CN112940158B - Supported metallocene catalyst and preparation method and application thereof - Google Patents
Supported metallocene catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN112940158B CN112940158B CN202110035707.6A CN202110035707A CN112940158B CN 112940158 B CN112940158 B CN 112940158B CN 202110035707 A CN202110035707 A CN 202110035707A CN 112940158 B CN112940158 B CN 112940158B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- metallocene compound
- alkyl
- polymerization
- metallocene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- 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
- C08F110/02—Ethene
-
- 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
Abstract
The inventionDisclosed is a supported metallocene catalyst, its preparation method and application, used for olefin polymerization, the supported metallocene catalyst comprises a carrier and a metallocene compound, the metallocene compound is supported on the carrier, the metallocene compound has cis and trans structures in the spatial structure, as shown in the following formula I:
wherein M is a transition metal element of IIIB, IVB, VB or VIB in the periodic table of elements; t is a group IVA element; x is independently selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, mercapto, carboxyl, amino, phosphino and OSO 2 CF 3 (ii) a Q is independently selected from hydrogen, halogen, alkyl, alkoxy, haloalkyl; e is a group VA element; r 1 ，R 2 ，R 3 ，R 4 The same or different from each other, independently hydrogen, alkyl, alkoxy, aryl or alkenyl. The polyethylene product obtained by using the catalyst of the invention in ethylene polymerization has a broad molecular weight distribution or a bimodal distribution through GPC analysis.
Description
Technical Field
The invention relates to a supported metallocene catalyst and a preparation method thereof, and relates to a method for preparing bimodal polyethylene by using a single reactor and a single metallocene catalyst system, and the obtained polyethylene.
Background
Polyolefin resin, as one of important synthetic materials, directly affects the development of national economy. At present, the polyolefin industry in China develops rapidly, but the yield and the performance can not meet the market demand, and particularly the demand of high-performance polyolefin materials increases rapidly, so that how to improve the performance of general high polymer materials such as polyethylene and the like is a hot spot of research of people. The bimodal polyethylene consists of high molecular weight polyethylene and low molecular weight polyethylene, the high molecular weight part can ensure the physical mechanical strength of the polymer, and the low molecular weight part can improve the processability of the polymer, so that compared with common polyethylene products, the bimodal molecular weight distribution polymer, particularly polyethylene, can give consideration to good mechanical properties and processability, and is widely applied in recent years.
To achieve these characteristics, there are three methods for industrially producing bimodal polyethylene currently, in which polymers having different molecular weights are produced through two reactors by a parallel reaction tank process and then blended in a molten state, but this method is expensive and it is difficult to control the uniformity of product quality.
The method has the advantages of flexible operation, convenient product switching and higher equipment investment cost. The currently used tandem production processes in industrial production mainly include Borstar process by Borealis corporation in finland, CX process by Mitsui corporation in japan, unipol ii process by UCC corporation in usa, and spherinene process by Basell corporation in england.
The method adopts a single reaction kettle process, uses a catalyst with multiple active points, or a single catalyst and multiple carriers, or a mixed catalyst, and common catalyst systems comprise a composite bimetallic catalyst system, a Ziegler-Natta/metallocene composite catalyst, a Ziegler-Natta/Ziegler-Natta composite catalyst, a double metallocene composite catalyst, a chromium-based/metallocene composite catalyst, a metallocene/late transition metal composite catalyst and the like. This process is considered a revolutionary advance due to the substantial reduction in equipment costs. At present, the method is realized in some chemical companies, for example, UCC of the United states adopts a gas phase method and a suitable mixed catalyst in a Unipol process unit to synthesize a bimodal polyethylene product. The university catalyst, developed by Univariation, can produce bimodal HDPE in a single reactor. Both british BP and Phillips companies have performed corresponding research and development work.
