CN114249775B - Metallocene compound and preparation method thereof, catalyst composition, supported metallocene catalyst and application thereof - Google Patents

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

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CN114249775B
CN114249775B CN202111468040.5A CN202111468040A CN114249775B CN 114249775 B CN114249775 B CN 114249775B CN 202111468040 A CN202111468040 A CN 202111468040A CN 114249775 B CN114249775 B CN 114249775B
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compound
methyl
reaction
metallocene
catalyst
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CN114249775A (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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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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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  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
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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 in the formula (1), R 1-R8 is a hydrogen atom or a C1-C12 alkyl group, and M is one or more of transition metal elements of groups III, IV, V and VI of the periodic Table of elements or lanthanoids. The metallocene compound has excellent catalytic activity in catalyzing olefin homo-polymerization and copolymerization.

Description

Metallocene compound and preparation method thereof, catalyst composition, supported metallocene catalyst and application thereof
Technical Field
The invention relates to the field of polymers, in particular to a metallocene compound and a preparation method thereof, a catalyst composition, a supported metallocene catalyst and application thereof.
Background
Metallocene catalysts refer to catalytic systems formed by complexation of a transition metal element with at least one cyclopentadiene or cyclopentadiene derivative as ligand. The polypropylene prepared by the metallocene catalyst has narrow molecular weight distribution, and is easy to adjust the structure and the performance, and is currently used for synthesizing syndiotactic polypropylene which is difficult to synthesize by Ziegler-Natta catalysts and has specific functions. The metallocene catalyst technology injects great vitality into the development of the polyolefin industry, and the properties of the polymer can be accurately regulated and controlled by using the metallocene catalyst, so that the polymer with uniform composition and molecular structure is prepared, and the characteristics show that the metallocene catalyst is more superior than the traditional catalyst. In addition, the activity of metallocene catalysts during polymerization is much higher than 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 to polypropylene synthesized by conventional Ziegler-Natta catalysts, mPP has better insulation and radiation resistance, and it is more compatible with other resins.
Metallocene catalysts have been developed that include general metallocene structures, bridged metallocene structures, and Constrained Geometry (CGC) metallocene structures; transition metals include iron, cobalt, zirconium, titanium, hafnium, and the like; the ligand includes cyclopentadiene, anchor group, indenyl group, fluorenyl group and the like. The mPP products include homo-polypropylene (highly isotactic, atactic and syndiotactic), atactic co-polypropylene and block polypropylene. There are thousands of metallocene catalysts, and a slight change in ligand structure can cause a great change in catalytic performance of the catalyst, so that development of new metallocene catalysts is still required to meet the demands in polyolefin production.
Disclosure of Invention
The object of the present invention is to provide a novel metallocene compound, a process for producing the same, a catalyst composition comprising the same, and a supported metallocene catalyst produced using the same. The metallocene compound has excellent catalytic activity in catalyzing olefin homo-polymerization and copolymerization.
In order to achieve the above object, the first aspect of the present invention provides a metallocene compound represented by the following chemical formula (1):
In the formula (1), R 1-R8 is a hydrogen atom or a C1-C12 alkyl group, and M is one or more of transition metal elements of groups III, IV, V and VI of the periodic table or lanthanoids.
Preferably, in formula (1), R 1-R8 is each 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 formula (1), each R 1-R8 is one or more of a hydrogen atom, methyl, ethyl, isopropyl and isobutyl.
Preferably, the compound represented by the formula (1) is selected from one or more of the following compounds,
Compound a-1: r 1-R4 is H, R 5-R8 is methyl, M is zirconium;
compound a-2: r 1-R4 is H, R 5-R8 is methyl, M is titanium;
Compound a-3: r 1-R4 is H, R 5-R8 is methyl, M is chromium;
compound a-4: r 1-R4 is H, R 5-R8 is methyl, M is hafnium;
Compound B-1: r 2-R4 is H, R 1 and R 5-R8 are methyl, M is zirconium;
Compound B-2: r 2-R4 is H, R 1 and R 5-R8 are methyl, M is titanium;
Compound B-3: r 2-R4 is H, R 1 and R 5-R8 are methyl, M is chromium;
Compound B-4: r 2-R4 is H, R 1 and R 5-R8 are methyl, M is hafnium;
Compound C-1: r 1-R8 is methyl, M is zirconium;
Compound C-2: r 1-R8 is methyl, M is titanium;
Compound C-3: r 1-R8 is methyl, M is chromium;
Compound C-4: r 1-R8 is methyl, M is hafnium;
Compound D-1: r 1-R4 is isopropyl, R 5-R8 is methyl, and M is zirconium;
Compound D-2: r 1-R4 is isopropyl, R 5-R8 is methyl, M is titanium;
Compound D-3: r 1-R4 is isopropyl, R 5-R8 is methyl, and M is chromium;
compound D-4: r 1-R4 is isopropyl, R 5-R8 is methyl, and M is hafnium;
Compound E-1: r 1-R4 is ethyl, R 5-R8 is methyl, M is zirconium;
compound E-2: r 1-R4 is ethyl, R 5-R8 is methyl, M is titanium;
Compound E-3: r 1-R4 is ethyl, R 5-R8 is methyl, and M is chromium;
compound E-4: r 1-R4 is ethyl, R 5-R8 is methyl, and M is hafnium;
Compound F-1: r 1-R4 is methyl, R 5-R8 is H, M is zirconium;
Compound F-2: r 1-R4 is methyl, R 5-R8 is H, M is titanium;
Compound F-3: r 1-R4 is methyl, R 5-R8 is H, M is chromium;
compound F-4: r 1-R4 is methyl, R 5-R8 is H, and M is hafnium;
Compound G-1: r 1R3 is H, R 2R4 and R 5-R8 are methyl, M is zirconium;
Compound G-2: r 1R3 is H, R 2R4 and R 5-R8 are methyl, M is titanium;
Compound G-3: r 1R3 is H, R2, R 4 and R 5-R8 are methyl, M is chromium;
Compound G-4: r 1R3 is H, R 2R4 and R 5-R8 are methyl, M is hafnium;
compound H-1: r 1-R8 is H, M is zirconium;
Compound H-2: r 1-R8 is H, M is titanium;
Compound H-3: r 1-R8 is H, M is chromium;
Compound H-4: r 1-R8 is H, M is hafnium;
Compound I-1: r 1R3 is isopropyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is zirconium;
compound I-2: r 1R3 is isopropyl, R 2R4 is hydrogen, R 5-R8 is methyl, M is titanium;
Compound I-3: r 1R3 is isopropyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is chromium;
Compound I-4: r 1R3 is isopropyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is hafnium;
Compound J-1: r 1R3 is methyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is zirconium;
Compound J-2: r 1R3 is methyl, R 2R4 is hydrogen, R 5-R8 is methyl, M is titanium;
Compound J-3: r 1R3 is methyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is chromium;
Compound J-4: r 1R3 is methyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is hafnium.
