CN114249775A - Metallocene compound, preparation method thereof, catalyst composition, supported metallocene catalyst and application thereof - Google Patents

Metallocene compound, preparation method thereof, catalyst composition, supported metallocene catalyst and application thereof Download PDF

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CN114249775A
CN114249775A CN202111468040.5A CN202111468040A CN114249775A CN 114249775 A CN114249775 A CN 114249775A CN 202111468040 A CN202111468040 A CN 202111468040A CN 114249775 A CN114249775 A CN 114249775A
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compound
methyl
reaction
metallocene
zirconium
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CN114249775B (en
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李磊
李化毅
黄河
李倩
袁炜
罗志
金政伟
申宏鹏
王芳
马金欣
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Institute of Chemistry CAS
National Energy Group Ningxia Coal Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/14—Monomers containing five or more carbon atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to the field of polymers, and discloses a metallocene compound, a preparation method thereof, a catalyst composition, a supported metallocene catalyst and application thereof. The metallocene compound of the present invention is represented by the following chemical formula (1), wherein R in the formula (1)1‑R8Each is a hydrogen atom or a C1-C12 alkyl group, and M is one or more of a transition metal element from groups III, IV, V, and VI of the periodic Table of the elements or a lanthanide. The metallocene compound has excellent catalytic activity in the homopolymerization and copolymerization of catalytic olefin.

Description

Metallocene compound, preparation method thereof, catalyst composition, supported metallocene catalyst and application thereof
Technical Field
The invention relates to the field of polymers, and particularly relates to a metallocene compound, a preparation method thereof, a catalyst composition, a supported metallocene catalyst and application thereof.
Background
The metallocene catalyst is a catalyst system formed by complexing a transition metal element and at least one cyclopentadiene or cyclopentadiene derivative serving as a ligand. The polypropylene prepared by the metallocene catalyst has narrow molecular weight distribution and easy adjustment of structure and performance, and is mostly used for synthesizing syndiotactic polypropylene with specific functions which is difficult to synthesize by the Ziegler-Natta catalyst at present. The metallocene catalyst technology injects great activity for the development of polyolefin industry, and the metallocene catalyst can be used for accurately regulating and controlling the properties of polymers, so that the polymers with uniform compositions and molecular structures are prepared. Furthermore, the activity of metallocene catalysts during polymerization is much higher than that of Ziegler-Natta catalysts. When the metallocene catalyst is applied to propylene polymerization, the synthesized mPP has the characteristics of smaller microcrystal, lower crystallinity, narrow molecular weight distribution, good molecular chain uniformity, excellent toughness and impact resistance, excellent glossiness and transparency and the like. Compared with polypropylene synthesized by traditional Ziegler-Natta catalyst, the mPP has better insulating property and radiation resistance, and is more compatible with other resins.
Metallocene catalysts have been developed that comprise a general metallocene structure, a bridged metallocene structure, and a Constrained Geometry (CGC) metallocene structure; transition metals include iron, cobalt, zirconium, titanium, hafnium, and the like; the ligand is cyclopentadiene, an anchor group, indenyl group, fluorenyl group, or the like. mPP products include homo polypropylene (high isotactic, atactic and syndiotactic), random copolymer polypropylene and block polypropylene. There are thousands of metallocene catalysts, and a slight change in the ligand structure can cause a great change in the catalytic performance of the catalyst, so that there is still a need to develop new metallocene catalysts to meet the demand in the preparation of polyolefins.
Disclosure of Invention
The invention aims to provide a novel metallocene compound, a preparation method of the metallocene compound, a catalyst composition containing the metallocene compound and a supported metallocene catalyst prepared by using the metallocene compound. The metallocene compound has excellent catalytic activity in the homopolymerization and copolymerization of catalytic olefin.
In order to achieve the above object, a first aspect of the present invention provides a metallocene compound represented by the following formula (1):
Figure BDA0003392355170000021
in the formula (1), R1-R8Each is a hydrogen atom or a C1-C12 alkyl group, and M is one or more of a transition metal element from groups III, IV, V, and VI of the periodic Table of the elements or a lanthanide.
Preferably, in the formula (1), R1-R8Each is a hydrogen atom or a C1-C4 alkyl group.
Preferably, in formula (1), M is one or more of zirconium, titanium, chromium and hafnium.
Preferably, in the formula (1), R1-R8Each is a hydrogen atom, a methyl group, an ethyl group,One or more of isopropyl and isobutyl.
Preferably, the compound represented by formula (1) is selected from one or more of the following compounds,
compound A-1: r1-R4Is H, R5-R8Is methyl, M is zirconium;
compound A-2: r1-R4Is H, R5-R8Is methyl, M is titanium;
compound A-3: r1-R4Is H, R5-R8Is methyl, M is chromium;
compound A-4: r1-R4Is H, R5-R8Is methyl, M is hafnium;
compound B-1: r2-R4Is H, R1And R5-R8Is methyl, M is zirconium;
compound B-2: r2-R4Is H, R1And R5-R8Is methyl, M is titanium;
compound B-3: r2-R4Is H, R1And R5-R8Is methyl, M is chromium;
compound B-4: r2-R4Is H, R1And R5-R8Is methyl, M is hafnium;
compound C-1: r1-R8Is methyl, M is zirconium;
compound C-2: r1-R8Is methyl, M is titanium;
compound C-3: r1-R8Is methyl, M is chromium;
compound C-4: r1-R8Is methyl, M is hafnium;
compound D-1: r1-R4Is isopropyl, R5-R8Is methyl, M is zirconium;
compound D-2: r1-R4Is isopropyl, R5-R8Is methyl, M is titanium;
compound D-3: r1-R4Is isopropyl, R5-R8Is methyl, M is chromium;
compound D-4: r1-R4Is isopropyl, R5-R8Is methyl, M is hafnium;
compound E-1: r1-R4Is ethyl, R5-R8Is methyl, M is zirconium;
compound E-2: r1-R4Is ethyl, R5-R8Is methyl, M is titanium;
compound E-3: r1-R4Is ethyl, R5-R8Is methyl, M is chromium;
compound E-4: r1-R4Is ethyl, R5-R8Is methyl, M is hafnium;
compound F-1: r1-R4Is methyl, R5-R8Is H, M is zirconium;
compound F-2: r1-R4Is methyl, R5-R8Is H, M is titanium;
compound F-3: r1-R4Is methyl, R5-R8Is H, M is chromium;
compound F-4: r1-R4Is methyl, R5-R8Is H, M is hafnium;
compound G-1: r1、R3Is H, R2、R4And R5-R8Is methyl, M is zirconium;
compound G-2: r1、R3Is H, R2、R4And R5-R8Is methyl, M is titanium;
compound G-3: r1、R3Is H, R2, R4And R5-R8Is methyl, M is chromium;
compound G-4: r1、R3Is H, R2、R4And R5-R8Is methyl, M is hafnium;
compound H-1: r1-R8Is H, M is zirconium;
compound H-2: r1-R8Is H, M is titanium;
compound H-3: r1-R8Is H, M is chromium;
compound H-4: r1-R8Is H, M is hafnium;
compound I-1: r1、R3Is isopropyl, R2、R4Is hydrogen, R5-R8Is methyl, M is zirconium;
compound I-2: r1、R3Is isopropyl, R2、R4Is hydrogen, R5-R8Is methyl, M is titanium;
compound I-3: r1、R3Is isopropyl, R2、R4Is hydrogen, R5-R8Is methyl, M is chromium;
compound I-4: r1、R3Is isopropyl, R2、R4Is hydrogen, R5-R8Is methyl, M is hafnium;
compound J-1: r1、R3Is methyl, R2、R4Is hydrogen, R5-R8Is methyl, M is zirconium;
compound J-2: r1、R3Is methyl, R2、R4Is hydrogen, R5-R8Is methyl, M is titanium;
compound J-3: r1、R3Is methyl, R2、R4Is hydrogen, R5-R8Is methyl, M is chromium;
compound J-4: r1、R3Is methyl, R2、R4Is hydrogen, R5-R8Is methyl and M is hafnium.