For example, WO99/03899 by Mobil corporation, this type of catalyst has been reported to have better copolymerization performance than Ziegler-Natta catalysts, and the molecular weight of the resulting polymer is relatively large, so that the high molecular weight portion of the resulting resin has low branching degree, even no branching, while the low molecular weight portion has high branching, and the material cannot achieve balance between processability and strength, and does not achieve ideal compounding effect.
In the prior art, chinese patent CN 109705242a discloses a supported metallocene catalyst, a preparation method and an application thereof, a single metallocene catalyst composite carrier, the supported catalyst has a double-activity center, and the composite carrier comprises a first carrier and a second carrier; the first carrier is an inorganic carrier modified by antimony chloride and alkyl aluminum, and the second carrier is carboxylated polystyrene, wherein the inorganic carrier is silicon dioxide or silica gel. Chinese patent CN 106589178A discloses a method for preparing a vanadium and metallocene bimetallic catalyst, which comprises the steps of obtaining vanadium oxide in an oxidation state by high-temperature roasting, reacting under a reduction condition to obtain pre-reduced vanadium oxide in a low oxidation state, then loading the pre-reduced vanadium oxide and a metallocene composition on an inorganic carrier to obtain a vanadium/metallocene composite catalyst, and applying the vanadium/metallocene composite catalyst to olefin preparation.
Both single metallocene catalyst composite supports and bimetallic catalysts require special design in the preparation of the catalyst, so that the prepared catalyst contains two active centers, one for producing low molecular weight polyethylene and the other for producing high molecular weight polyethylene. Therefore, the synergistic effect of a bimetallic catalyst or a dual-carrier system needs to be considered when a catalytic system is designed, so that the limitation of catalyst selection is increased, and the important significance is provided for developing a single-carrier supported single metallocene catalyst to prepare a bimodal polyethylene product.
Disclosure of Invention
The invention mainly aims to provide a supported metallocene catalyst and a preparation method thereof, an ethylene polymerization method and prepared polyethylene, so as to overcome the defects that a composite carrier or a bimetallic catalyst in the prior art is low in catalyst activity, limited in selection and undesirable in the prepared polymer when the polyethylene with wide molecular weight distribution is prepared.
In order to achieve the above object, the present invention provides a supported metallocene catalyst for olefin polymerization, the supported metallocene catalyst comprising a support and a metallocene compound, the metallocene compound being supported on the support, the metallocene compound having both cis and trans structures in a steric structure, as shown in formula i or formula ii below:
wherein M is a transition metal element of IIIB, IVB, VB or VIB in the periodic table of elements; t is a group IVA element; x is independently selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, mercapto, carboxyl, amino, phosphino and OSO 2 CF 3 (ii) a Q is independently selected from hydrogen, halogen, alkyl, alkoxy, haloalkyl; e is a group VA element; r 1 ，R 2 ，R 3 ，R 4 The same or different from each other, and are independently hydrogen, alkyl, alkoxy, aryl or alkenyl.
The supported metallocene catalyst is characterized in that M is an IIIB or IVB element in a periodic table of elements; the X phaseAre the same or different from each other and are independently selected from halogen; q is the same or different and is independently selected from alkyl; the R is 1 ，R 2 ，R 3 ，R 4 Is hydrogen, C1-C10 alkyl, C3-C10 alkenyl, C3-C6 alkoxy or aryl.
The supported metallocene catalyst of the invention, wherein M is zirconium, hafnium or titanium; x is chlorine or bromine; the R is 1 ，R 2 ，R 3 ，R 4 Independently hydrogen, C1-C4 alkyl, C3-C4 alkenyl, C3-C5 alkoxy or aryl.
The supported metallocene catalyst of the present invention, wherein R is 1 ，R 2 ，R 3 ，R 4 Independently hydrogen, methyl, isopropyl, butyl, a benzene ring or substituted benzene.