According to a second method of the present invention there is provided a process for the preparation of a metallocene compound according to the present invention, wherein the process comprises the steps of:
1) Formylating the compound 1 with an organolithium reagent and/or TurboGrignard reagent and an amide in the presence of a first organic solvent to obtain a compound 2;
2) Subjecting compound 2 to wittig reaction with wittig reagent and/or wittig-hopanax 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) Performing Friedel-crafts acylation reaction on the compound 4 in the presence of polyphosphoric acid to obtain a compound 5;
5) Subjecting compound 5 to carbonyl reduction and elimination in the presence of a fifth organic solvent to obtain compound 6;
6) In the presence of a seventh organic solvent, enabling the compound 6 to react with a deprotonating reagent and then react with halogenated hydrocarbon in a nucleophilic addition reaction, and then enabling the obtained nucleophilic addition product to react with dihalogenated dimethyl silane in a silicon bridging reaction to obtain a compound 7;
7) Reacting compound 7 with a deprotonating agent in the presence of an eighth organic solvent, and then with a salt of metal M to give metallocene compound 8,
Wherein, the compounds 1-8 are respectively compounds with the following structures:
In compounds 1-8, R 1R2R5 and R 6, which may be the same or different, are each a hydrogen atom or a C1-C12 alkyl group, and M is one or more of transition metal elements of groups III, IV, V and VI of the periodic Table of the elements or lanthanides.
According to a third aspect of the present invention there is provided a catalyst composition comprising a metallocene compound according to 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 a metallocene compound according to the first aspect of the present invention supported on said support.
Preferably, the carrier is one or more of SiO 2Al2O3, carbon material and polymer carrier.
Preferably, the supported metallocene catalyst further comprises a cocatalyst supported on the support.
Preferably, the cocatalyst is one or more of methylaluminoxane, modified methylaluminoxane and triisobutylaluminum.
Preferably, the carrier is a micron carbon sphere carrier with a 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.
Through the technical scheme, the invention provides a novel metallocene compound, a catalyst composition containing the metallocene compound and a supported metallocene catalyst obtained by using the metallocene compound, and the supported metallocene catalyst using the metallocene compound has excellent catalytic activity in olefin homo-polymerization and copolymerization catalysis.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a metallocene compound represented by the following chemical formula (1):
In formula (1), R 1-R8, which may be the same or different, are each a hydrogen atom or a C1-C12 alkyl group, and M is one or more of transition metal elements of groups III, IV, V and VI of the periodic Table of the elements or lanthanides.
The C1-C12 alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group, and examples of the C1-C12 alkyl group include: methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and the like.
According to the present invention, as R 1-R8, the smaller the number of atoms, the smaller the steric hindrance, the more active the compound represented by formula (1), preferably, in formula (1), R 1-R8 is each a hydrogen atom or a C1-C4 alkyl group; more preferably, in formula (1), each R 1-R8 is one or more of a hydrogen atom, methyl, ethyl, isopropyl, and isobutyl.
In the present invention, examples of the M include: scandium, titanium, vanadium, chromium, yttrium, zirconium, niobium, molybdenum, lanthanum, cerium, hafnium, tantalum, tungsten, and the like.
According to the present invention, when M is a specific element, the compound represented by formula (1) has higher catalytic activity, and preferably, in formula (1), M is one or more of zirconium, titanium, chromium and hafnium.
In a preferred embodiment of the present invention, the compound represented by the formula (1) is selected from one or more of the following compounds,
Compound a-1: r 1-R4 is H, R 5-R8 is methyl, M is zirconium;
compound a-2: r 1-R4 is H, R 5-R8 is methyl, M is titanium;
Compound a-3: r 1-R4 is H, R 5-R8 is methyl, M is chromium;
compound a-4: r 1-R4 is H, R 5-R8 is methyl, M is hafnium;
Compound B-1: r 2-R4 is H, R 1 and R 5-R8 are methyl, M is zirconium;
Compound B-2: r 2-R4 is H, R 1 and R 5-R8 are methyl, M is titanium;
Compound B-3: r 2-R4 is H, R 1 and R 5-R8 are methyl, M is chromium;
Compound B-4: r 2-R4 is H, R 1 and R 5-R8 are methyl, M is hafnium;
Compound C-1: r 1-R8 is methyl, M is zirconium;
Compound C-2: r 1-R8 is methyl, M is titanium;
Compound C-3: r 1-R8 is methyl, M is chromium;
Compound C-4: r 1-R8 is methyl, M is hafnium;
Compound D-1: r 1-R4 is isopropyl, R 5-R8 is methyl, and M is zirconium;
Compound D-2: r 1-R4 is isopropyl, R 5-R8 is methyl, M is titanium;
Compound D-3: r 1-R4 is isopropyl, R 5-R8 is methyl, and M is chromium;
compound D-4: r 1-R4 is isopropyl, R 5-R8 is methyl, and M is hafnium;
Compound E-1: r 1-R4 is ethyl, R 5-R8 is methyl, M is zirconium;
compound E-2: r 1-R4 is ethyl, R 5-R8 is methyl, M is titanium;
Compound E-3: r 1-R4 is ethyl, R 5-R8 is methyl, and M is chromium;
compound E-4: r 1-R4 is ethyl, R 5-R8 is methyl, and M is hafnium;
Compound F-1: r 1-R4 is methyl, R 5-R8 is H, M is zirconium;
Compound F-2: r 1-R4 is methyl, R 5-R8 is H, M is titanium;
Compound F-3: r 1-R4 is methyl, R 5-R8 is H, M is chromium;
compound F-4: r 1-R4 is methyl, R 5-R8 is H, and M is hafnium;
Compound G-1: r 1R3 is H, R 2R4 and R 5-R8 are methyl, M is zirconium;
Compound G-2: r 1R3 is H, R 2R4 and R 5-R8 are methyl, M is titanium;
Compound G-3: r 1R3 is H, R2, R 4 and R 5-R8 are methyl, M is chromium;
Compound G-4: r 1R3 is H, R 2R4 and R 5-R8 are methyl, M is hafnium;
compound H-1: r 1-R8 is H, M is zirconium;
Compound H-2: r 1-R8 is H, M is titanium;
Compound H-3: r 1-R8 is H, M is chromium;
Compound H-4: r 1-R8 is H, M is hafnium;
Compound I-1: r 1R3 is isopropyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is zirconium;
compound I-2: r 1R3 is isopropyl, R 2R4 is hydrogen, R 5-R8 is methyl, M is titanium;
Compound I-3: r 1R3 is isopropyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is chromium;
Compound I-4: r 1R3 is isopropyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is hafnium;
Compound J-1: r 1R3 is methyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is zirconium;
Compound J-2: r 1R3 is methyl, R 2R4 is hydrogen, R 5-R8 is methyl, M is titanium;
Compound J-3: r 1R3 is methyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is chromium;
Compound J-4: r 1R3 is methyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is hafnium.
