1-1000 g of olefin polymer/g of the solid catalyst component.
The same α -olefin as previously described can be used for the prepolymerization, wherein the olefin to be prepolymerized is preferably ethylene or propylene, in particular it is particularly preferred to prepolymerize with ethylene or a mixture of one or more α -olefins in a balance of up to 20 mol% preferably the prepolymerized catalyst component has a degree of conversion of about 0.2 to 500 g polymer/g solid catalyst component.
The prepolymerization step can be carried out at a temperature of-20 to 80 ℃, preferably 0 to 50 ℃, in a liquid or in a 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. For the preparation of polymers in amounts of 0.5 to 20g/g of catalyst component, batch prepolymerization of the catalyst of the invention with ethylene is particularly preferred. The polymerization pressure is 0.01 to 10 MPa.
The invention has the following characteristics:
1. the cyclic compound shown in the formula I contained in the catalyst component for olefin polymerization is a novel cyclic compound and is not reported in the literature.
2. The novel cyclic compound is used as an internal electron donor to prepare a catalyst component and a catalyst, so that the catalyst with excellent comprehensive performance can be obtained. Especially when the catalyst is used for propylene polymerization, the catalyst has high activity and good hydrogen regulation sensitivity, the isotactic index of the obtained polymer can be regulated, and the molecular weight distribution of the obtained polypropylene resin is wide.
Detailed Description
The cyclic compound shown as the formula I is used for preparing an olefin polymerization reaction catalyst to form a novel catalytic polymerization reaction system, and the catalytic behavior of the system in the propylene polymerization reaction is researched, and the results are shown in Table 1.
Examples
Synthesis of Compound (I)
Example Synthesis of 12, 4-dimethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione (FE-1)
In a 250 ml three-necked flask, after nitrogen purging, 2.08 g of 2, 4-pentanediol, 100ml of acetonitrile, 2.15 ml of triethylamine, and 0.15 g of potassium chloride were added, and 5.00 g of 1, 8-naphthalenedicarboxylic acid chloride was added dropwise at room temperature and stirred uniformly. After stirring for 4 hours, the reaction was refluxed for 8 hours at elevated temperature. After concentration under reduced pressure, the mixture was recrystallized from a mixed solution of ether/petroleum ether (1:50) to give pale yellow crystals, which were dried under vacuum to give 2.04 g of a product (yield 36%).1H-NMR(δ,ppm,TMS,CDCl3):8.33-8.32(2H,m,ArH),7.98-7.97(2H,m,ArH),7.47-7.46(2H,m,ArH),4.15-4.13(2H,m,OCH),2.25-2.24(1H,m,CH2),2.02-2.01(1H,m,CH2),1.44-1.42(6H,m,CH3)。
The following compounds were synthesized using similar preparation methods.
2, 4-dimethyl-7, 8-benzo [ g ]]-1, 5-dioxononane-6, 9-dione (FE-2): pale yellow crystals, yield 37%.1H-NMR(δ,ppm,TMS,CDCl3):8.12～8.10(2H,m,＝CH),7.58～7.56(2H,m,ArH),4.15～4.13(2H,m,OCH),2.25～2.24(1H,m,CH2),2.01～2.00(1H,m,CH2),1.44～1.42(6H,m,CH3)。
2,3, 4-trimethyl-7, 8-benzo [ g ]]-1, 5-dioxononane-6, 9-dione (FE-3): pale yellow crystals, yield 34%.1H-NMR(δ,ppm,TMS,CDCl3):8.12～8.11(2H,m,＝CH),7.57～7.56(2H,m,ArH),4.13～4.12(2H,m,OCH),2.84～2.83(1H,m,CH),2.01～2.00(1H,m,CH),1.44～1.42(6H,m,CH3),1.05～1.03(3H,d,CH3)。