In order to achieve the above object, the present invention also provides a method for preparing a supported metallocene catalyst for olefin polymerization, the supported metallocene catalyst comprising a support and a metallocene compound, the method for preparing the metallocene compound comprising:
step 1, ligands A1 and Q 2 TA 2 Preparing an intermediate product 1 through reaction, carrying out lithiation reaction on a ligand A2 and an alkyl lithium reagent to prepare an intermediate product 2, and carrying out salt elimination reaction on the intermediate product 1 and the intermediate product 2 to obtain an intermediate product 3, wherein the formula is shown as a formula III;
step 2, intermediate 3 with MX 4 The metallocene compound is obtained by salt elimination reaction, and comprises a cis structure and a trans structure, which are shown in the following formula IV;
wherein M is a transition metal element of IIIB, IVB, VB or VIB in the periodic table of elements; t is group IVAAn element; x is independently selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, mercapto, carboxyl, amino, phosphino and OSO 2 CF 3 (ii) a Q is independently selected from hydrogen, halogen, alkyl, alkoxy, haloalkyl; e is a group VA element; r 1 ，R 2 ，R 3 ，R 4 Are the same or different from each other and are independently hydrogen, alkyl, alkoxy, aryl or alkenyl; a is halogen.
The preparation method of the supported metallocene catalyst comprises the steps that T is C or Si, Q is alkyl, and the ligand A1 is subjected to lithiation reaction with an alkyl lithium reagent and then subjected to lithiation reaction with Q 2 TA 2 The salt elimination reaction takes place to give intermediate 1.
The preparation method of the supported metallocene catalyst comprises the steps of enabling X to be halogen, enabling M to be zirconium, hafnium or titanium, enabling an intermediate product 3 to be subjected to lithiation reaction with an alkyl lithium reagent, and enabling the intermediate product to be subjected to lithiation reaction with MX 4 The salt elimination reaction occurs to obtain the metallocene compound.
The preparation method of the supported metallocene catalyst provided by the invention has the advantages that the metallocene compounds with cis-structure and trans-structure are directly supported on the carrier without separation to obtain the supported metallocene catalyst.
In order to achieve the above object, the present invention provides an ethylene polymerization process using the above supported metallocene catalyst.
The ethylene polymerization process of the present invention, wherein the process is carried out in a single reactor.
The polyethylene prepared by the ethylene polymerization method has a bimodal distribution and/or a molecular weight distribution width of 5-7.
The invention has the beneficial effects that:
the invention provides a supported single metallocene catalyst, wherein an active component metallocene compound has a quasi-C2 symmetrical structure, although the metallocene compound is a single compound, a cis (syn) structure and a trans (anti) structure exist in a spatial structure, and the compounds with the two different spatial structures are freely transformed in an ethylene polymerization process to respectively obtain polymers with different molecular weights, so that finally obtained polyethylene has wide molecular weight distribution and even bimodal distribution.
The invention also provides a preparation method of the metallocene compound, the prepared cis-structure and trans-structure metallocene compound can be directly loaded on a carrier to obtain the metallocene catalyst without separation operation, and the process is simple and is suitable for industrial production.
When the supported single metallocene catalyst is used for ethylene polymerization, the cis-structure metallocene compound and the trans-structure metallocene compound have the same requirements on reaction conditions, the reaction conditions are easy to select, the molecular weight distribution of the obtained polyethylene is wide, and the balance between the processability and the strength can be realized.
Drawings
FIG. 1 shows the nuclear magnetic spectrum of the product obtained in example 2.
FIG. 2 shows the nuclear magnetic spectrum of the product obtained in example 3.
FIG. 3 is the nuclear magnetic spectrum of the product obtained in example 5.
Detailed Description
The following examples of the present invention are described in detail, and the present invention is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and procedures are given, but the scope of the present invention is not limited to the following examples, and the following examples are experimental methods without specific conditions noted, and generally follow conventional conditions.