According to a second aspect of the present invention there is provided a process for the preparation of a metallocene compound, the process comprising the steps of:
1) Formylating the compound 1 with an organolithium reagent and/or Turbogrignard reagent and an amide in the presence of a first organic solvent to obtain a compound 2;
2) Subjecting compound 2 to wittig reaction with wittig reagent and/or wittig-hopanax 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) Performing Friedel-crafts acylation reaction on the compound 4 in the presence of polyphosphoric acid to obtain a compound 5;
5) Subjecting compound 5 to carbonyl reduction and elimination in the presence of a fifth organic solvent to obtain compound 6;
6) In the presence of a seventh organic solvent, enabling the compound 6 to react with a deprotonating reagent and then react with halogenated hydrocarbon in a nucleophilic addition reaction, and then enabling the obtained nucleophilic addition product to react with dihalogenated dimethyl silane in a silicon bridging reaction to obtain a compound 7;
7) Reacting compound 7 with a deprotonating agent in the presence of an eighth organic solvent, and then with a salt of metal M to give metallocene compound 8,
Wherein, the compounds 1-8 are respectively compounds with the following structures:
In compounds 1-8, R 1R2R5 and R 6, which may be the same or different, are each a hydrogen atom or a C1-C12 alkyl group, and M is one or more of transition metal elements of groups III, IV, V and VI of the periodic Table of the elements or lanthanides.
In the present invention, two monomers connected by a silicon bridge structure exist in the structures of the compounds 7 and 8, the above compounds 1 to 6 are used for representing the monomers with the substituent R 1R2R5R6, and R 1R2R5R6 in the compounds 1 to 6 and the following synthetic route (1) is replaced by R 3R4R8R7 respectively to prepare another monomer.
Examples of the R 1-R8 include: methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and the like.
Preferably, in formula (1), R 1-R8 is each a hydrogen atom or a C1-C4 alkyl group; more preferably, in formula (1), each R 1-R8 is one or more of a hydrogen atom, methyl, ethyl, isopropyl, and isobutyl.
Examples of the M include: 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 are 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 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 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 is not particularly limited as long as the reaction proceeds smoothly, and may be a conventional amount 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 TurboGringnard reagents are used, the molar ratio of compound 1 to TurboGringnard reagent may be 1:1.0 to 1.5, preferably 1:1.1-1.3.
The formylation reaction may be a variety of conditions commonly used in the art, for example, the reaction conditions of the formylation reaction may include: the reaction temperature is between-78 and 0 and the reaction time is between 8 and 12 hours.
After the reaction, the reaction product may be purified by various purification methods commonly used in the art, for example, a dilute hydrochloric acid quenching reaction may be employed, extraction may be performed using an organic solvent (for example, ethyl acetate), and the crude product may be purified by separation by a chromatography column or recrystallization after the solvent is removed.
In a specific embodiment of the present invention, formylation is carried out using iodo-N-phenylimidazole as a starting material under the action of an organolithium reagent and N, N-dimethylformamide to give compound 2.
2) Wittig reaction
In the present invention, compound 2 is subjected to wittig reaction with a wittig reagent or wittig-hall 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 is not particularly limited as long as the reaction proceeds smoothly, and may be a conventional amount in the art.
As the base, for example, one or more of NaH, alkyl lithium, 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 reagent may be: ph 3PCR6 COOEt.
The wittig-hall reagent may be (EtO) 2POCHR6CO2 Et and/or (EtO) 2POCHR6CO2 Me, preferably (EtO) 2POCHR6CO2 Et.
R 6 in the above chemical formula can be correspondingly replaced by R 7 to prepare a compound with a substituent of R 7.
The molar ratio of compound 2 to wittig or wittig-hall 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 5-20h; preferably, the reaction conditions of the wittig reaction include: the reaction temperature is 0-40 and the reaction time is 8-15h.
After the reaction, 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) may be used, and purification of the crude product by separation by a column chromatography or recrystallization after removal of the solvent.
3) Hydrogenation and hydrolysis reactions
In the present invention, compound 3 is hydrogenated with hydrogen in the presence of a third organic solvent and a hydrogenation catalyst, and then subjected to hydrolysis to obtain compound 4.
Specifically, the compound 3 was subjected to hydrogenation to obtain the following compound 9, and the compound 9 was subjected to hydrolysis to obtain the compound 4.
The hydrogenation catalyst may be a palladium-carbon catalyst.
The amount of the hydrogenation catalyst may be 0.5 to 1.5% by mass based on the total mass of the hydrogenation reaction system.
The third organic solvent can be an alcohol solvent, and can be one or more of ethanol, methanol and isopropanol; ethanol is preferred. The amount of the solvent is not particularly limited as long as the reaction proceeds smoothly, and may be a conventional amount in the art.
The hydrogenation conditions include: the reaction temperature is 5-40 and the reaction time is 10-48h; preferably, the hydrogenation conditions include: the reaction temperature is 5-30 and the reaction time is 20-30h.
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 the solvent may be removed, and the resulting 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 a conventional amount used in the art for hydrolysis.
The fourth organic solvent may be an alcohol solvent, and the alcohol solvent may be one or more of methanol, ethanol, and isopropanol; preferably methanol.
The conditions of the hydrolysis reaction are not particularly limited as long as the hydrolysis reaction proceeds sufficiently, and preferably the hydrolysis reaction is performed under reflux, and the reaction time may be, for example, 10 to 50 hours.
The concentration of the acid as the hydrolysis reaction may be 15 to 40 mass%, preferably 25 to 37 mass%.
The post-treatment of the hydrolysis reaction may be performed by a method conventional in the art, and may be, for example: after the solvent is removed, water is added for washing, then an organic solvent (for example, ethyl acetate can be used) is used for extraction, and after the solvent is removed, the crude product is separated by a chromatographic column or is recrystallized, etc. for purification.
4) Friedel-crafts acylation reaction
In the present invention, compound 4 is subjected to friedel-crafts acylation in the presence of polyphosphoric acid to give compound 5.
The amount of the polyphosphoric acid to be used may be in excess as long as the reaction proceeds sufficiently, and for example, may be 1 to 10 parts by weight, preferably 1 to 5 parts by weight, more preferably 1.5 to 2 parts by weight, relative to 1 part by weight of the compound 4.
The reaction conditions of the friedel-crafts acylation reaction include: the reaction temperature is 50-90 and the reaction time is 3-20h; preferably, the conditions of the friedel-crafts acylation reaction include: the reaction temperature is 70-90 and the reaction time is 5-10h.