According to a second aspect of the present invention, there is provided a process for producing a metallocene compound according to the present invention, wherein the process comprises the steps of:
1) formylating compound 1 with an organolithium reagent and/or a TurboGrignard reagent and an amide in the presence of a first organic solvent to obtain compound 2;
2) subjecting compound 2 to wittig reaction with wittig reagent and/or wittig-horner reagent in the presence of a second organic solvent and a base to obtain compound 3;
3) in the presence of a third organic solvent and a hydrogenation catalyst, carrying out hydrogenation reaction on the compound 3 and hydrogen, and then carrying out hydrolysis reaction to obtain a compound 4;
4) carrying out Friedel-crafts acylation reaction on the compound 4 in the presence of polyphosphoric acid to obtain a compound 5;
5) in the presence of a fifth organic solvent, carrying out carbonyl reduction reaction and elimination reaction on the compound 5 to obtain a compound 6;
6) in the presence of a seventh organic solvent, reacting the compound 6 with a deprotonating reagent, then carrying out nucleophilic addition reaction with halogenated hydrocarbon, and then carrying out silicon bridging reaction on the obtained nucleophilic addition product and dihalo-dimethylsilane to obtain a compound 7;
7) reacting the compound 7 with a deprotonating agent in the presence of an eighth organic solvent, and then with a salt of a metal M to give a metallocene compound 8,
wherein compounds 1-8 are each a compound having the structure:
Figure BDA0003392355170000051
in the compounds 1 to 8, R1、R2、R5And R6Which may be the same or different, are each a hydrogen atom or an alkyl group of C1-C12, and M is one or more of a transition metal element of groups III, IV, V and VI of the periodic Table of the elements or a lanthanide.
According to a third aspect of the present invention, there is provided a catalyst composition comprising the metallocene compound of the first aspect of the present invention and a cocatalyst.
Preferably, the cocatalyst is one or more of methylaluminoxane, modified methylaluminoxane and triisobutylaluminum.
According to a fourth aspect of the present invention, there is provided a supported metallocene catalyst, wherein the supported metallocene catalyst comprises a support and the metallocene compound of the first aspect of the present invention supported on the support.
Preferably, the carrier is SiO2、Al2O3One or more of carbon materials and polymer carriers.
Preferably, the supported metallocene catalyst further comprises a cocatalyst supported on the carrier.
Preferably, the cocatalyst is one or more of methylaluminoxane, modified methylaluminoxane and triisobutylaluminum.
Preferably, the carrier is a micron carbon sphere carrier with the surface covered with silicon dioxide.
According to a fifth aspect of the present invention there is provided the use of a metallocene compound according to the first aspect of the present invention, a catalyst composition according to the third aspect of the present invention or a supported metallocene catalyst according to the fourth aspect of the present invention in the polymerisation of olefins.
According to the above technical scheme, the present invention provides a novel metallocene compound, a catalyst composition comprising the metallocene compound, and a supported metallocene catalyst obtained using the metallocene compound, which has excellent catalytic activity in the homopolymerization and copolymerization of olefins.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides a metallocene compound represented by the following chemical formula (1):
Figure BDA0003392355170000071
in the formula (1), R1-R8Which may be the same or different, are each a hydrogen atom or an alkyl group of C1-C12, and M is one or more of a transition metal element of groups III, IV, V and VI of the periodic Table of the elements or a lanthanide.
The alkyl group having 1 to 12 may be a straight-chain alkyl group or a branched-chain alkyl group, and examples of the alkyl group having 1 to 12 include: methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl and the like.
According to the invention, as R1-R8And, when the number of atoms is smaller, the steric hindrance is smaller and the activity of the compound represented by the formula (1) is higher, preferably, in the formula (1), R is1-R8Each is a hydrogen atom or an alkyl group of C1 to C4; more preferably, in the formula (1), R1-R8Each is one or more of a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, and an isobutyl group.
In the present invention, examples of M include: scandium, titanium, vanadium, chromium, yttrium, zirconium, niobium, molybdenum, lanthanum, cerium, hafnium, tantalum, tungsten, and the like.
According to the present invention, the compound represented by formula (1) has higher catalytic activity when M is a specific element, and preferably, M in formula (1) is one or more of zirconium, titanium, chromium and hafnium.
In a preferred embodiment of the present invention, the compound represented by formula (1) is selected from one or more of the following compounds,
compound A-1: r1-R4Is H, R5-R8Is methyl, M is zirconium;
compound A-2: r1-R4Is H, R5-R8Is methyl, M is titanium;
compound A-3: r1-R4Is H, R5-R8Is methyl, M is chromium;
compound A-4: r1-R4Is H, R5-R8Is methyl, M is hafnium;
compound B-1: r2-R4Is H, R1And R5-R8Is methyl, M is zirconium;
compound B-2: r2-R4Is H, R1And R5-R8Is methyl, M is titanium;
compound B-3: r2-R4Is H, R1And R5-R8Is methyl, M is chromium;
compound B-4: r2-R4Is H, R1And R5-R8Is methyl, M is hafnium;
compound C-1: r1-R8Is methyl, M is zirconium;
compound C-2: r1-R8Is methyl, M is titanium;
compound C-3: r1-R8Is methyl, M is chromium;
compound C-4: r1-R8Is methyl, M is hafnium;
compound D-1: r1-R4Is isopropyl, R5-R8Is methyl, M is zirconium;
compound D-2: r1-R4Is isopropyl, R5-R8Is methyl, M is titanium;
compound D-3: r1-R4Is isopropyl, R5-R8Is methyl, M is chromium;
compound D-4: r1-R4Is isopropyl, R5-R8Is methyl, M is hafnium;
compound E-1: r1-R4Is ethyl, R5-R8Is methyl, M is zirconium;
compound E-2: r1-R4Is ethyl, R5-R8Is methyl, M is titanium;
compound E-3: r1-R4Is ethyl, R5-R8Is methyl, M is chromium;
compound E-4: r1-R4Is ethyl, R5-R8Is methyl, M is hafnium;
compound F-1: r1-R4Is methyl, R5-R8Is H, M is zirconium;
compound F-2: r1-R4Is methyl, R5-R8Is H, M is titanium;
compound F-3: r1-R4Is methyl, R5-R8Is H, M is chromium;
compound F-4: r1-R4Is methyl, R5-R8Is H, M is hafnium;
compound G-1: r1、R3Is H, R2、R4And R5-R8Is methyl, M is zirconium;
compound G-2: r1、R3Is H, R2、R4And R5-R8Is methyl, M is titanium;
compound G-3: r1、R3Is H, R2, R4And R5-R8Is methyl, M is chromium;
compound G-4: r1、R3Is H, R2、R4And R5-R8Is methyl, M is hafnium;
compound H-1: r1-R8Is H, M is zirconium;
compound H-2: r1-R8Is H, M is titanium;
compound H-3: r1-R8Is H, M is chromium;
compound H-4: r1-R8Is H, M is hafnium;
compound I-1: r1、R3Is isopropyl, R2、R4Is hydrogen, R5-R8Is methyl, M is zirconium;
compound I-2: r1、R3Is isopropyl, R2、R4Is hydrogen, R5-R8Is methyl, M is titanium;
compound I-3: r1、R3Is isopropyl, R2、R4Is hydrogen, R5-R8Is methyl, M is chromium;
compound I-4: r1、R3Is isopropyl, R2、R4Is hydrogen, R5-R8Is methyl, M is hafnium;
compound J-1: r1、R3Is methyl, R2、R4Is hydrogen, R5-R8Is methyl, M is zirconium;
compound J-2: r1、R3Is methyl, R2、R4Is hydrogen, R5-R8Is methyl, M is titanium;
compound J-3: r1、R3Is methyl, R2、R4Is hydrogen, R5-R8Is methyl, M is chromium;
compound J-4: r1、R3Is methyl, R2、R4Is hydrogen, R5-R8Is methyl and M is hafnium.
According to a second aspect of the present invention, there is provided a process for producing a metallocene compound, the process comprising the steps of:
1) subjecting compound 1 to formylation reaction with an organolithium reagent and/or a Turbogrignard reagent and an amide in the presence of a first organic solvent to obtain compound 2;
2) subjecting compound 2 to wittig reaction with wittig reagent and/or wittig-horner reagent in the presence of a second organic solvent and a base to obtain compound 3;
3) in the presence of a third organic solvent and a hydrogenation catalyst, carrying out hydrogenation reaction on the compound 3 and hydrogen, and then carrying out hydrolysis reaction to obtain a compound 4;
4) carrying out Friedel-crafts acylation reaction on the compound 4 in the presence of polyphosphoric acid to obtain a compound 5;
5) in the presence of a fifth organic solvent, carrying out carbonyl reduction reaction and elimination reaction on the compound 5 to obtain a compound 6;
6) in the presence of a seventh organic solvent, reacting the compound 6 with a deprotonating reagent, then carrying out nucleophilic addition reaction with halogenated hydrocarbon, and then carrying out silicon bridging reaction on the obtained nucleophilic addition product and dihalo-dimethylsilane to obtain a compound 7;
7) reacting the compound 7 with a deprotonating agent in the presence of an eighth organic solvent, and then with a salt of a metal M to give a metallocene compound 8,
wherein compounds 1-8 are each a compound having the structure:
Figure BDA0003392355170000101
in the compounds 1 to 8, R1、R2、R5And R6Which may be the same or different, are each a hydrogen atom or an alkyl group of C1-C12, and M is one or more of a transition metal element of groups III, IV, V and VI of the periodic Table of the elements or a lanthanide.