2, 4-diethyl-7, 8-benzo [ g ]]-1, 5-dioxononane-6, 9-dione (FE-4): a colorless viscous liquid, yield 32%.1H-NMR(δ,ppm,TMS,CDCl3):8.12～8.10(2H,m,＝CH),7.57～7.56(2H,m,ArH),3.96～3.96(2H,m,OCH),2.27～2.25(1H,m,CH2),2.01～2.00(1H,m,CH2),1.75～1.73(4H,m,CH2),0.97～0.95(6H,m,CH3)。
2, 4-dimethyl-3-ethyl-7, 8-benzo [ g]-1, 5-dioxononane-6, 9-dione (FE-5): a colorless viscous liquid, yield 30%.1H-NMR(δ,ppm,TMS,CDCl3):8.12～8.10(2H,m,＝CH),7.57～7.56(2H,m,ArH),4.13～4.11(2H,m,OCH),2.66～2.65(1H,m,CH),1.40～1.37(6H,m,CH3),1.28～1.26(2H,m,CH2),0.97～0.95(3H,m,CH3)。
2, 4-dimethyl-7, 8- (2' -methylbenzo) [ g]-1, 5-dioxononane-6, 9-dione (FE-6): a colorless viscous liquid, yield 32%.1H-NMR(δ,ppm,TMS,CDCl3):7.93～7.92(1H,m,＝CH),7.46～7.45(1H,m,ArH),7.38～7.37(1H,m,ArH),4.13～4.11(2H,m,OCH),2.36～2.35(3H,m,CH3),2.27～2.26(1H,m,CH2),2.02～2.01(1H,m,CH2),1.42～1.40(6H,m,CH3)。
2, 4-diethyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower ring-6, 10-dione (FE-7): pale yellow crystals, yield 35%.1H-NMR(δ,ppm,TMS,CDCl3):8.34～8.33(2H,m,ArH),7.98～7.97(2H,m,ArH),7.45～7.44(2H,m,ArH),3.96～3.94(2H,m,OCH),2.26～2.25(1H,m,CH2),2.02～2.01(1H,m,CH2),1.75～1.73(4H,m,CH2),0.98～0.96(6H,m,CH3)。
2, 4-dimethyl-3-ethyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower ring-6, 10-dione (FE-8): pale yellow crystals, yield 35%.1H-NMR(δ,ppm,TMS,CDCl3):8.35～8.34(2H,m,ArH),7.98～7.96(2H,m,ArH),7.47～7.46(2H,m,ArH),4.13～4.11(2H,m,OCH),2.66～2.65(1H,m,CH),1.40～1.37(6H,m,CH3),1.29～1.27(2H,m,CH2),0.97～0.95(3H,m,CH3)。
3-isopropyl-3-isopentyl-7, 8-benzo [ g)]-1, 5-dioxononane-6, 9-dione (FE-9): colorless liquid, yield 30%.1H-NMR(δ,ppm,TMS,CDCl3):8.10～8.09(2H,m,＝CH),7.57～7.55(2H,m,ArH),4.30～4.28(2H,m,OCH2),4.06～4.04(2H,m,OCH2),1.84～1.83(1H,m,CH),1.79～1.78(1H,m,CH),1.25～1.23(2H,m,CH2),1.21～1.20(2H,m,CH2),1.02～1.0 0(6H,m,CH3),0.97～0.95(6H,m,CH3)。
3-isopropyl-3-isoamyl-7, 9-naphtho [1',8' -gh]-1, 5-dioxosunflower ring-6, 10-dione (FE-10): a colorless viscous liquid, yield 30%.1H-NMR(δ,ppm,TMS,CDCl3):8.33～8.32(2H,m,＝CH),7.97～7.95(2H,m,ArH),7.45～7.43(2H,m,ArH),4.31～4.29(2H,m,OCH2),4.06～4.05(2H,m,OCH2),1.84～1.83(1H,m,CH),1.80～1.79(1H,m,CH),1.25～1.23(2H,m,CH2),1.21～1.20(2H,m,CH2),1.03～1.0 0(6H,m,CH3),0.96～0.93(6H,m,CH3)。
Preparation of solid component in catalyst and propylene polymerization
Examples
(1) Preparation of solid catalyst component
4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate (TBP) were sequentially added to a reactor fully replaced with high-purity nitrogen, and the mixture was heated to 50 ℃ with stirring and maintained for 2.5 hours. After the solid is completely dissolved, 1.4g of phthalic anhydride is added, the solution is continuously maintained for 1 hour, the solution is cooled to the temperature below minus 25 ℃, and TiCl is dropwise added within 1 hour460mL, slowly heating to 80 ℃, gradually separating out the solid, adding 6mmol of corresponding electron donor compound, and maintaining the temperature for 1 hour. After hot filtration, 150mL of toluene was added and washed twice to obtain a solid. 100mL of toluene was added, the temperature was raised to 110 ℃ and three washes were carried out for 10 minutes each. Then 60mL of hexane is added for washing three times, and the solid component of the catalyst is obtained after vacuum drying.