The post-treatment of the friedel-crafts acylation reaction may be performed by a method conventional in the art, for example, may be: the reaction mixture is diluted with ice water, extracted with an organic solvent (for example, ethyl acetate), and the solvent is removed to purify the crude product by separation with a column chromatography or recrystallization.
5) Carbonyl reduction and elimination reactions
In the present invention, the compound 5 is subjected to carbonyl reduction and elimination in the presence of a fifth organic solvent to obtain a compound 6.
Specifically, the carbonyl reduction reaction gives the following compound 10, and the elimination reaction of the compound 10 gives the compound 6.
The fifth organic solvent may be one or more of tetrahydrofuran, toluene, n-hexane and diethyl ether, and preferably diethyl ether. The amount of the solvent is not particularly limited as long as the reaction proceeds smoothly, and may be a conventional amount in the art.
As the reducing agent for the carbonyl reduction reaction, a reducing agent commonly used in the art for reducing carbonyl groups can be used, and LiAlH 4, for example, can be used.
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 10-50h; preferably, the conditions of the carbonyl reduction reaction include: the reaction temperature is 10-30 and the reaction time is 20-30h.
The post-treatment of the carbonyl reduction reaction may be performed by a method conventional in the art, and may be, for example: after filtering to remove solid substances, the filter cake is washed with an organic solvent (for example, diethyl ether), and the washing solution and the filtered solution 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 toluene may be used as the sixth organic solvent. The amount of the solvent is not particularly limited as long as the reaction proceeds smoothly, and may be a conventional amount in the art.
The catalyst for the elimination reaction may be one or more of TsOH, H 2SO4H3PO4 and Al 2O3, preferably TsOH.
The molar ratio of the catalyst of the elimination reaction to compound 5 may be 0.05 to 0.3:1, preferably 0.08-0.15:1.
The reaction conditions of the elimination reaction include: the reaction temperature is 80-130 and the reaction time is 10-48h; preferably, the reaction conditions of the elimination reaction include: the reaction temperature is 105-125 and the reaction time is 20-30h.
The post-treatment of the elimination reaction may be performed by a method conventional in the art, and may be, for example: after the solvent is removed, water is added, and then extraction is performed using an organic solvent (for example, ethyl acetate may be used), and after the solvent is removed, the crude product is purified by separation by a column, recrystallization, or the like.
6) Deprotonation addition reactions and silane bridging reactions.
In the invention, in the presence of a seventh organic solvent, reacting a 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 reaction product and dihalogenated dimethyl silane to obtain a compound 7;
Specifically, the compound 6 reacts with a deprotonating agent and then carries out nucleophilic addition reaction with halogenated hydrocarbon to obtain a compound 11, and the compound 11 and dihalodimethylsilane carry out silicon bridging reaction to obtain the following compound 7.
The deprotonating agent may be one or more of n-butyllithium, isobutyllithium and tert-butyllithium, preferably n-butyllithium.
The halogenated hydrocarbon is a compound represented by the following formula (2):
R 6 X is represented by 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 1-1.3:1.
The seventh organic solvent may be one or more of tetrahydrofuran, toluene, n-hexane and diethyl ether, preferably tetrahydrofuran. The amount of the solvent is not particularly limited as long as the reaction proceeds smoothly, and may be a conventional amount in the art.
The reaction conditions of the deprotonation reaction include: the reaction temperature is-78 to 0 , the reaction time is 5 to 50min, and the preferable reaction time is 25 to 35min.
The molar ratio of halogenated hydrocarbon to compound 6 may be from 1 to 1.5:1, preferably 1-1.3:1.
The reaction conditions for nucleophilic addition reaction with halogenated hydrocarbon include: the reaction temperature is 5-40 and the reaction time is 0.5-5h; preferably, the reaction conditions for nucleophilic addition reaction with a halogenated hydrocarbon include: the reaction temperature is 10-30 and the reaction time is 1-2h.
In addition, the above-mentioned deprotonation and nucleophilic addition reaction may not be performed to obtain a compound in which R 6 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 dihalodimethylsilane comprises: the deprotonating agent reacts with the compound 11 in the presence of a solvent, and then dihalodimethylsilane is dropped into the reaction mixture to carry out silicon bridging reaction. The deprotonating agent, solvent and reaction conditions may be the same as those used when the compound 6 reacts with the deprotonating agent.
The dihalodimethylsilane may be dichlorodimethylsilane and/or dibromodimethylsilane.
Since the reaction product is used for the silicon bridging reaction by simple treatments such as extraction after the reaction of the compound 6 with the deprotonating agent and then with the halogenated hydrocarbon, the amount of the dihalodimethylsilane may be selected according to 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 1-1.3:1.
The reaction conditions of the silicon bridging reaction include: the reaction temperature is 5-40 and the reaction time is 0.5-5h; preferably, the reaction conditions of the silicon bridging reaction include: the reaction temperature is 10-30 and the reaction time is 1-2h.
The post-treatment of the silicon bridging reaction may be performed by a method conventional in the art, for example, may be: the reaction is quenched with water, extracted with an organic solvent (preferably ethyl acetate), and the solvent is removed, and the crude product is purified by column chromatography or recrystallization.
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 then 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, preferably tetrahydrofuran. The amount of the solvent is not particularly limited as long as the reaction proceeds smoothly, and may be a conventional amount in the art.
The conditions under which the compound 7 reacts with the deprotonating agent include: the reaction temperature is-78 to 0 , the reaction time is 5 to 50min, and the preferable reaction time is 25 to 35min.
The deprotonating agent may be one or more of n-butyllithium, isobutyllithium and tert-butyllithium, preferably n-butyllithium.
The molar ratio of the deprotonating agent to compound 7 may be 1-1.5:1, preferably 1-1.3:1.
The salt of the metal M may be, for example, hydrochloride.
Specific examples of the metal M include MCl 4.
The molar ratio of the salt of the metal M to the compound 7 may be between 0.5 and 2:1, preferably 0.5 to 1.5:1, more preferably 0.5 to 1:1.
After reaction with the deprotonating agent, the conditions for further reaction with the salt of the metal M may include, for example: the reaction temperature is 5-40 and the reaction time is 10-48h; preferably, the conditions for further reaction with the salt of metal M include: the reaction temperature is 10-30 and the reaction time is 20-30h.
The post-treatment for the reaction with the salt of the metal M may be carried out by a method conventional in the art, and may be, for example: filtering the reaction solution, washing the precipitate with toluene, combining the filtrates, distilling off part of the solvent under reduced pressure, dropwise adding n-hexane until the precipitate is generated, adding a small amount of toluene to dissolve the precipitate, and crystallizing the solution at-30-0 .