In the present invention, two monomers linked by a silicon bridge structure are present in the structures of compounds 7 and 8, and the above compounds 1 to 6 are used to represent that the substituent is R1、R2、R5、R6The compounds 1 to 6 and R in the following synthetic scheme (1)1、R2、R5、R6Are respectively replaced by R3、R4、R8、R7The other monomer can be prepared.
As said R1-R8Examples thereof include: methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl and the like.
Preferably, in the formula (1), R1-R8Each is a hydrogen atom or an alkyl group of C1 to C4; more preferably, in the formula (1), R1-R8Each is one or more of a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, and an isobutyl group.
Examples of M include: one or more of scandium, titanium, vanadium, chromium, yttrium, zirconium, niobium, molybdenum, lanthanum, cerium, hafnium, tantalum, tungsten, and the like; preferably, in formula (1), M is one or more of zirconium, titanium, chromium and hafnium.
The steps will be described in detail below.
1) Formylation reaction
In the present invention, compound 2 is obtained by subjecting compound 1 to formylation reaction with an organolithium reagent and/or a Turbogrignard reagent and an amide in the presence of a first organic solvent.
The amide may be DMF (N, N-dimethylformamide).
The molar amount of compound 1 to the amide used may be, for example, 1: 1-3, preferably 1: 2-2.5.
The first organic solvent may be one or more of tetrahydrofuran, toluene, n-hexane, and diethyl ether. The amount of the solvent to be used is not particularly limited as long as the reaction proceeds smoothly, and may be an amount conventionally used in the art.
When an organolithium reagent is used, the molar ratio of compound 1 to organolithium reagent may be 1: 1-1.5, preferably 1: 1.1-1.3.
In addition, when using a TurboGringnard reagent, the molar ratio of compound 1 to TurboGringnard reagent can be 1: 1.0 to 1.5, preferably 1: 1.1-1.3.
The formylation reaction may be various conditions commonly used in the art, for example, the reaction conditions of the formylation reaction may include: the reaction temperature is-78-0 ℃, and the reaction time is 8-12 h.
After the reaction is completed, the reaction product may be purified by various purification methods commonly used in the art, for example, quenching the reaction with dilute hydrochloric acid, extraction with an organic solvent (for example, ethyl acetate), and after removing the solvent, the crude product may be purified by column separation, recrystallization, or the like.
In a specific embodiment of the invention, iodo-N-phenylimidazole is used as a starting material, and formylation is carried out under the action of an organic lithium reagent and N, N-dimethylformamide to obtain a compound 2.
2) Wittig reaction
In the present invention, compound 2 is subjected to wittig reaction with wittig reagent or wittig-horner reagent in the presence of a second organic solvent and a base to give compound 3.
The second organic solvent may be one or more of tetrahydrofuran, toluene, n-hexane and diethyl ether. The amount of the solvent to be used is not particularly limited as long as the reaction proceeds smoothly, and may be an amount conventionally used in the art.
As the base, for example, one or more of NaH, alkyllithium, sodium alkoxide, and sodium amide; NaH is preferred.
The molar ratio of compound 2 to the base may be, for example, 1: 1-1.5, preferably 1: 1.1-1.3.
The wittig agent may be: ph3P＝CR6COOEt。
The Wittig-horner reagent may be (EtO)2POCHR6CO2Et and/or (EtO)2POCHR6CO2Me, preferably (EtO)2POCHR6CO2Et。
R in the above formula6Can be replaced by R7To prepare the substituent as R7The compound of (1).
The molar ratio of compound 2 to wittig or wittig-horner agent is 1: 1-1.5, preferably 1: 1-1.3.
The reaction conditions of the wittig reaction include: the reaction temperature is 0-45 ℃, and the reaction time is 5-20 h; preferably, the reaction conditions of the wittig reaction include: the reaction temperature is 0-40 ℃, and the reaction time is 8-15 h.
After the reaction is completed, the reaction product may be purified by various purification methods commonly used in the art, for example, water quenching reaction, extraction with an organic solvent (for example, ethyl acetate) and purification of the crude product by column separation or recrystallization after removal of the solvent.
3) Hydrogenation and hydrolysis reactions
In the present invention, in the presence of a third organic solvent and a hydrogenation catalyst, the compound 3 is subjected to a hydrogenation reaction with hydrogen and then to a hydrolysis reaction to obtain a compound 4.
Specifically, the compound 3 is subjected to hydrogenation to obtain the following compound 9, and the compound 9 is further subjected to hydrolysis to obtain the compound 4.
Figure BDA0003392355170000131
The hydrogenation catalyst may be a palladium on carbon catalyst.
The amount of the hydrogenation catalyst used may be 0.5 to 1.5% by mass based on the total mass of the hydrogenation reaction system.
The third organic solvent may be an alcohol solvent, and specifically may be one or more of ethanol, methanol, and isopropanol; ethanol is preferred. The amount of the solvent to be used is not particularly limited as long as the reaction proceeds smoothly, and may be an amount conventionally used in the art.
The conditions of the hydrogenation reaction include: the reaction temperature is 5-40 ℃, and the reaction time is 10-48 h; preferably, the conditions of the hydrogenation reaction include: the reaction temperature is 5-30 ℃, and the reaction time is 20-30 h.
After the hydrogenation reaction is completed, the reaction product may be purified by various purification methods commonly used in the art, for example, the catalyst may be removed by filtration, and after the solvent is removed, the obtained solid product may be used for the next hydrolysis reaction.
The hydrolysis reaction may be a hydrolysis reaction in the presence of a fourth organic solvent and an acid, and the acid may be hydrochloric acid. The amount of the acid is not particularly limited and may be an amount conventionally used in hydrolysis in the art.
The fourth organic solvent may be an alcohol solvent, and the alcohol solvent may be one or more of methanol, ethanol and isopropanol; methanol is preferred.
The conditions of the hydrolysis reaction are not particularly limited as long as the hydrolysis reaction proceeds sufficiently, and the hydrolysis reaction is preferably performed under reflux, and the reaction time may be, for example, 10 to 50 hours.
The concentration of the acid for the hydrolysis reaction may be 15 to 40% by mass, preferably 25 to 37% by mass.
The post-treatment of the hydrolysis reaction may be carried out by a method conventional in the art, and may be, for example: after the solvent is removed, the crude product is washed with water, extracted with an organic solvent (for example, ethyl acetate), and then purified by column separation, recrystallization, or the like.
4) Friedel-crafts acylation reaction
In the present invention, compound 4 is subjected to Friedel-crafts acylation reaction in the presence of polyphosphoric acid to give compound 5.
The polyphosphoric acid may be used in an excess amount as long as the reaction proceeds sufficiently, and for example, the polyphosphoric acid may be used in an amount of 1 to 10 parts by weight, preferably 1 to 5 parts by weight, and more preferably 1.5 to 2 parts by weight, based on 1 part by weight of the compound 4.
The reaction conditions of the Friedel-crafts acylation reaction comprise: the reaction temperature is 50-90 ℃, and the reaction time is 3-20 h; preferably, the conditions of the friedel-crafts acylation reaction comprise: the reaction temperature is 70-90 ℃ and the reaction time is 5-10 h.
The post-treatment of the friedel-crafts acylation reaction can be carried out by methods conventional in the art, and can be, for example: the reaction solution is diluted by pouring into ice water, extracted with an organic solvent (for example, ethyl acetate), and the crude product is purified by column separation, recrystallization, or the like after the solvent is removed.
5) Carbonyl reduction and elimination reactions
In the present invention, the compound 5 is subjected to the carbonyl reduction reaction and elimination reaction in the presence of the fifth organic solvent to obtain the compound 6.
Specifically, the carbonyl reduction reaction gives the following compound 10, and the elimination reaction of the compound 10 gives the compound 6.