The invention provides a supported metallocene catalyst for olefin polymerization, which comprises a carrier and a metallocene compound, wherein the metallocene compound is supported on the carrier, and the metallocene compound has a cis structure and a trans structure in a spatial structure, and is shown as the following formula I or formula II:
wherein M is a transition metal element of the IIIB, IVB, VB or VIB group in the periodic Table of the elements; t is a group IVA element; x is independently selected fromHydrogen, halogen, alkyl, alkoxy, mercapto, carboxyl, amino, phosphino and OSO 2 CF 3 (ii) a Q is independently selected from hydrogen, halogen, alkyl, alkoxy, haloalkyl; e is a group VA element; r 1 ，R 2 ，R 3 ，R 4 The same or different from each other, and are independently hydrogen, alkyl, alkoxy, aryl or alkenyl.
The active component metallocene compound of the load type single metallocene catalyst has a quasi C2 symmetrical structure, although the metallocene compound is a single compound, cis (syn) and trans (anti) structures exist on the space structure, the two compounds with different space structures are freely transformed in the ethylene polymerization process to respectively obtain polymers with different molecular weights, so that the finally obtained polyethylene has wide molecular weight distribution and even bimodal distribution.
In one embodiment, M is an iiib or ivb element of the periodic table of elements, including the lanthanides and series elements; x, equal to or different from each other, are independently selected from halogen; q is the same or different and is independently selected from alkyl; the R is 1 ，R 2 ，R 3 ，R 4 Independently hydrogen, C1-C10 alkyl, C3-C10 alkenyl, C3-C6 alkoxy or aryl.
In another embodiment, M is zirconium, hafnium or titanium; x is chlorine or bromine; the R is 1 ，R 2 ，R 3 ，R 4 Independently hydrogen, C1-C4 alkyl, C3-C4 alkenyl, C3-C5 alkoxy or aryl.
In yet another embodiment, the R is 1 ，R 2 ，R 3 ，R 4 Independently hydrogen, methyl, isopropyl, butyl, a benzene ring or substituted benzene.
The supported metallocene catalyst of the present invention is not particularly limited in the proportional relationship between the cis-structured and trans-structured metallocene compounds, and the cis-structured and trans-structured metallocene compounds are converted with each other during the ethylene polymerization process.
The carrier used in the present invention is not particularly limited, and may be any carrier conventionally used in the art, such as silica gel. The relation of the amount of the active ingredient and the carrier can be reasonably adjusted by a person skilled in the art according to the needs.
The invention also provides a preparation method of the supported metallocene catalyst, which can obtain a product shown in formula I or formula II according to the structure of the ligand A1, wherein the preparation method of the metallocene compound used as an active component comprises the following steps:
step 1, ligands A1 and Q 2 TA 2 Preparing an intermediate product 1 through reaction, carrying out lithiation reaction on a ligand A2 and an alkyl lithium reagent to prepare an intermediate product 2, and carrying out salt elimination reaction on the intermediate product 1 and the intermediate product 2 to obtain an intermediate product 3, wherein the formula is shown as a formula III;
step 2, intermediate 3 with MX 4 The metallocene compound is obtained by salt elimination reaction, and comprises a cis structure and a trans structure, which are shown in the following formula IV;
wherein M is a transition metal element of IIIB, IVB, VB or VIB in the periodic table of elements; t is a group IVA element; x is independently selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, mercapto, carboxyl, amino, phosphino and OSO 2 CF 3 (ii) a Q is independently selected from hydrogen, halogen, alkyl, alkoxy, haloalkyl; e is a group VA element; r 1 ，R 2 ，R 3 ，R 4 Are the same or different from each other and are independently hydrogen, alkyl, alkoxy, aryl or alkenyl; a is halogen.
According to the preparation method of the metallocene compound, the prepared cis-structure and trans-structure metallocene compounds can be directly loaded on a carrier to obtain the metallocene catalyst without separation operation, the process is simple, the synthesis yield is high, the product purification is easy, and the preparation method is suitable for industrial production.