Preferably, the preparation of the compound represented by the formula (1) can be carried out according to the method represented by the following synthesis scheme (1).
In a third aspect the present invention provides a catalyst composition comprising a 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 and 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 higher catalytic activity.
According to the present invention, in order to further improve the catalytic activity of the catalyst composition, preferably, the ratio of the mole number of the cocatalyst in terms of Al/B element to the mole number of the metallocene compound represented by the formula (1) in terms of M in the catalyst composition is 100 to 3000:1.
In a third aspect, the present invention provides a supported metallocene catalyst comprising a support and a metallocene compound of the present invention supported on the support.
According to the present invention, in order to facilitate use, to enhance the reactivity, it is preferable that the supported metallocene catalyst further comprises a cocatalyst supported on the carrier; as the cocatalyst, one or more of methylaluminoxane, modified methylaluminoxane and triisobutylaluminum may be used in the catalyst composition according to the present invention, preferably the cocatalyst; 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 carrier is not particularly limited, and a supporting method generally used in the art may be used, and for example, an impregnation method may be used.
According to the present invention, the carrier may be a carrier of a supported catalyst commonly used in the art, and as the carrier, for example, one or more of SiO 2Al2O3, a carbon material, and a polymer carrier; more preferably, the support is a silica-coated carbon microsphere support.
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 support and actual needs, and preferably, the mass ratio of the support to the metallocene compound is 1:0.001-0.1; more preferably, the mass ratio of the support to the metallocene compound is 1:0.01-0.05. When the mass ratio of the carrier 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 carbon microsphere carrier with the surface covered with silicon dioxide can be prepared by the following method:
Dissolving halogen-containing polymer in good solvent to obtain mixed solution, mixing the obtained mixed solution with poor solvent to obtain halogen-containing polymer microsphere liquid, performing hydrothermal reaction on the halogen-containing polymer microsphere liquid, performing solid-liquid separation on the obtained reaction product, carbonizing, mixing the obtained carbonized product with siloxane, and roasting to obtain the carrier.
According to the present invention, as the halogen-containing polymer, a halogen-substituted olefin monomer may be polymerized to obtain a halogen-containing polymer, and in order to obtain a microsphere having a suitable size and pore, the halogen content in 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 in the halogen-containing polymer is 60 to 70 mass% of 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 the halogen is preferably Cl and/or Br from the viewpoints of polymer production cost and polymer solubility.
According to the present invention, the halogen-containing polymer may contain other elements than carbon, hydrogen and halogen, but from the viewpoint of improving the solubility of the polymer and promoting the subsequent hydrothermal reaction, it is preferable that the total content of carbon, hydrogen and halogen in the halogen-containing polymer is 90 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 polyolefin and/or halogenated polyhaloolefin.
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, 2-trichloroethylene, halogenated poly-3-chloropropene, halogenated polychloroprene, halogenated poly-bromoethylene, halogenated poly-3-bromopropene, and halogenated poly-bromobutene; 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, 2-trichloroethylene, chlorinated poly-3-chloropropene, chlorinated polychloroprene, chlorinated poly-bromoethylene, chlorinated poly-3-bromopropene, chlorinated poly-bromobutene, brominated polyethylene, brominated polypropylene, brominated poly-1-butene, brominated polyvinyl chloride, brominated poly-1, 1-dichloroethylene, brominated poly-1, 2-dichloroethylene, brominated poly-1, 2-trichloroethylene, brominated poly-3-chloropropene, brominated polychloroprene, brominated poly-bromoethylene, brominated poly-3-bromopropene, and brominated poly-bromobutene; 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 dissolution method is not particularly limited as long as the halogen-containing polymer is sufficiently dissolved, and may be, for example: the polymer was added to the good solvent and heated to reflux while stirring.
The temperature of the heating reflux is 40-150 for 1-5h, preferably the temperature of the heating reflux is 60-120 for 2-4h.
In order to facilitate the subsequent precipitation of carbon spheres of suitable size, preferably, the concentration of the halogenated polyolefin polymer in the good solvent is 0.5 to 20 mass%; more preferably, the concentration of the halogenated polyolefin polymer in the good solvent is 0.5 to 10 mass%.
The good solvent is not particularly limited as long as it sufficiently dissolves the halogen-containing polymer, and examples of such good solvents include tetrahydrofuran, dimethyl sulfoxide, aromatic hydrocarbon, amides, chlorinated hydrocarbons, and the like, and preferably one, two, or more of tetrahydrofuran, toluene, xylene, chloroform, trichlorobenzene, o-dichlorobenzene, p-dichlorobenzene, 2, 4-dichlorophenol, dimethyl sulfoxide, N-dimethylformamide, and N, N-dimethylacetamide; more preferably, the good solvent is one or more of tetrahydrofuran, xylene and dimethyl sulfoxide in order to obtain a carrier with more suitable size and pore diameter.
The ratio of the amount of the good solvent to the amount of the poor solvent may be adjusted in a wide range as long as the mixed solution can precipitate microspheres, 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 of suitable and uniform size, the volume ratio of good solvent to poor solvent is preferably 1:20-80.
The poor solvent is not particularly limited as long as the mixed solution can be precipitated into microspheres, and the good solvent may be, for example, one or more of water, ammonia, alcohols, ketones, ethers, alkanes and esters, and specifically one or more of water, ammonia, methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, glycerol, isopropanol, n-octanol, benzyl alcohol, acetone, butanone, n-hexane, cyclohexane, methyl ether, diethyl 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, the poor solvent is preferably one or more of water, methanol, ethanol, ethyl acetate and acetone.
The mixing method is not particularly limited as long as the microspheres can be precipitated from the mixed solution, and the mixing conditions preferably include: the mixing temperature is-20-60 and the mixing time is 0.5-5h; more preferably, the mixing conditions include: the mixing temperature is 0-40deg.C, and the mixing time is 0.5-3h. When the mixing conditions are as described above, precipitation of the microspheres is more complete.
In order to facilitate the hydrothermal reaction, preferably, the method further comprises a step of concentrating the mixed solution obtained in the step 1) after mixing the mixed solution with the poor solvent;
The concentration is not particularly limited as to the manner of concentration for reducing the amount of the solvent to promote the hydrothermal reaction, and a concentration manner generally used in the art may be used, and for example, the solvent may be evaporated by heating, and the solvent may be removed by filtration.
The concentration may be performed in an amount of 10 to 90% by weight, and in order to further enhance the subsequent hydrothermal reaction rate, it is preferable that the concentration is performed in an amount of 20 to 80% by weight
Of course, all solvents may be removed and new solvents may be added to prepare the halogen-containing polymer microsphere fluid. Specifically, the halogen-containing polymer microsphere liquid can be prepared by mixing, then carrying out solid-liquid separation to remove the liquid phase, and then 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 one or more of filtration and centrifugation, which are commonly used in the art.