Figure BDA0003392355170000141
The fifth organic solvent may be one or more of tetrahydrofuran, toluene, n-hexane and diethyl ether, and is preferably diethyl ether. The amount of the solvent to be used is not particularly limited as long as the reaction proceeds smoothly, and may be an amount conventionally used in the art.
As the reducing agent for the carbonyl group reduction reaction, a reducing agent generally used in the art for reducing a carbonyl group can be used, and for example, LiAlH can be used4。
The molar ratio of the compound 5 to the reducing agent may be, for example, 1: 1-5, preferably 1: 1-3, more preferably 1: 2-2.5.
The reaction conditions of the carbonyl reduction reaction include: the reaction temperature is 10-40 ℃, and the reaction time is 10-50 h; preferably, the conditions of the carbonyl reduction reaction include: the reaction temperature is 10-30 ℃, and the reaction time is 20-30 h.
The post-treatment of the carbonyl reduction reaction may be carried out by a method conventional in the art, and may be, for example: the solid material is removed by filtration, and after the filter cake is washed with an organic solvent (which may be, for example, diethyl ether), the washing liquid and the filtered liquid phase are combined and the solvent is removed for the next reaction.
The elimination reaction is an elimination reaction performed in the presence of a sixth organic solvent and a catalyst, and the sixth organic solvent may be, for example, toluene. The amount of the solvent to be used is not particularly limited as long as the reaction proceeds smoothly, and may be an amount conventionally used in the art.
The catalyst for the elimination reaction may be TsOH, H2SO4、H3PO4And Al2O3Preferably TsOH.
The molar ratio of the catalyst of the elimination reaction to compound 5 may be from 0.05 to 0.3: 1, preferably 0.08 to 0.15: 1.
the reaction conditions of the elimination reaction include: the reaction temperature is 80-130 ℃, and the reaction time is 10-48 h; preferably, the reaction conditions of the elimination reaction include: the reaction temperature is 105-125 ℃, and the reaction time is 20-30 h.
The post-treatment of the elimination reaction may be carried out by a method conventional in the art, and may be, for example: after the solvent is removed, water is added and the mixture is washed, and then extracted with an organic solvent (for example, ethyl acetate), and after the solvent is removed, the crude product is purified by column separation, recrystallization, or the like.
6) Deprotonation addition reactions and silane bridging reactions.
In the invention, in the presence of a seventh organic solvent, a compound 6 is reacted with a deprotonating reagent and then subjected to nucleophilic addition reaction with a halogenated hydrocarbon, and then the obtained reaction product is subjected to silicon bridging reaction with dihalodimethylsilane to obtain a compound 7;
specifically, compound 6 is reacted with a deprotonating agent, and then subjected to nucleophilic addition reaction with a halogenated hydrocarbon to give compound 11, and compound 11 is subjected to silicon-bridging reaction with dihalodimethylsilane to give the following compound 7.
Figure BDA0003392355170000161
The deprotonating agent may be one or more of n-butyllithium, isobutyllithium and tert-butyllithium, and n-butyllithium is preferred.
The halogenated hydrocarbon is a compound represented by the following formula (2):
R6x is a group represented by the formula (2),
wherein, X is one or more of chlorine, bromine and iodine.
The molar ratio of the deprotonating agent to compound 6 may be 1-1.5: 1, preferably 1 to 1.3: 1.
the seventh organic solvent may be one or more of tetrahydrofuran, toluene, n-hexane, and diethyl ether, and is preferably tetrahydrofuran. The amount of the solvent to be used is not particularly limited as long as the reaction proceeds smoothly, and may be an amount conventionally used in the art.
The reaction conditions of the deprotonation reaction include: the reaction temperature is-78-0 ℃, and the reaction time is 5-50min, preferably 25-35 min.
The molar ratio of the halogenated hydrocarbon to compound 6 may be 1 to 1.5: 1, preferably 1 to 1.3: 1.
the reaction conditions for the nucleophilic addition reaction with the halogenated hydrocarbon include: the reaction temperature is 5-40 ℃, and the reaction time is 0.5-5 h; preferably, the reaction conditions for the nucleophilic addition reaction with the halogenated hydrocarbon include: the reaction temperature is 10-30 ℃ and the reaction time is 1-2 h.
In addition, the above deprotonation and nucleophilic addition reaction may not be carried out to obtain R6A compound which is a hydrogen atom.
Preferably, after the nucleophilic addition reaction is completed, the reaction is quenched with water, extracted with an organic solvent (preferably ethyl acetate), and the solvent is removed and used directly in the next reaction.
Preferably, the silicon-bridging reaction with the dihalodimethylsilane comprises: in the presence of a solvent, a deprotonating reagent is reacted with the compound 11, and a dihalodimethylsilane is added dropwise to carry out a silicon bridging reaction. Here, the deprotonating reagent, the solvent and the reaction conditions may be the same as those used in the reaction of the compound 6 with the deprotonating reagent.
The dihalodimethylsilane may be dichlorodimethylsilane and/or dibromodimethylsilane.
Since the reaction product is used for the silicon bridging reaction after the reaction of the compound 6 with the deprotonating agent and the nucleophilic addition reaction with the halogenated hydrocarbon by a simple treatment such as extraction, the amount of the dihalodimethylsilane to be used may be selected depending on the amount of the compound 6, and preferably, the molar ratio of the dihalodimethylsilane to the compound 6 may be 1 to 1.5: 1, more preferably 1 to 1.3: 1.
the reaction conditions of the silicon bridging reaction comprise: the reaction temperature is 5-40 ℃, and the reaction time is 0.5-5 h; preferably, the reaction conditions of the silicon bridging reaction include: the reaction temperature is 10-30 ℃ and the reaction time is 1-2 h.
The post-treatment of the silicon bridging reaction may be performed by a method conventional in the art, and may include, for example: the reaction is quenched with water, extracted with an organic solvent (preferably ethyl acetate), and the crude product is purified by column separation or recrystallization after removal of the solvent.
7) Preparation of metallocene compounds
In the present invention, compound 7 is reacted with a deprotonating agent in the presence of an eighth organic solvent, and further reacted with a salt of metal M to give compound 8.
The eighth organic solvent may be one or more of tetrahydrofuran, toluene, n-hexane, and diethyl ether, and is preferably tetrahydrofuran. The amount of the solvent to be used is not particularly limited as long as the reaction proceeds smoothly, and may be an amount conventionally used in the art.
The conditions under which the compound 7 is reacted with the deprotonating agent include: the reaction temperature is-78-0 ℃, and the reaction time is 5-50min, preferably 25-35 min.
The deprotonating agent may be one or more of n-butyllithium, isobutyllithium and tert-butyllithium, and n-butyllithium is preferred.
The molar ratio of the deprotonating agent to compound 7 may be 1-1.5: 1, preferably 1 to 1.3: 1.
the salt of the metal M may be, for example, a hydrochloride.
Specific examples of the metal M include MCl4。
The molar ratio of the salt of the metal M to the compound 7 may be 0.5 to 2: 1, preferably 0.5 to 1.5: 1, more preferably 0.5 to 1: 1.
the conditions for the reaction with the salt of the metal M after the reaction with the deprotonating agent may include, for example: the reaction temperature is 5-40 ℃, and the reaction time is 10-48 h; preferably, the conditions for the further reaction with the salt of the metal M include: the reaction temperature is 10-30 ℃, and the reaction time is 20-30 h.
The work-up as a reaction with the salt of the metal M can be carried out by methods customary in the art, such as: filtering the reaction liquid, washing the precipitate with toluene, combining the filtrates, distilling under reduced pressure to remove part of the solvent, dropwise adding n-hexane until the precipitate is generated, then adding a small amount of toluene to dissolve the precipitate, and crystallizing the solution at-30-0 ℃.
Preferably, the compound represented by formula (1) can be prepared according to the method represented by the following synthetic scheme (1).
Figure BDA0003392355170000181
In a third aspect, the present invention provides a catalyst composition comprising the metallocene compound of the present invention and a cocatalyst.
The cocatalyst may be an aluminum-containing cocatalyst and/or a boron-containing cocatalyst which are generally used in the art, and examples of the cocatalyst include: methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylaluminum chloride, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylmethoxyaluminum, dimethylethoxyaluminum, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, or the like; preferably, the cocatalyst is one or more of methylaluminoxane, modified methylaluminoxane and triisobutylaluminum; more preferably, the cocatalyst is one or more of methylaluminoxane, modified methylaluminoxane and triisobutylaluminum. When the cocatalyst is the above-mentioned preferred cocatalyst, the catalyst composition has a higher catalytic activity.