(2) Polymerization of propylene
The stainless steel reaction kettle with the volume of 5L is fully replaced by gaseous propylene, and then AlEt is added32.5mL of methylcyclohexyldimethoxysilane (CHMMS)5mL of Al/Si (mol) () 25, 10mg of the solid fraction prepared in the above example and 1.2NL of hydrogen gas were added thereto, 2.5L of liquid propylene was introduced, the temperature was raised to 70 ℃ and maintained at this temperature for 1 hour, and the temperature was lowered and the pressure was released to obtain a PP resin, and the results are shown in Table 1.
TABLE 1
Figure BDA0001811714040000141
Figure BDA0001811714040000151
DNBP: di-n-butyl phthalate;
PPDB: 2, 4-dibenzylcarboxypentane;
the amounts of FE-1, DNBP and PPDB added were all 3 mmol.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. A catalyst component for olefin polymerization comprises magnesium, titanium, halogen and an internal electron donor, wherein the internal electron donor comprises a cyclic compound shown as a formula I,
Figure FDA0001811714030000011
wherein R is1And R2The same or different, are independently selected from hydrogen and C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C6-C30Aryl radical, C4-C30Heterocyclic group, halogen atom, hydroxyl group and C1-C30Alkoxy radical, said C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C6-C30Aryl radical, C4-C30Heterocyclyl and C1-C30The hydrogen on the carbon of the alkoxy group is optionally selected from halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group;
a is (CR)3R4)m-Gn-(CR5R6)pWherein G is selected from NR7、PR8O, S and SiR9R10，R3To R10The same or different, are independently selected from hydrogen and C1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C3-C30And aliphatic cyclic hydrocarbon group of6-C30An aromatic group of1-C30Alkyl radical, C2-C30Alkenyl radical, C2-C30Alkynyl, C3-C30And aliphatic cyclic hydrocarbon group of6-C30The hydrogen on carbon of the aromatic radical being optionally selected from halogenAtom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10Alkyl, m, n and p are independently selected from integers of 0 to 6, such as 0, 1, 2,3,4, 5 or 6, or R3And R4Linked to form a ring, and/or R5And R6Connecting to form a ring;
ar is C6-C30Arylene radicals or C4-C30Heteroarylene radical, C6-C30Arylene group and/or C4-C30The heteroarylene group is optionally substituted by a halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Substituted by one or more substituents of alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group;
x and Y are the same or different and are selected from O, S and NR11，R11Selected from hydrogen and C1-C30An alkyl group.
2. The catalyst component according to claim 1, wherein R is1And R2The same or different, are independently selected from hydrogen and C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C6-C20Aryl radical, C4-C20Heterocyclic group, halogen atom, hydroxyl group and C1-C20Alkoxy, preferably selected from hydrogen, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C20Alkynyl, C6-C15Aryl radical, C4-C10Heterocyclic group, halogen atom, hydroxyl group and C1-C10Alkoxy, more preferably selected from hydrogen, C1-C8Alkyl radical, C2-C8Alkenyl radical, C6-C10Aryl radical, C2-C8Alkynyl, C4-C8Heterocyclic group, halogen atom, hydroxyl group and C1-C8An alkoxy group.
3. The catalyst component according to claim 1 or 2, characterized in that R3To R10The same or different, are independently selected from hydrogen and C1-C20Alkyl radical, C2-C20Alkenyl radical, C2-C20Alkynyl, C3-C20And C is an aliphatic cyclic hydrocarbon6-C20Aromatic radicals, preferably selected from hydrogen, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, C3-C10And C is an aliphatic cyclic hydrocarbon6-C15An aromatic group.