The conditions of the hydrothermal reaction preferably include, in order to make the halogen-containing polymer microsphere react more sufficiently: the reaction temperature is 200-400 and the reaction time is 1-10h; more preferably, the hydrothermal reaction conditions include: the reaction temperature is 250-350 and the reaction time is 2-8h.
The carbonization is used to convert the hydrothermal reaction product into carbon spheres, and as such conversion conditions include: heating for 1-10h at 200-1000 under inert atmosphere; more preferably, the carbonization conditions include: under inert atmosphere, the carbonization temperature is 250-800 and the carbonization time is 2-7.
Preferably, the heating carbonization conditions include: heating to 200-1000 deg.C at 1-20deg.C/min under inert atmosphere, and heating at the temperature for 1-10 hr; more preferably, the conditions for heating carbonization further include: heating to 250-800 deg.C at 1-20deg.C/min under inert atmosphere, and heating at the temperature for 2-7 hr.
Preferably, the method further comprises the step of drying the solid phase obtained by the solid-liquid separation, prior to the carbonization, the drying being used to remove the solvent for the carbonization.
Preferably, the drying conditions include: the drying temperature is 50-200 and the drying time is 1-8h; more preferably, the drying conditions include: the drying temperature is 80-150 and the drying time is 3-8h.
The siloxane is used for being combined with the carbon sphere and then converted into silicon dioxide to form a structure that the silicon dioxide covers the surface of the carbon sphere, and the siloxane can be one or more of tetramethyl siloxane, tetraethoxy siloxane, trimethoxy chlorosilane, triethoxy chlorosilane, dimethoxy dichlorosilane and ethoxy trichlorosilane; in order to more tightly bond with the carbon sphere, preferably, the siloxane is one or more of tetramethylsiloxane, tetraethoxysiloxane, and trimethoxychlorosilane.
The amount of the siloxane may be such that the carbon sphere is sufficiently bonded to the siloxane, and for example, the mass ratio of the carbon sphere to the siloxane may be 1:20-100; in order to improve the bonding efficiency and facilitate the calcination treatment, it is preferable that the mass ratio of the carbon sphere to the siloxane is 1:20-50.
In order to allow the siloxane to be sufficiently bonded to the carbon spheres, preferably, the conditions of the mixed adsorption include: the mixing temperature is 20-200 , and the mixing time is 1-10h; more preferably, the conditions of the mixed adsorption include: the mixing temperature is 50-150 and the mixing time is 2-8h.
According to the invention, the firing is used to convert the siloxane to silica, and as such firing conditions may include: roasting at 400-800 deg.c for 1-8 hr; in order to further improve the conversion efficiency, preferably, the conditions of the firing include: the roasting temperature is 400-700 and the roasting time is 2-7h.
When the metallocene compound of the present invention is supported on the above-mentioned carrier, there is an advantage of high activity.
In a fourth aspect, the present invention provides the use of a metallocene compound, a catalyst composition or a supported metallocene catalyst according to the invention in the polymerization of olefins.
The invention provides a metallocene catalyst with excellent catalytic activity and a preparation method thereof, which can be used for catalyzing olefin homo-polymerization and copolymerization. The invention also provides a catalyst composition for catalyzing olefin polymerization, which contains the metallocene catalyst and a supported metallocene catalyst.
The present invention will be described in detail 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 company Legend Xia Meiye, inc., which 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
The metallocene compound (the compound of the structure represented by the formula (2) wherein R 1-R4 is hydrogen and R 5-R8 is methyl) was synthesized according to the following synthesis scheme (2)
(1) Formylation reaction
100G (0.37 mol) of iodo-N-phenylimidazole is added into a 1000mL three-necked flask, 200mL of anhydrous tetrahydrofuran is added after nitrogen is fully replaced, and the temperature is cooled to-78 ; then 148mL of n-butyllithium solution (2.5M n-hexane solution) was slowly added dropwise; subsequently, 54g (0.74 mol) of anhydrous N, N-dimethylformamide was added dropwise; finally, the temperature is slowly raised to room temperature, and the reaction is carried out overnight. Post-treatment: the reaction was quenched by adding 100mL of dilute hydrochloric acid (10 wt%) and the organic phase was extracted with ethyl acetate, dried and separated by chromatography. Compound 1-2 was obtained in 45.2g and yield was 71%.
(2) Wittig reaction
Taking a 500mL three-neck flask, adding 4.8g of sodium hydride (0.12 mol,60wt% of which is dispersed in mineral oil) and 100mL of dry tetrahydrofuran under the protection of nitrogen, and cooling to 0 ; then (EtO) 2POCH(CH3)CO2 Et 28.6g (0.12 mol) was added dropwise and reacted for half an hour; next, a tetrahydrofuran solution (100 mL) of Compound 1-2 (17.2 g,0.1 mol) was added dropwise; finally, the reaction temperature is slowly raised to room temperature for reaction for 10 hours. Post-treatment: adding water to quench reaction, extracting organic phase with ethyl acetate, drying, and separating with chromatographic column. Compound 1-3 was obtained in 25.3g in 99% yield.
(3) Hydrogenation and hydrolysis reactions
A500 mL single-necked flask was charged with 20.5g (0.08 mol) of Compound 1-3, 100mL of ethanol and 1.0g of palladium on carbon (palladium content: 10%) and then a hydrogen balloon was attached thereto, followed by stirring at room temperature for reaction for 24 hours. Post-treatment: the catalyst was removed by filtration and the solvent was evaporated. The obtained solid compound was directly subjected to the next reaction without further purification.
The product obtained in the previous step was dissolved in 200mL of methanol, 20mL of concentrated hydrochloric acid (37 wt%) was added, and the mixture was heated under reflux for 48 hours. Post-treatment: evaporating the solvent, washing with water, extracting the organic phase with ethyl acetate, drying, and separating with chromatographic column. Compounds 1 to 4 were obtained in 15.6g and in 85% yield in two steps.
(4) Friedel-crafts acylation reaction
A250 mL single-necked flask was charged with 11.5g (0.05 mol) of Compound 1-4 and 20g of polyphosphoric acid, and the temperature was raised to 80for reaction for 8 hours. Post-treatment: the reaction solution was poured into ice water, extracted with ethyl acetate, dried and separated by a chromatographic column. The yield of the compound 1-5 was 9.5g and 90%.
(5) Carbonyl reduction and elimination reactions
Taking a 100mL single-neck flask, adding 8.5g (0.04 mol) of compound 1-5 and 100mL of anhydrous diethyl ether, and cooling to 0 ; 3.0g (0.08 mol) of lithium aluminum hydride are then added in portions; finally, the reaction was carried out at room temperature overnight. Post-treatment: the solid matter is removed by filtration, the filter cake is washed three times with diethyl ether, the filtrates are combined, and the solvent is evaporated for use.