In one embodiment, the preparation of the metallocene compounds of the invention is carried out under protection of an inert gas, such as nitrogen or the like.
In one embodiment, T is C or Si, Q is alkyl, and the ligand A1 is lithiated with an alkyllithium reagent prior to lithiation with Q 2 TA 2 The salt elimination reaction takes place to give intermediate 1. X is halogen, M is zirconium, hafnium or titanium, the intermediate product 3 is firstly subjected to lithiation reaction with an alkyl lithium reagent and then is subjected to lithiation reaction with MX 4 The salt elimination reaction occurs to obtain the metallocene compound.
In another embodiment, the alkyllithium reagent is, for example, n-butyllithium, and ligand A1 is reacted with the alkyllithium reagent in an organic solvent, for example, anhydrous diethyl ether, at a temperature of, for example, 0 deg.C to room temperature. The reaction product is further reacted with Q 2 TA 2 A salt elimination reaction takes place to give intermediate 1, the temperature of which is, for example, -78 ℃ to room temperature.
In another embodiment, ligand A2 is reacted with an alkyllithium reagent, such as n-butyllithium, in an organic solvent, such as anhydrous diethyl ether, at a temperature of, for example, 0 deg.C to room temperature, to provide intermediate 2.
The reaction of intermediate 1 and intermediate 2 is: intermediate 1 and intermediate 2 are each dissolved in an organic solvent, such as anhydrous ether, and intermediate 2 is then slowly added dropwise to intermediate 1, for example at a temperature below 0 ℃, and after completion of the addition, the reaction is carried out at room temperature to give intermediate 3.
In another embodiment, intermediate 3 is reacted with an alkyllithium reagent, such as n-butyllithium, in an organic solvent, such as anhydrous methyl t-butyl ether, at a temperature of, for example, 0 ℃ to room temperature. Reaction product with MX 4 The salt elimination reaction takes place to give the metallocene compound, the reaction temperature being, for example, -78 ℃ to room temperature.
The invention also provides an ethylene polymerization method, the catalyst is the supported metallocene catalyst, and the method is carried out in a single reactor to obtain a polyethylene product with wide molecular weight distribution.
In one embodiment, the ethylene polymerization process of the present invention is as follows:
pretreating a polymerization kettle, and vacuumizing the polymerization kettle at 80 ℃ for replacing nitrogen for three times; at room temperature, under the protection of nitrogen, 2.8Kg of hexane is injected into the polymerization kettle; according to the experimental plan, a quantitative 10% strength by mass solution of triethylaluminum in hexane was added. Then heating to 55 ℃, stirring the polymerization kettle for 15min, and then cooling to room temperature; adding the obtained supported metallocene catalyst into a polymerization kettle, and washing with 0.2kg of hexane to ensure that the catalyst is completely added into the polymerization kettle; introducing nitrogen in the polymerization kettle, replacing the nitrogen with ethylene, increasing the stirring speed to 900RPM, setting the polymerization pressure to be 2MPa, ensuring pressure control of ethylene feeding, heating to the polymerization temperature, starting polymerization, paying attention to the polymerization temperature change and the ethylene consumption rate change in the whole process, reacting for 60 minutes, cooling and discharging polyethylene, and cleaning the polymerization kettle.
The amount of the solvent used in the present invention is not strictly limited, and can be controlled by those skilled in the art according to the actual reaction and the need for convenient post-treatment.