According to the present invention, in order to further improve the catalytic activity of the catalyst composition, it is preferred that the ratio of the number of moles of the cocatalyst calculated as Al/B element to the number of moles of the metallocene compound represented by the formula (1) calculated as M in the catalyst composition is 100-: 1.
the third aspect of the present invention provides a supported metallocene catalyst comprising a carrier and the metallocene compound of the present invention supported on the carrier.
According to the present invention, for the convenience of use, the reactivity is improved, and preferably, a cocatalyst supported on the carrier may be further included as the supported metallocene catalyst; the cocatalyst can be the cocatalyst used in the catalyst composition of the present invention, preferably, the cocatalyst is one or more of methylaluminoxane, modified methylaluminoxane and triisobutylaluminum; more preferably, the cocatalyst is one or more of methylaluminoxane, modified methylaluminoxane and triisobutylaluminum.
The method for supporting the metallocene compound or the cocatalyst on the support is not particularly limited, and a supporting method generally used in the art, for example, an impregnation method may be used.
According to the invention, the support may be a support for a supported catalyst as is commonly used in the art, and the support may be, for example, SiO2、Al2O3One or more of a carbon material and a polymer carrier; more preferably, the carrier is a micron carbon sphere carrier with the surface covered with silicon dioxide.
When the carrier is a micron carbon sphere carrier with the surface covered with silicon dioxide, the catalytic activity of the obtained supported catalyst is higher.
In the present invention, the amounts of the support and the metallocene compound represented by the formula (1) may be adjusted according to the kind of the support and the actual need, and preferably, the mass ratio of the support and the metallocene compound is 1: 0.001-0.1; more preferably, the mass ratio of the support and the metallocene compound is 1: 0.01-0.05. When the mass ratio of the support to the metallocene compound is the above value, the metallocene compound is distributed more uniformly, the contact with the olefin is more sufficient, and the activity of the obtained supported metallocene catalyst is higher.
The micron carbon sphere carrier with the surface covered with the silicon dioxide can be prepared by the following method:
dissolving a halogen-containing polymer in a good solvent to obtain a mixed solution, mixing the mixed solution with a poor solvent to obtain a halogen-containing polymer microsphere solution, carrying out hydrothermal reaction on the halogen-containing polymer microsphere solution, carrying out solid-liquid separation on the obtained reaction product, then carbonizing the reaction product, mixing the obtained carbonized product with siloxane, and roasting to obtain the carrier.
According to the present invention, the halogen-containing polymer may be a halogen-containing polymer obtained by polymerizing a halogen-substituted olefin monomer, and in order to obtain microspheres having an appropriate size and porosity, the halogen content of the halogen-containing polymer is preferably 40 to 85 mass% based on the total mass of the halogen-containing polymer; more preferably, the halogen content of the halogen-containing polymer is 45 to 80 mass% of the total mass of the halogen-containing polymer; further preferably, the halogen content of the halogen-containing polymer is 60 to 70 mass% based on the total mass of the halogen-containing polymer.
According to the present invention, the halogen in the halogen-containing polymer is not particularly limited, and may be, for example, one or more of F, Cl, Br and I, and is preferably Cl and/or Br from the viewpoint of the production cost of the polymer and the solubility of the polymer.
According to the present invention, the halogen-containing polymer may contain elements other than carbon, hydrogen and halogen, but from the viewpoint of improving the solubility of the polymer and promoting the subsequent hydrothermal reaction, the total content of carbon, hydrogen and halogen in the halogen-containing polymer is preferably 90% by mass or more of the total mass of the halogen-containing polymer; more preferably, the total content of carbon, hydrogen and halogen in the halogen-containing polymer is 95 mass% or more of the total mass of the halogen-containing polymer.
Examples of the halogen-containing polymer include halogenated polyolefins and/or halogenated polyhaloolefins.
Specifically, the halogen-containing polymer may be one or more of halogenated polyethylene, halogenated polypropylene, halogenated poly-1-butene, halogenated polyvinyl chloride, halogenated poly-1, 1-dichloroethylene, halogenated poly-1, 2-dichloroethylene, halogenated poly-1, 1, 2-trichloroethylene, halogenated poly-3-chloropropene, halogenated polychloroprene, halogenated polybromoethylene, halogenated poly-3-bromopropylene, and halogenated polybromobutene; preferably, the halogen-containing polymer is one or more of chlorinated polyethylene, chlorinated polypropylene, chlorinated poly-1-butene, chlorinated polyvinyl chloride, chlorinated poly-1, 1-dichloroethylene, chlorinated poly-1, 2-dichloroethylene, chlorinated poly-1, 1, 2-trichloroethylene, chlorinated poly-3-chloropropene, chlorinated polychloroprene, chlorinated polybromoethylene, chlorinated poly-3-bromopropene, chlorinated polybromobutene, brominated polyethylene, brominated polypropylene, brominated poly-1-butene, brominated polyvinyl chloride, brominated poly-1, 1-dichloroethylene, brominated poly-1, 2-dichloroethylene, brominated poly-1, 1, 2-trichloroethylene, brominated poly-3-chloropropene, brominated polychlorobutene, brominated polybromoethylene, brominated poly-3-bromopropene and brominated polybromobutene; more preferably, the halogen-containing polymer is one or more of chlorinated polyethylene, chlorinated polypropylene, chlorinated polyvinyl chloride, brominated polyethylene and brominated polypropylene; further preferably, the halogen-containing polymer is chlorinated polyethylene and/or chlorinated polypropylene.
When the halogen-containing polymer is selected from the polymers, the prepared carrier has more pore channel structures, and the obtained supported catalyst has higher catalytic activity.
The dissolving method is not particularly limited as long as the halogen-containing polymer is sufficiently dissolved, and examples thereof include: the polymer was added to a good solvent and heated under reflux while stirring.
The temperature of the heating reflux is 40-150 ℃ and the time is 1-5h, preferably, the temperature of the heating reflux is 60-120 ℃ and the time is 2-4 h.
In order to facilitate the subsequent precipitation of carbon spheres with appropriate size, the concentration of the halogenated polyolefin polymer in the good solvent is preferably 0.5 to 20 mass%; more preferably, the concentration of the halogenated polyolefin-based polymer in the good solvent is 0.5 to 10 mass%.
The good solvent is not particularly limited as long as the halogen-containing polymer can be sufficiently dissolved, and examples of such good solvents include tetrahydrofuran, dimethyl sulfoxide, aromatic hydrocarbons, amides, chlorinated hydrocarbons, and the like, and preferably include one, two, or more kinds of tetrahydrofuran, toluene, xylene, chloroform, trichlorobenzene, o-dichlorobenzene, p-dichlorobenzene, 2, 4-dichlorophenol, dimethyl sulfoxide, N-dimethylformamide, and N, N-dimethylacetamide; in order to obtain a carrier with more suitable size and pore size, more preferably, the good solvent is one or more of tetrahydrofuran, xylene and dimethyl sulfoxide.
The amount ratio of the good solvent to the poor solvent may be adjusted within a wide range as long as the microspheres can be precipitated from the mixed solution, and for example, the volume ratio of the good solvent to the poor solvent may be 1: 1-100; in order to further obtain microspheres having a suitable and uniform size, the volume ratio of the good solvent to the poor solvent is preferably 1: 20-80.
The poor solvent is not particularly limited as long as it can precipitate microspheres from the mixed solution, and examples of such a good solvent include one or more of water, ammonia water, alcohols, ketones, ethers, alkanes, and esters, and specifically, one or more of water, ammonia water, methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerol, isopropanol, n-octanol, benzyl alcohol, acetone, methyl ethyl ketone, n-hexane, cyclohexane, methyl ether, ethyl ether, n-propyl ether, n-butyl ether, ethyl acetate, and butyl acetate. In order to obtain a carrier with more suitable size and pore size, preferably, the poor solvent is one or more of water, methanol, ethanol, ethyl acetate and acetone.
The mixing method is not particularly limited as long as the mixed solution can precipitate microspheres, and preferably, the mixing conditions include: the mixing temperature is-20-60 ℃, and the mixing time is 0.5-5 h; more preferably, the mixing conditions include: the mixing temperature is 0-40 deg.C, and the mixing time is 0.5-3 hr. When the mixing conditions are the above conditions, the precipitation of the microspheres is more complete.