The above product was dissolved in 100mL of toluene, 0.76g (0.004 mol) of p-toluenesulfonic acid monohydrate was added, and the mixture was heated under reflux for 24 hours. Post-treatment: evaporating the solvent, washing with water, extracting with ethyl acetate, and separating with chromatographic column. Compound 1-6 was obtained in 5.7g and yield was 73%.
(6) Deprotonation nucleophilic addition reaction and silicon bridging reaction
Under the protection of nitrogen, adding 19.6g (0.1 mol) of compound 1-6 and 100mL of tetrahydrofuran subjected to drying treatment into a 500mL three-neck flask, and cooling to-78 ; then, 40mL (2.5M in n-hexane) of n-butyllithium was added dropwise, and after stirring for 30 minutes, 14.2g (0.1 mol) of methyl iodide was added; finally, the temperature is slowly raised to room temperature, and the reaction is carried out for 1 hour. Post-treatment: adding water to quench the reaction, extracting by adopting ethyl acetate, and evaporating the solvent for later use.
Under the protection of nitrogen, dissolving the product into 100mL of tetrahydrofuran subjected to drying treatment, and cooling to-78 ; then, 40mL (2.5M in n-hexane) of n-butyllithium was added dropwise, and after stirring for 30 minutes, 6.45g (0.05 mol) of dichlorodimethylsilane was added; finally, the temperature is slowly raised to room temperature, and the reaction is carried out for 1 hour. Post-treatment: adding water to quench the reaction, extracting with ethyl acetate, and separating with chromatographic column. Compound 1-7 was obtained in 12.2g and yield was 51%.
(7) Preparation of metallocene compounds
Under the protection of nitrogen, 4.79g (0.01 mol) of compound 1-7 is taken and dissolved into 50mL of tetrahydrofuran after drying treatment, and the solution is cooled to-78 ; then, 4mL (2.5M in n-hexane) of n-butyllithium was added dropwise, and after stirring for 30 minutes, 1.17g (0.005 mol) of zirconium tetrachloride was added; the reaction was allowed to slowly warm to room temperature for 24 hours. Post-treatment: the precipitate was filtered, washed with 50mL toluene and the filtrates combined. Part of the solvent was distilled off under reduced pressure, n-hexane was added dropwise until precipitation was generated, and then a very small amount of toluene was added to dissolve the precipitate. The solution was crystallized at-20and filtered to give orange-red crystals, which were dried to give 3.35g of Compound 1-8 in 60% yield. The structure was confirmed by single crystal diffraction.
Preparation examples 2 to 5: synthesizing a compound of the structure represented by formula (3) to a compound of the structure represented by formula (6) respectively
A compound of the structure shown in formula (3): in the compound with the structure shown in the formula (1), R 1-R4 is methyl, R 5-R8 is methyl, and M is zirconium;
A compound of the structure shown in formula (4): in the compound with the structure shown in the formula (1), R 1R3 is isopropyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is zirconium;
A compound of the structure shown in formula (5): in the compound with the structure shown in the formula (1), R 1-R4 is methyl, R 5-R8 is hydrogen, and M is zirconium;
A compound of the structure shown in formula (6): in the compound with the structure shown in the formula (1), R 1R3 is methyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is zirconium;
Preparation examples 2 to 5 were conducted in the same manner as in preparation example 1 except that starting materials corresponding to R 1-R8 in the obtained objective product were used as the respective starting materials, and the compound represented by the formula (3) to the compound represented by the formula (6) were obtained.
Example 1
In a 500mL polymerization apparatus which was sufficiently replaced with nitrogen gas, 100mL of dry hexane was added, the polymerization apparatus was warmed to 70 , and then 2mL of 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 polymerizer (also, the molar ratio of the cocatalyst to the compound represented by the formula (2) in the catalyst composition was 1000:1, based on the number of moles of the Al element in the cocatalyst and M in the compound represented by the formula (2)), and the molar ratio of hydrogen to the propylene was 0.002:1, and then adding propylene to the pressure of 0.1Mpa to continuously supplement the mixed gas of propylene and hydrogen. Polymerization is carried out at an internal temperature of 70 for 2 hours. After pressure relief, the solution in the apparatus was added with methanol to obtain a precipitated polymer, which was dried under vacuum at 50for 8 hours to obtain 8g of polypropylene having a catalyst activity of 4X 10 6 g PP/molZr. The physical properties of the obtained polypropylene 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 metallocene catalyst, the kind of cocatalyst, the amounts of metallocene catalyst and cocatalyst, the molar ratio of hydrogen and propylene were used, and the polymerization temperature and time were the values shown in table 1.
Example 6
In a 500mL polymerization apparatus fully replaced with nitrogen, 50mL of dry hexane was added, and then the internal temperature of the polymerization apparatus was raised to 60and 150mL of C8-C12 Fischer-Tropsch synthesized alpha-olefin was added. Thereafter, 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 polymerizer (i.e. the molar ratio of the cocatalyst to the compound represented by the formula (2) was 1000:1 in terms of the molar number 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 40and then the polymerization was terminated by adding an acid alcohol. After pressure relief, the solution in the apparatus was taken up in methanol to give a precipitated polymer which was dried under vacuum at 50for 6h. 16.74g of a copolymer alpha-olefin was obtained, and the physical properties of the obtained copolymer alpha-olefin are shown in Table 2.
Example 7
Preparation of the Carrier
1G of chlorinated polypropylene (the content of chlorine element is 70 mass percent, the molar ratio of Cl/C is 0.92:1, the CPP-70 model is purchased from Shandong Fangfang Gao Xin chemical industry Co., ltd.) is dissolved in 100ml of tetrahydrofuran as a good solvent, fully stirred and heated to 60 , and nitrogen is used as protective gas for condensation and reflux, and fully dissolved for 2 hours; 1000ml of acetone is placed in a beaker and is rapidly stirred, and a disposable injection needle tube is used for rapidly injecting tetrahydrofuran solution dissolved with chlorinated polypropylene into the rapidly stirred acetone serving as a poor solvent; after all the solutions are injected, preparing chlorinated polypropylene microspheres; taking 100ml of the solution containing chlorinated polypropylene microspheres, adding 100ml of distilled water, and distilling under reduced pressure to remove tetrahydrofuran and acetone; pouring the rest solution into a 50ml high-pressure reaction kettle, heating to 350 at 10 /min, reacting for 8 hours to obtain liquid containing black precipitate, removing supernatant, washing with ethanol solution, and drying to obtain black powder; and (3) placing the black powder into a quartz tube of a tube furnace, and filling nitrogen into the system to ensure that the quartz tube is free of active gases such as oxygen and the like. The black powder was heated at a rate of 10 c/min to a final carbonization temperature of 800 c and held at that temperature for 3 hours. Slowly cooling to 30 under nitrogen to obtain the carbon microsphere. Mixing the obtained micron carbon spheres with tetramethoxy siloxane according to a mass ratio of 1:2, mixing and adsorbing for 4 hours at 100 , and roasting the mixed and adsorbed product for 6 hours at 400 to obtain the catalyst carrier.