4. The catalyst component according to any of claims 1 to 3 in which Ar is C6-C20Arylene radicals or C4-C20A heteroarylene group, preferably Ar is C6-C15Arylene radicals or C4-C15A heteroarylene group; and/or R11Selected from hydrogen and C1-C20Alkyl, preferably hydrogen and C1-C10An alkyl group; more preferably, Ar is selected from
Figure FDA0001811714030000021
Wherein each R is1Independently selected from hydrogen, halogen atom, OH, OR, SR, C1-C10Alkyl radical, C2-C10Alkenyl radical, C2-C10Alkynyl, nitro and cyano, wherein R is C1-C10An alkyl group.
5. The catalyst component according to any of claims 1 to 4 in which the cyclic compound of formula I is selected from the group consisting of 7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane-6, 10-dione, 3-methyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane-6, 10-dione, 3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane-6, 10-dione, 3-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxetane-6, 10-dione, 3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2, 3-dimethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-methyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-methyl-3-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-methyl-3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-methyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2, 3-diethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-ethyl-3-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, 2-ethyl-3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxosunflower ring-6, 10-dione, and mixtures thereof, 2, 4-dimethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-diethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dipropyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dibutyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-methyl-4-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxopelargonyl-6, 10-dione, 2-methyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxopelargonyl-6, 10-dione, 2-methyl-4-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxopelargonyl-6, 10-dione, 2-ethyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxopelargonyl-6, 10-dione, 2,3, 4-trimethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxopelargonyl-6, 10-dione, 2, 4-diethyl-3-methyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dipropyl-3-methyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dibutyl-3-methyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 3-dimethyl-4-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 3-dimethyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 3-dimethyl-4-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-ethyl-3-methyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dimethyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2,3, 4-triethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dipropyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 4-dibutyl-3-ethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-methyl-3, 4-diethyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-methyl-4-dioxol-6, 10-dione, and mixtures thereof, 2-methyl-3-ethyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2-methyl-3-ethyl-4-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 2, 3-diethyl-4-propyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 7, 8-benzo [ g ] -1, 5-dioxol-6, 9-dione, 3-methyl-7, 8-benzo [ g ] -1, 5-Dioxononane-6, 9-dione, 3-ethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-propyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-butyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopropyl-3-isopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxodecanyl-6, 10-dione, 3-methyl-3-isopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxocyno-6, 10-dione, 3-ethyl-3-isoamyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxocyno-6, 10-dione, 3-butyl-3-isoamyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxocyno-6, 10-dione, 3-pentyl-3-isoamyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxocyno-6, 10-dione, 3-cyclopentyl-3-isoamyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxocyno-6, 10-dione, 3-cyclohexyl-3-isoamyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-isopropyl-3-butyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-isopropyl-3-cyclopentyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, 3-isopropyl-3-cyclohexyl-7, 9-naphtho [1',8' -gh ] -1, 5-dioxol-6, 10-dione, a salt thereof, a hydrate thereof, a salt thereof, a hydrate thereof, a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable salt thereof, 3-isopropyl-3-isopentyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-methyl-3-isopentyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopropyl-3-ethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopropyl-3-butyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopropyl-3-cyclopentyl-7, 8-benzo [ g ] -1, 5-Dioxononane-6, 9-dione, 3-isopropyl-3-cyclohexyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopropyl-3-cyclopropyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopentyl-3-cyclopentyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopentyl-3-cyclohexyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 3-isopentyl-3-cyclopropyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 3-dimethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2-methyl-3-ethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2-methyl-3-propyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2-methyl-3-butyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 3-diethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2-ethyl-3-propyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2-ethyl-3-butyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8-benzo [ g ] -1, 5-Dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipentyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2,3, 4-trimethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-3-methyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-3-methyl-7, 8-benzo [ g ] -1, 5-Dioxononane-6, 9-dione, 2, 4-dibutyl-3-methyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-3-ethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2,3, 4-triethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-3-ethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-3-ethyl-7, 8-benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (2 '-methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (2' -methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (2 '-methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (2' -methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, a salt thereof, a hydrate thereof, a salt thereof, and a salt thereof, 2, 4-dipentyl-7, 8- (2 ' -methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (3 ' -methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (3 ' -methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (3 ' -methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (3 ' -methyl) benzo [ g ] -1, 5-Dioxononane-6, 9-dione, 2, 4-dipentyl-7, 8- (3 '-methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4' -methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (4 '-methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (4' -methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4 ' -methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipentyl-7, 8- (4 ' -methyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4 ' -ethyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (4 ' -ethyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (4 ' -ethyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4 ' -ethyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diamyl-7, 8- (4 ' -ethyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4 ' -propyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (4 ' -propyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (4 ' -propyl) benzo [ g ] -1, 5-Dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4 '-propyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipentyl-7, 8- (4' -propyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4 '-butyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (4' -butyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (4 ' -butyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4 ' -butyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipentyl-7, 8- (4 ' -butyl) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4 ' -chloro) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (4 ' -chloro) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (4 ' -chloro) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4 ' -chloro) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dipentyl-7, 8- (4 ' -chloro) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dimethyl-7, 8- (4 ' -methoxy) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-diethyl-7, 8- (4 ' -methoxy) benzo [ g ] -1, 5-Dioxononane-6, 9-dione, 2, 4-dipropyl-7, 8- (4 ' -methoxy) benzo [ g ] -1, 5-dioxononane-6, 9-dione, 2, 4-dibutyl-7, 8- (4 ' -methoxy) benzo [ g ] -1, 5-dioxononane-6, 9-dione and 2, 4-dipentyl-7, 8- (4 ' -methoxy) benzo [ g ] -1, 5-dioxononane-6, 9-dione.
6. The catalyst component according to any of claims 1 to 5, characterized in that it comprises a titanium compound, a magnesium compound and an internal electron donor compound or the reaction product of a titanium compound, a magnesium compound and an internal electron donor compound.
7. The catalyst component according to claim 6, characterized in that the magnesium compound is selected from one of magnesium dihalides, hydrates or alcoholates of magnesium dihalides and derivatives of magnesium dihalides of the formula in which one of the halogen atoms is replaced by a hydrocarbyloxy or halohydrocarbyloxy group, or mixtures thereof, preferably from the group consisting of magnesium dihalides or alcoholates, such as magnesium dichloride, magnesium dibromide, magnesium diiodide and alcoholates thereof;
the titanium compound has a general formula of TiXm(OR1)4-mA compound of (1), wherein R1A hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, m is 1 to 4, preferably at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, and trichloromonoethoxytitanium, preferably titanium tetrachloride;
the organophosphorus compound is selected from alkyl esters or halogenated alkyl esters of orthophosphoric acid or phosphorous acid, and is preferably selected from at least one of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite and trityl phosphite.
8. The catalyst component according to any of claims 1 to 7, characterized in that the internal electron donor further comprises other internal electron donor compounds selected from ketones, ethers, amines and esters, such as alcohol esters.
9. A catalyst for the polymerization of olefins comprising:
A) the catalyst component according to any one of claims 1 to 8;
B) an alkyl aluminum compound; and
C) optionally, an external electron donor component.
10. A process for the polymerization of olefins having the general formula CH, in the presence of a solid catalyst component according to any one of claims 1 to 8 or of a catalyst according to claim 92Wherein R is hydrogen or C1～C6Alkyl groups of (a); the olefin is preferably ethylene, propylene and/or 1-butene.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000230011A (en) * 1999-02-10 2000-08-22 Tosoh Corp Transition metal compound, olefin polymerization catalyst, and production of polyolefin using the catalyst
US20050239636A1 (en) * 2002-02-07 2005-10-27 Mingzhi Gao Solid catalyst component for polymerization of olefins, catalyst comprising the same and use thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000230011A (en) * 1999-02-10 2000-08-22 Tosoh Corp Transition metal compound, olefin polymerization catalyst, and production of polyolefin using the catalyst
US20050239636A1 (en) * 2002-02-07 2005-10-27 Mingzhi Gao Solid catalyst component for polymerization of olefins, catalyst comprising the same and use thereof

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