In order to facilitate the hydrothermal reaction, the method preferably further comprises the step of concentrating the mixed solution obtained in the step 1) after mixing the mixed solution with a poor solvent;
the concentration is performed to reduce the amount of the solvent to promote the hydrothermal reaction, and the concentration method is not particularly limited, and may be a concentration method generally used in the art, for example, a method of evaporating the solvent by heating and removing the solvent by filtration.
The amount of the solvent removed when the concentration is carried out may be 10 to 90%, and in order to further increase the rate of the subsequent hydrothermal reaction, it is preferable that the amount of the solvent removed when the concentration is carried out is 20 to 80%
It is needless to say that the halogen-containing polymer microsphere solution may be prepared by removing all the solvent and then adding a new solvent. Specifically, after mixing, solid-liquid separation is performed to remove a liquid phase to obtain halogen-containing polymer microspheres, and the halogen-containing polymer microspheres solution is prepared by adding the poor solvent. Thus, the solvent in the halogen-containing polymer microsphere liquid can be replaced by a new poor solvent as much as possible, so that the hydrothermal reaction efficiency is higher, the specific surface area of the prepared carrier is larger, and the catalyst activity is higher.
The solid-liquid separation method is not particularly limited, and may be a solid-liquid separation method generally used in the art, and may be one or more of filtration and centrifugation, for example.
In order to make the halogen-containing polymer microspheres react more fully, the hydrothermal reaction conditions preferably include: the reaction temperature is 200 ℃ and 400 ℃, and the reaction time is 1-10 h; more preferably, the conditions of the hydrothermal reaction include: the reaction temperature is 250 ℃ to 350 ℃, and the reaction time is 2-8 h.
The carbonization is used to convert the hydrothermal reaction product into carbon spheres, and as such conversion conditions include: heating for 1-10h at the heating temperature of 200-1000 ℃ under the inert atmosphere; more preferably, the carbonization conditions include: under the inert atmosphere, the carbonization temperature is 250-800 ℃, and the carbonization time is 2-7.
Preferably, the conditions for the heat carbonization include: heating to 200-1000 ℃ at 1-20 ℃/min under inert atmosphere, and heating for 1-10h at the temperature; more preferably, the conditions for heat carbonization further include: heating to 250-800 ℃ at the speed of 1-20 ℃/min under inert atmosphere, and then heating for 2-7h at the temperature.
Preferably, the method further comprises the step of drying the solid phase obtained by the solid-liquid separation before the carbonization, wherein the drying is used for removing the solvent to facilitate the carbonization.
Preferably, the drying conditions include: the drying temperature is 50-200 ℃, and the drying time is 1-8 h; more preferably, the drying conditions include: the drying temperature is 80-150 ℃, and the drying time is 3-8 h.
The siloxane is used for combining with the carbon spheres and then converting into silicon dioxide to form a structure that the silicon dioxide covers the surfaces of the carbon spheres, and the siloxane can be one or more of tetramethylsiloxane, tetraethoxysiloxane, trimethoxychlorosilane, triethoxy chlorosilane, dimethoxy dichlorosilane and ethoxy trichlorosilane; in order to be more closely combined with the carbon spheres, preferably, the siloxane is one or more of tetramethylsiloxane, tetraethoxysiloxane and trimethoxychlorosilane.
The siloxane may be used in an amount sufficient to bond the carbon spheres and the siloxane, and the amount may be, for example, such that the mass ratio of the carbon spheres to the siloxane is 1: 20-100 parts of; in order to improve the bonding efficiency and facilitate the firing treatment, it is preferable that the mass ratio of the carbon spheres to the siloxane is 1: 20-50.
In order to make the siloxane sufficiently bound to the carbon spheres, preferably, the conditions of the mixed adsorption include: the mixing temperature is 20-200 ℃, and the mixing time is 1-10 h; more preferably, the conditions of the mixed adsorption include: the mixing temperature is 50-150 ℃, and the mixing time is 2-8 h.
According to the invention, the calcination is used to convert the siloxane to silica, as such calcination conditions may include: the roasting temperature is 400-; in order to further improve the conversion efficiency, preferably, the roasting conditions include: the roasting temperature is 400-700 ℃, and the roasting time is 2-7 h.
When the metallocene compound of the present invention is supported on the above-mentioned carrier, it has an advantage of high activity.
In a fourth aspect, the present invention provides the use of a metallocene compound, catalyst composition or supported metallocene catalyst of the invention in the polymerisation of olefins.
The invention provides a metallocene catalyst with excellent catalytic activity and a preparation method thereof, which can be used for catalyzing olefin homopolymerization and copolymerization. The invention also provides a catalyst composition and a supported metallocene catalyst comprising the metallocene catalyst of the invention for catalyzing the polymerization of olefins.
The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.
In the following examples, Fischer-Tropsch synthesized alpha olefins were obtained from the limited liability company of the Shenhua Ningxia coal industry group and contained 6 wt% C8 olefins, 13 wt% C9 olefins, 30 wt% C10 olefins, 14 wt% C11 olefins, 5 wt% C12 olefins, and 32 wt% saturated C8-C12 alkanes.
Preparation example 1
A metallocene compound (compound having a structure represented by the formula (2) wherein R is R in the compound having a structure represented by the formula (1) was synthesized according to the following synthesis scheme (2)1-R4Is hydrogen, R5-R8Is methyl group)
(1) Formylation reaction
Adding 100g (0.37mol) of iodo N-phenylimidazole into a 1000mL three-neck flask, fully replacing nitrogen, adding 200mL of anhydrous tetrahydrofuran, and cooling to-78 ℃; then, 148mL of n-butyllithium solution (2.5M n-hexane solution) was slowly added dropwise; then, 54g (0.74 mol) of anhydrous N, N-dimethylformamide is added dropwise; finally, the temperature was slowly raised to room temperature, and the reaction was carried out overnight. And (3) post-treatment: the reaction was quenched by addition of 100mL of dilute hydrochloric acid (10 wt%), and the organic phase was extracted with ethyl acetate, dried and separated by column chromatography. 45.2g of the compound 1-2 was obtained in 71% yield.
(2) Wittig reaction
Taking a 500mL three-neck flask, adding 4.8g (0.12mol, 60 wt% dispersed in mineral oil) of sodium hydride and 100mL of dried tetrahydrofuran under the protection of nitrogen, and cooling to 0 ℃; then dropwise (EtO)2POCH(CH3)CO2Et 28.6g (0.12mol), and then reacted for half an hour; then, a tetrahydrofuran solution (100mL) of Compound 1-2(17.2g, 0.1mol) was added dropwise; finally, slowly raising the temperature to room temperature for reaction for 10 hours. And (3) post-treatment: adding water to quench the reaction, extracting the organic phase with ethyl acetate, drying, and separating with chromatographic column. 25.3g of the compounds 1 to 3 were obtained in a yield of 99%.
(3) Hydrogenation and hydrolysis reactions
A500 mL single-tube flask was charged with 20.5g (0.08mol) of the compounds 1 to 3, 100mL of ethanol, and 1.0g of palladium on carbon (palladium content: 10%), followed by connecting a hydrogen balloon, and the reaction was stirred at room temperature for 24 hours. And (3) post-treatment: the catalyst was removed by filtration and the solvent was evaporated to dryness. The solid compound obtained was not further purified and was directly subjected to the next reaction.
The product obtained in the previous step was dissolved in 200mL of methanol, and 20mL of concentrated hydrochloric acid (37 wt%) was added and heated under reflux for 48 hours. And (3) post-treatment: evaporating the solvent to dryness, washing with water, extracting organic phase with ethyl acetate, drying, and separating with chromatographic column. 15.6g of the compounds 1 to 4 were obtained in 85% yield in two steps.
(4) Friedel-crafts acylation reaction
A250 mL single-neck flask was charged with 11.5g (0.05mol) of Compound 1-4 and 20 g of polyphosphoric acid, and the temperature was raised to 80 ℃ to react for 8 hours. And (3) post-treatment: pouring the reaction solution into ice water, extracting with ethyl acetate, drying, and separating with a chromatographic column. 9.5g of the compounds 1 to 5 were obtained in a yield of 90%.
(5) Carbonyl reduction and elimination reactions
Taking a 100mL single-neck flask, adding 8.5g (0.04mol) of compound 1-5 and 100mL of anhydrous ether, and cooling to 0 ℃; then 3.0g (0.08mol) of lithium aluminium hydride is added in portions; finally, the reaction was carried out at room temperature overnight. And (3) post-treatment: filtering to remove solid substances, washing the filter cake with diethyl ether for three times, combining the filtrates, and evaporating the solvent to dryness for later use.