Preparation of supported metallocene catalysts
1.0G of the support was dispersed in 5mL of toluene, heated with stirring to 60and immersed in 5mL of a toluene solution of Methylaluminoxane (MAO) (1.4 mol/L concentration) for 7 hours, and then washed 5 times with 10mL of toluene to remove excess MAO, and the obtained SiO 2/MAO was suspended in 10mL of toluene. Then, 30mg of the compound represented by the formula (2) was added to the toluene suspension of SiO 2/MAO. After mixing, the mixture was reacted at 50for 7 hours, and the unsupported metallocene catalyst was removed by washing 5 times with 10ml of toluene. And (5) drying in vacuum for 5 hours to obtain the supported metallocene catalyst. The mole 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 carrier to the metallocene compound is 1:0.05.
100Mg of metallocene carrier catalyst and 1.2 kg of propylene are added into a 5L steel kettle, the mixture is stirred and reacted for 1 hour at 70 , the reaction is stopped, the material is discharged, and the mixture is dried in a vacuum drying oven for 8 hours to obtain polypropylene. The resulting polypropylene was weighed and the catalyst activity calculated as 25.7KgPP/gCat based on the weight of catalyst added.
Comparative example 1
Polypropylene was prepared according to the method of example 1, except that the metallocene catalyst used was dimethylsilylbis (2-methyl-4-phenylindenyl) zirconium dichloride (available from Innoci, having the structure shown below, also referred to below as formula D). The physical properties of the obtained polypropylene are shown in Table 2.
TABLE 1
In the table, modified methylaluminoxane was purchased from enoKai (Innochem) as a 7 wt% heptane solution.
TABLE 2
As can be seen from the results of Table 2, the examples using the preparation method of the present invention were high in catalytic activity.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (12)

1. A metallocene compound characterized by being represented by the following chemical formula (1):
(1),
In the formula (1), R 1-R8 is a hydrogen atom or C1-C12 alkyl, and M is one or more of zirconium, titanium and hafnium.
2. The metallocene compound according to claim 1, wherein in the formula (1), each of R 1-R8 is a hydrogen atom or a C1-C4 alkyl group.
3. The metallocene compound according to claim 1, wherein in the formula (1), each of R 1-R8 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 the formula (1) is selected from one or more of the following compounds,
Compound a-1: r 1-R4 is H, R 5-R8 is methyl, M is zirconium;
compound a-2: r 1-R4 is H, R 5-R8 is methyl, M is titanium;
compound a-4: r 1-R4 is H, R 5-R8 is methyl, M is hafnium;
Compound B-1: r 2-R4 is H, R 1 and R 5-R8 are methyl, M is zirconium;
Compound B-2: r 2-R4 is H, R 1 and R 5-R8 are methyl, M is titanium;
Compound B-4: r 2-R4 is H, R 1 and R 5-R8 are methyl, M is hafnium;
Compound C-1: r 1-R8 is methyl, M is zirconium;
Compound C-2: r 1-R8 is methyl, M is titanium;
Compound C-4: r 1-R8 is methyl, M is hafnium;
Compound D-1: r 1-R4 is isopropyl, R 5-R8 is methyl, and M is zirconium;
Compound D-2: r 1-R4 is isopropyl, R 5-R8 is methyl, M is titanium;
compound D-4: r 1-R4 is isopropyl, R 5-R8 is methyl, and M is hafnium;
Compound E-1: r 1-R4 is ethyl, R 5-R8 is methyl, M is zirconium;
compound E-2: r 1-R4 is ethyl, R 5-R8 is methyl, M is titanium;
compound E-4: r 1-R4 is ethyl, R 5-R8 is methyl, and M is hafnium;
Compound F-1: r 1-R4 is methyl, R 5-R8 is H, M is zirconium;
Compound F-2: r 1-R4 is methyl, R 5-R8 is H, M is titanium;
compound F-4: r 1-R4 is methyl, R 5-R8 is H, and M is hafnium;
Compound G-1: r 1R3 is H, R 2R4 and R 5-R8 are methyl, M is zirconium;
Compound G-2: r 1R3 is H, R 2R4 and R 5-R8 are methyl, M is titanium;
Compound G-4: r 1R3 is H, R 2R4 and R 5-R8 are methyl, M is hafnium;
compound H-1: r 1-R8 is H, M is zirconium;
Compound H-2: r 1-R8 is H, M is titanium;
Compound H-4: r 1-R8 is H, M is hafnium;
Compound I-1: r 1R3 is isopropyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is zirconium;
compound I-2: r 1R3 is isopropyl, R 2R4 is hydrogen, R 5-R8 is methyl, M is titanium;
Compound I-4: r 1R3 is isopropyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is hafnium;
Compound J-1: r 1R3 is methyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is zirconium;
Compound J-2: r 1R3 is methyl, R 2R4 is hydrogen, R 5-R8 is methyl, M is titanium;
Compound J-4: r 1R3 is methyl, R 2R4 is hydrogen, R 5-R8 is methyl, and M is hafnium.
5. A catalyst composition comprising the metallocene compound of any one of claims 1 to 4 and a cocatalyst.
6. The catalyst composition of claim 5, wherein the cocatalyst is one or more of methylaluminoxane, modified methylaluminoxane, and triisobutylaluminum.
7. A supported metallocene catalyst comprising a support and the metallocene compound of any one of claims 1 to 4 supported on said support.
8. The supported metallocene catalyst of claim 7, wherein the support is one or more of SiO 2Al2O3, a carbon material, and a polymeric support.
9. The supported metallocene catalyst of claim 7, wherein the supported metallocene catalyst further comprises a cocatalyst supported on the support.
10. The supported metallocene catalyst of claim 7, wherein the cocatalyst is one or more of methylaluminoxane, modified methylaluminoxane, and triisobutylaluminum.
11. The supported metallocene catalyst of claim 7, wherein the support is a silica-coated carbon microsphere support.
12. Use of the metallocene compound according to any one of claims 1 to 4, the catalyst composition according to claim 5 or 6 or the supported metallocene catalyst according to any one of claims 7 to 11 for the polymerization of olefins.
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CN112940158A (en) * 2021-01-12 2021-06-11 中国石油天然气股份有限公司 Supported metallocene catalyst and preparation method and application thereof

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CN103554308A (en) * 2013-10-15 2014-02-05 天津西青区润天金成科技发展有限公司 Supported metallocene catalyst, its preparation method and application
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