The process of the present invention is illustrated below by means of specific examples, but the present invention is not limited thereto.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1:
synthesis of intermediate 1 in the reaction scheme:
weighing ligand A in a glove box 1 (Fw =281.35, 28.14 grams, 100 mmol) was placed in a 1000mL two-necked round bottom flask,the flask was removed from the glove box and transferred to a Sclenk system. Dissolved in 500mL of anhydrous ether under a high-purity nitrogen atmosphere. The round-bottom flask was cooled in an ice-water bath below 0 ℃ and a solution of n-butyllithium in hexane (2.40M/L solution, 44ml, 105mmol) was slowly added dropwise with constant stirring under a high purity nitrogen atmosphere. After the dropwise addition, the reaction system naturally rises to room temperature, and the solution is dark red. The reaction was incubated at 25 ℃ for 4h. The organolithium solution prepared above was slowly added dropwise to a solution containing dimethyldichlorosilane (Me) using a Teflon capillary under nitrogen blanket 2 SiCl 2 Fw =129.06, d =1.07g/mL,60.0mL, 500mmol) of dehydrated ether (30 mL,<0 ℃) in solution. The reaction is stirred overnight under the protection of nitrogen, liCl is filtered out by a siphon filtration method under the protection of nitrogen, and the residual solid LiCl is extracted and washed by a small amount of anhydrous ether and siphoned and filtered. The combined filtrates were vacuumed to remove the solvent and unreacted Me 2 SiCl 2 Intermediate 1 was obtained in 98% yield.
Synthesis of intermediate 2 in the reaction scheme:
the 2-methylbenzindene organic molecule (Fw =180.25,18.02g, 100mmol) was weighed into a 1000mL two-necked round-bottomed flask in an inert gas glove box, and the round-bottomed flask was transferred from the glove box to a Schlenk system. The 2-methylbenzindene is dissolved in 500mL of anhydrous ether under the protection of high-purity nitrogen, and the round-bottom flask is placed in an ice-water bath below 0 ℃. To the above 2-methylbenzindene ethyl ether solution was slowly dropped an n-butyllithium hexane solution (2.40M/L, 41.6mL, 100mmol), and after completion of the dropping, the reaction system was allowed to react while keeping at 25 ℃ for 5 hours to obtain an ethyl ether solution of 2-methylbenzindene lithium salt (intermediate 2).
Synthesis of intermediate 3 in the reaction scheme:
dissolving intermediate product 1 in anhydrous ether (500 mL) under nitrogen protection, cooling to less than 0 deg.C, slowly adding ether solution of intermediate product 2 dropwise into ether solution of intermediate product 1 by capillary siphon method, naturally heating to room temperature after dropwise addition, and stirring at 28 deg.C under high purity nitrogen atmosphere overnight. And removing LiCl from the deep red solution by a siphon filtration method, extracting and washing the residual solid once by using a small amount of anhydrous ether, and siphoning and filtering. The combined filtrates were vacuum decompressed to remove the solvent and vacuum dried to a constant weight to give intermediate 3 with a purity of greater than 95%.
Example 2:
to an ampoule containing 3.177g of intermediate (517.74 g/mol,10 mmol) was added 150mL of anhydrous methyl tert-butyl ether to give a suspension of ligand. At room temperature, add 8.33mL with a syringe n BuLi/hexane (2.4 mol/L) gave a red-brown solution. Stirring was continued at room temperature for 4h. Taking 3.773g ZrCl out of glove box 4 (thf) 2 (377.25 g/mol,10 mmol) in a 350mL Schlenk reaction flask in N 2 150mL of anhydrous methyl tert-butyl ether was added under protection to give a suspension. Slowly adding lithium salt solution of ligand into ZrCl at room temperature 4 (thf) 2 After completion of the dropwise addition, the suspension of (1.5) was stirred at room temperature for 8 hours. The reaction suspension was cherry red. And (5) pumping out the volatile matters till the weight is constant to obtain the complex. The product was a red solid with finer particles (dark red on suction from dichloro). The nuclear magnetization is shown in FIG. 1, and the dichloro and hexane in nuclear magnetization are contained in the deuterated solvent, and the product contains 0.5eq of tetrahydrofuran and 0.8eq of methyl tert-butyl ether. The nuclear magnetic purity is more than 90%. The product contained 2eq LiCl.