The above product was dissolved in 100mL of toluene, 0.76g (0.004mol) of p-toluenesulfonic acid monohydrate was added, and the mixture was refluxed for 24 hours. And (3) post-treatment: evaporating the solvent to dryness, washing with water, extracting with ethyl acetate, and separating with chromatographic column. Compounds 1-6 were obtained in 5.7g, 73% yield.
(6) Deprotonation nucleophilic addition reaction and silicon bridging reaction
Under the protection of nitrogen, adding compound 1-6 of 19.6g (0.1mol) and 100mL of dried tetrahydrofuran into a 500mL three-neck flask, and cooling to-78 ℃; then, 40mL (2.5M, n-hexane solution) of n-butyllithium was added dropwise, and after stirring for 30 minutes, 14.2g (0.1mol) of methyl iodide was added; finally, the temperature is slowly raised to the room temperature, and the reaction is carried out for 1 hour. And (3) post-treatment: adding water to quench the reaction, extracting with ethyl acetate, and evaporating the solvent for later use.
Under the protection of nitrogen, dissolving the product into 100mL of dried tetrahydrofuran, and cooling to-78 ℃; then, 40mL (2.5M, n-hexane solution) of n-butyllithium was added dropwise, and after stirring for 30 minutes, 6.45g (0.05mol) of dichlorodimethylsilane was added; finally, the temperature is slowly raised to the room temperature, and the reaction is carried out for 1 hour. And (3) post-treatment: adding water to quench the reaction, extracting with ethyl acetate, and separating with chromatographic column. Compounds 1-7 were obtained in 12.2g with a yield of 51%.
(7) Preparation of metallocene compounds
Under the protection of nitrogen, taking 4.79g (0.01mol) of the compound 1-7, dissolving into 50mL of dried tetrahydrofuran, and cooling to-78 ℃; then, 4mL (2.5M, n-hexane solution) of n-butyllithium was added dropwise, and after stirring for 30 minutes, 1.17g (0.005mol) of zirconium tetrachloride was added; slowly warmed to room temperature for 24 hours. And (3) post-treatment: the precipitate was filtered, washed with 50mL of toluene and the filtrates combined. Part of the solvent was distilled off under reduced pressure, n-hexane was added dropwise until precipitation occurred, and then a very small amount of toluene was added to dissolve the precipitate. The solution was crystallized at-20 c, filtered to give orange red crystals, and dried to obtain 3.35g of compound 1-8 with a yield of 60%. The structure was confirmed to be error-free by single crystal diffraction.
Figure BDA0003392355170000261
Preparation examples 2 to 5: synthesis of Compounds having the structures represented by the formulae (3) to (6)
A compound having a structure represented by formula (3): in the compound of the structure represented by the formula (1), R1-R4Is methyl, R5-R8Is methyl, M is zirconium;
a compound having the structure represented by formula (4): in the compound of the structure represented by the formula (1), R1、R3Is isopropyl, R2、R4Is hydrogen, R5-R8Is methyl, M is zirconium;
formula (5) isA compound of the structure: in the compound of the structure represented by the formula (1), R1-R4Is methyl, R5-R8Is hydrogen, M is zirconium;
a compound having a structure represented by formula (6): in the compound of the structure represented by the formula (1), R1、R3Is methyl, R2、R4Is hydrogen, R5-R8Is methyl, M is zirconium;
preparation examples 2 to 5 the procedure of preparation example 1 was followed, except that R in the target product obtained was used in each raw material1-R8Corresponding raw materials respectively obtain a compound with a structure shown in a formula (3) and a compound with a structure shown in a formula (6).
Example 1
In a 500mL polymerization apparatus sufficiently purged with nitrogen, 100mL of dry hexane was charged, the temperature in the polymerization apparatus was raised to 70 ℃ and then 2mL of a toluene solution containing 2. mu. mol of the compound represented by formula (2) as a metallocene catalyst and 2mmol of methylaluminoxane as a cocatalyst was added to the polymerization apparatus (also, the molar ratio of the cocatalyst to the compound represented by formula (2) was 1000: 1 in terms of the number of moles of the Al element in the cocatalyst and M in the compound represented by formula (2)), and hydrogen and the propylene were added in a molar ratio of 0.002: 1, then adding propylene to the pressure of 0.1Mpa, and continuously supplementing the mixed gas of the propylene and the hydrogen. Polymerization was carried out at an internal temperature of 70 ℃ for 2 hours. After pressure relief, methanol was added to the solution in the apparatus to obtain a precipitated polymer, which was vacuum dried at 50 ℃ for 8 hours to obtain 8g of polypropylene having a catalyst activity of 4X 106gPP/molZr. The physical properties of the polypropylene thus obtained are shown in Table 2.
Examples 2 to 5
Polypropylene was prepared in the same manner as in example 1, except that the kind of the metallocene catalyst, the kind of the cocatalyst, the amounts of the metallocene catalyst and the cocatalyst, the molar ratio of hydrogen to propylene, and the polymerization temperature and time were the values shown in table 1.
Example 6
50mL of dry hexane was charged into a 500mL polymerization apparatus purged with nitrogen sufficiently, and then 150mL of Fischer-Tropsch synthesized alpha-olefin of C8 to C12 was charged while the internal temperature of the polymerization apparatus was raised to 60 ℃. Then, a toluene solution containing 2. mu. mol of the compound represented by the formula (2) as a metallocene catalyst and 2mmol of methylaluminoxane as a cocatalyst was added to the polymerization vessel (also, the molar ratio of the cocatalyst to the compound represented by the formula (2) was 1000: 1 in terms of the number of moles of the Al element in the cocatalyst and M in the compound represented by the formula (2)), polymerization was carried out at an internal temperature of 40 ℃ and 1 hour of polymerization was followed by addition of an acid alcohol to terminate the polymerization. After pressure relief, methanol was added to the solution in the apparatus to obtain a precipitated polymer, which was vacuum dried at 50 ℃ for 6 hours. 16.74g of a copolymerized α -olefin was obtained, and the physical properties of the obtained copolymerized α -olefin are shown in Table 2.
Example 7
Preparation of the support
Dissolving 1g of chlorinated polypropylene (the content of chlorine element is 70 mass percent, the Cl/C molar ratio is 0.92: 1, the CPP-70 model purchased from Shandong Weifang Gaofu chemical Co., Ltd.) in 100ml of tetrahydrofuran as a good solvent, fully stirring and heating to 60 ℃, condensing and refluxing nitrogen serving as protective gas, and fully dissolving for 2 hours; putting 1000ml of acetone into a beaker, quickly stirring, and quickly injecting a tetrahydrofuran solution dissolved with chlorinated polypropylene into the quickly stirred acetone serving as a poor solvent by using a disposable injection needle tube; when all the solutions are injected, preparing chlorinated polypropylene microspheres; taking 100ml of the solution containing the chlorinated polypropylene microspheres, adding 100ml of distilled water, and distilling under reduced pressure to remove tetrahydrofuran and acetone; pouring the remaining solution into a 50ml high-pressure reaction kettle, heating to 350 ℃ at the temperature of 10 ℃/min, reacting for 8 hours to obtain liquid containing black precipitates, removing supernatant, cleaning with ethanol solution, and drying to obtain black powder; and (3) putting the black powder into a quartz tube of a tube furnace, and filling nitrogen into the system to ensure that the quartz tube does not contain active gases such as oxygen and the like. Heating the black powder at the speed of 10 ℃/min, raising the temperature to the final carbonization temperature of 800 ℃, and keeping the temperature for 3 h. And slowly cooling to 30 ℃ under nitrogen to obtain the micron carbon spheres. And (3) mixing the obtained micron carbon spheres with tetramethoxysiloxane according to the mass ratio of 1: 2 at the temperature of 100 ℃ for 4h, and roasting the mixed adsorption product at the temperature of 400 ℃ for 6h to obtain the catalyst carrier.
Preparation of supported metallocene catalysts
Dispersing 1.0g of carrier in 5mL of toluene, heating to 60 deg.C while stirring, adding 5mL of Methyl Aluminoxane (MAO) in toluene (1.4 mol/L) and soaking for 7h, washing with 10mL of toluene 5 times to remove excess MAO, and obtaining SiO2MAO was suspended in 10ml of toluene. Then, 30mg of the compound represented by the formula (2) was added to SiO2MAO in toluene. After mixing, the reaction was carried out at 50 ℃ for 7 hours, and the metallocene catalyst not supported on the carrier was removed by washing 5 times with 10ml of toluene. Vacuum drying for 5h to obtain the supported metallocene catalyst. The molar ratio of the cocatalyst to the metallocene compound in the obtained supported metallocene catalyst calculated by Al element and Zr element is 24: 1, the mass ratio of the support to the metallocene compound is 1: 0.05.