Example 3:
synthesis of (2-methyl-4-phenyl-indene) (N-methyl-indene [2,1-b ] indole) dimethylsilyl ] zirconium dichloride complex
0.64g of the starting material a (Fw =219.28,2.9 mmol) was weighed into an ampoule and dissolved by adding 30mL of anhydrous diethyl ether. In high purity N 2 The ampoule was cooled in an ice-water bath at 0 ℃ with stirring under protection, and 1.75mL of nBuLi/hexane (2.01 mol/L,3.5 mmol) was slowly added dropwise thereto using a syringe. After the dropwise addition, the reaction system naturally rises to room temperature, and the solution turns into black red. The reaction was stirred at rt for 4h. N is a radical of 2 Under protection in ice-water bath at 0 DEG CThe above lithium salt solution was slowly added dropwise (20 min) to 1.75mL dimethyldichlorosilane (Me) 2 SiCl 2 Fw =129.04, d =1.07g/mL,14.5 mmol) in anhydrous ether (20 mL). The solution appeared dark red, producing a large amount of LiCl, the reaction was stirred overnight at room temperature and was suction dried to give an off-white solid.
0.60g of the starting material b (Fw =206.28,2.9 mmol) was weighed into an ampoule and dissolved in 20mL of anhydrous ether, and the solution was colorless. In high purity N 2 The ampoule was placed in an ice-water bath at 0 ℃ under protection, cooled and stirred, and 1.45mL of nBuLi/hexane (2.01 mol/L,2.9 mmol) was slowly added dropwise thereto using a syringe. And (3) naturally heating the reaction system, changing the solution from colorless to yellow and finally to orange, and stirring at room temperature for 5 hours to obtain a product 2.
The product 1 which had been drained off was dissolved in 30mL of anhydrous ether, and the solution was dark red. And (3) placing the ether solution of the product 1 in a low-temperature cooling bath at the temperature of-30 ℃ for cooling and stirring, slowly dropwise adding the ether solution of the product 2 into the product 1 (15 min), naturally heating the reaction system after dropwise adding, enabling the solution to be black-red, and stirring at room temperature overnight. LiCl was removed, the solvent was spin dried, and recrystallized from petroleum ether to give 300mg of an off-white solid as product 3.
The above product 3 (Fw =481.70,1.12mmol,540 mg) was dissolved in anhydrous ether as an off-white suspension. Placing the ampoule in ice-water bath at 0 deg.C, cooling and stirring, adding water, stirring, and adding water 2 1.42mL of nBuLi/hexane (1.6 mol/L,2.24 mmol) was added slowly with the protection, the insoluble material gradually dissolved and the solution turned yellow. Naturally heating to room temperature, and stirring for 5 hours at room temperature to obtain the ligand lithium salt solution. 0.262g ZrCl was taken out of the glove box 4 (Fw =233.04, 1.12mmol) in ampoules under N 2 Under protection, 30mL of anhydrous ether was added. Reacting ZrCl 4 The ether solution is placed in a low-temperature cooling bath at the temperature of minus 40 ℃ for cooling and stirring, and the lithium salt solution of the ligand is slowly added into ZrCl 4 After the completion of the dropwise addition, the temperature was naturally raised to room temperature, and the mixture was stirred at room temperature overnight. Yellow solid is separated out, filtered and drained, and the product is orange482mg of solid, 66.7% yield. The nuclear magnetic results are shown in FIG. 2.
Example 4:
(2-methyl-4-phenyl-indene) (N-methyl-indene [2,1-b]Indole) dimethylsilyl group]Synthesis of hafnium dichloride Complex, procedure as in example 3, hfCl 4 Substitution of ZrCl 4 。
Example 5:
synthesis of [ (2-methyl-4-phenyl-indene) (N-methyl-indene [1,2-b ] indole) dimethylsilyl ] zirconium dichloride complex (procedure same as example 3), product nuclear magnetization as shown in FIG. 3.