100mg of metallocene catalyst and 1.2 kg of propylene are added into a 5L steel kettle, stirred and reacted for 1 hour at 70 ℃, the reaction is stopped, and the material is discharged and dried in a vacuum drying oven for 8 hours to obtain the polypropylene. The resulting polypropylene was weighed and the catalyst activity calculated from the weight of catalyst added was 25.7 KgPP/gCat.
Comparative example 1
Polypropylene was prepared according to the procedure of example 1, except that the metallocene catalyst used was dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride (available from ImmunoKa, the structure of which is shown below and is also referred to below as formula D). The physical properties of the polypropylene thus obtained are shown in Table 2.
Figure BDA0003392355170000291
TABLE 1
Figure BDA0003392355170000301
In the table, the modified methylaluminoxane was purchased from Innochem (Innochem) as a 7% by weight heptane solution.
TABLE 2
Figure BDA0003392355170000302
As can be seen from the results of Table 2, the examples using the production process of the present invention are high in catalytic activity.
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 metallocene compound characterized by being represented by the following chemical formula (1):
Figure FDA0003392355160000011
in the formula (1), R1-R8Each is a hydrogen atom or a C1-C12 alkyl group, and M is one or more of a transition metal element from groups III, IV, V, and VI of the periodic Table of the elements or a lanthanide.
2. The metallocene compound according to claim 1, wherein in formula (1), R is1-R8Each is a hydrogen atom or an alkyl group of C1 to C4;
preferably, in formula (1), M is one or more of zirconium, titanium, chromium and hafnium.
3. The metallocene compound according to claim 1, wherein in formula (1), R is1-R8Each is one or more of a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, and an isobutyl group.
4. The metallocene compound according to claim 1, wherein the compound represented by formula (1) is selected from one or more of the following compounds,
compound A-1: r1-R4Is H, R5-R8Is methyl, M is zirconium;
compound A-2: r1-R4Is H, R5-R8Is methyl, M is titanium;
compound A-3: r1-R4Is H, R5-R8Is methyl, M is chromium;
compound A-4: r1-R4Is H, R5-R8Is methyl, M is hafnium;
compound B-1: r2-R4Is H, R1And R5-R8Is methyl, M is zirconium;
compound B-2: r2-R4Is H, R1And R5-R8Is methyl, M is titanium;
compound B-3: r2-R4Is H, R1And R5-R8Is methyl, M is chromium;
compound B-4: r2-R4Is H, R1And R5-R8Is methyl, M is hafnium;
compound C-1: r1-R8Is methyl, M is zirconium;
compound C-2: r1-R8Is methyl, M is titanium;
compound C-3: r1-R8Is methyl, M is chromium;
compound C-4: r1-R8Is methyl, M is hafnium;
compound D-1: r1-R4Is isopropyl, R5-R8Is methyl, M is zirconium;
compound D-2: r1-R4Is isopropyl, R5-R8Is methyl, M is titanium;
compound D-3: r1-R4Is isopropyl, R5-R8Is a methyl group, and the compound is,m is chromium;
compound D-4: r1-R4Is isopropyl, R5-R8Is methyl, M is hafnium;
compound E-1: r1-R4Is ethyl, R5-R8Is methyl, M is zirconium;
compound E-2: r1-R4Is ethyl, R5-R8Is methyl, M is titanium;
compound E-3: r1-R4Is ethyl, R5-R8Is methyl, M is chromium;
compound E-4: r1-R4Is ethyl, R5-R8Is methyl, M is hafnium;
compound F-1: r1-R4Is methyl, R5-R8Is H, M is zirconium;
compound F-2: r1-R4Is methyl, R5-R8Is H, M is titanium;
compound F-3: r1-R4Is methyl, R5-R8Is H, M is chromium;
compound F-4: r1-R4Is methyl, R5-R8Is H, M is hafnium;
compound G-1: r1、R3Is H, R2、R4And R5-R8Is methyl, M is zirconium;
compound G-2: r1、R3Is H, R2、R4And R5-R8Is methyl, M is titanium;
compound G-3: r1、R3Is H, R2, R4And R5-R8Is methyl, M is chromium;
compound G-4: r1、R3Is H, R2、R4And R5-R8Is methyl, M is hafnium;
compound H-1: r1-R8Is H, M is zirconium;
compound H-2: r1-R8Is H, M is titanium;
compound H-3: r1-R8Is H, M is chromium;
compound H-4: r1-R8Is H, M is hafnium;
compound I-1: r1、R3Is isopropyl, R2、R4Is hydrogen, R5-R8Is methyl, M is zirconium;
compound I-2: r1、R3Is isopropyl, R2、R4Is hydrogen, R5-R8Is methyl, M is titanium;
compound I-3: r1、R3Is isopropyl, R2、R4Is hydrogen, R5-R8Is methyl, M is chromium;
compound I-4: r1、R3Is isopropyl, R2、R4Is hydrogen, R5-R8Is methyl, M is hafnium;
compound J-1: r1、R3Is methyl, R2、R4Is hydrogen, R5-R8Is methyl, M is zirconium;
compound J-2: r1、R3Is methyl, R2、R4Is hydrogen, R5-R8Is methyl, M is titanium;
compound J-3: r1、R3Is methyl, R2、R4Is hydrogen, R5-R8Is methyl, M is chromium;
compound J-4: r1、R3Is methyl, R2、R4Is hydrogen, R5-R8Is methyl and M is hafnium.
5. A process for preparing a metallocene compound according to any of claims 1 to 4, characterized in that it comprises the following steps:
1) formylating compound 1 with an organolithium reagent and/or a TurboGrignard reagent and an amide in the presence of a first organic solvent to obtain compound 2;
2) subjecting compound 2 to wittig reaction with wittig reagent and/or wittig-horner reagent in the presence of a second organic solvent and a base to obtain compound 3;
3) in the presence of a third organic solvent and a hydrogenation catalyst, carrying out hydrogenation reaction on the compound 3 and hydrogen, and then carrying out hydrolysis reaction to obtain a compound 4;
4) carrying out Friedel-crafts acylation reaction on the compound 4 in the presence of polyphosphoric acid to obtain a compound 5;
5) in the presence of a fifth organic solvent, carrying out carbonyl reduction reaction and elimination reaction on the compound 5 to obtain a compound 6;
6) in the presence of a seventh organic solvent, reacting the compound 6 with a deprotonating reagent, then carrying out nucleophilic addition reaction with halogenated hydrocarbon, and then carrying out silicon bridging reaction on the obtained nucleophilic addition product and dihalo-dimethylsilane to obtain a compound 7;
7) reacting the compound 7 with a deprotonating agent in the presence of an eighth organic solvent, and then with a salt of a metal M to give a metallocene compound 8,
wherein compounds 1-8 are each a compound having the structure:
Figure FDA0003392355160000041
in the compounds 1 to 8, R1、R2、R5And R6Which may be the same or different, are each a hydrogen atom or an alkyl group of C1-C12, and M is one or more of a transition metal element of groups III, IV, V and VI of the periodic Table of the elements or a lanthanide.
6. A catalyst composition comprising the metallocene compound according to any one of claims 1 to 4 and a cocatalyst.
7. The catalyst composition of claim 6, wherein the cocatalyst is one or more of methylaluminoxane, modified methylaluminoxane, and triisobutylaluminum.
8. A supported metallocene catalyst comprising a carrier and the metallocene compound according to any one of claims 1 to 4 supported on the carrier.
9. The supported metallocene catalyst of claim 8, wherein the support is SiO2、Al2O3One or more of a carbon material and a polymer carrier;
preferably, the supported metallocene catalyst further comprises a cocatalyst supported on the carrier;
preferably, the cocatalyst is one or more of methylaluminoxane, modified methylaluminoxane and triisobutylaluminum;
preferably, the carrier is a micron carbon sphere carrier with the surface covered with silicon dioxide.
10. Use of a metallocene compound as defined in any one of claims 1 to 4, a catalyst composition as defined in claim 6 or 7 or a supported metallocene catalyst as defined in claim 8 or 9 in the polymerisation of olefins.
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