Example 6:
[ (2-methyl-4-phenyl-indene) (N-methyl- [1,2-b)]Indole) dimethylsilyl group]Synthesis of hafnium dichloride Complex, procedure of example 3 4 Substitution of ZrCl 4 。
A catalyst loading step: under the protection of nitrogen, suspension A was prepared by mixing 1g of the support at 40 ℃ with 20ml of a toluene solution, and 2ml of MAO (methylaluminoxane) solution at a concentration of 1.1mol/L in toluene was added dropwise to suspension A and reacted for 2 hours to obtain suspension B. Meanwhile, 25. Mu.mol of the complex obtained in example 2-6 was weighed and dissolved in 10ml of a toluene solution to obtain a solution C, and 2.3ml of a 1.1mol/L MAO/toluene solution was added dropwise to the solution C, and the reaction was stirred at 40 ℃ for 1 hour to obtain an activated catalyst solution D. The solution D was added dropwise to the suspension B and the reaction was stirred at 40 ℃ for 2h. And (3) standing for layering, removing a supernatant, washing for 3 times by using 20ml of toluene, and vacuumizing and drying for 4 hours at the temperature of 40 ℃ to finally obtain the catalyst with good fluidity.
Example 7:
polymerization experiment: the catalyst is [ (2-methyl-4-phenyl-indene) (N-phenyl-indene [1,2-b ] indole) dimethylsilyl ] zirconium dichloride complex.
Pretreating a polymerization kettle, and vacuumizing the polymerization kettle at 80 ℃ for replacing nitrogen for three times; at room temperature, under the protection of nitrogen, 2.8Kg of hexane is injected into the polymerization kettle; according to the experimental plan, a quantitative 10% strength by mass solution of triethylaluminum in hexane was added. Then heating to 55 ℃, stirring the polymerization kettle for 15min, and then cooling to room temperature; adding 310mg of catalyst into a polymerization kettle, and washing with 0.2Kg of hexane to ensure that the catalyst is completely added into the polymerization kettle; introducing nitrogen in the polymerization kettle, replacing the nitrogen with ethylene, increasing the stirring speed to 900RPM, setting the polymerization pressure to be 2MPa, ensuring the pressure to control the feeding of ethylene, heating to the polymerization temperature of 60 ℃, starting polymerization, paying attention to the polymerization temperature change and the ethylene consumption rate change in the whole process, reacting for 60 minutes, cooling and discharging 850g of polyethylene, and cleaning the polymerization kettle. The catalytic activity of the catalyst is 2740g PE/gcat, the molecular weight distribution is 5.9, and the molecular weight Mw 360100.
Example 8:
polymerization experiment: the catalyst was (2-methyl-4-phenyl-indene) (N-methyl-indene [2,1-b ] indole) dimethylsilyl ] zirconium dichloride complex (example 3 catalyst).
Pretreating a polymerization kettle, and vacuumizing the polymerization kettle at 80 ℃ for replacing nitrogen for three times; at room temperature, under the protection of nitrogen, 2.8Kg of hexane is injected into the polymerization kettle; according to the experimental plan, a quantitative 10% strength by mass solution of triethylaluminum in hexane was added. Then heating to 55 ℃, stirring the polymerization kettle for 15min, and then cooling to room temperature; 305mg of the catalyst is added into a polymerization kettle, and 0.2Kg of hexane is used for washing to ensure that the catalyst is completely added into the polymerization kettle; introducing nitrogen in the polymerization kettle, replacing the nitrogen with ethylene, increasing the stirring speed to 900RPM, setting the polymerization pressure to be 2MPa, ensuring the pressure to control the feeding of ethylene, heating to the polymerization temperature of 80 ℃, starting polymerization, paying attention to the polymerization temperature change and the ethylene consumption rate change in the whole process, reacting for 60 minutes, cooling and discharging 1200g of polyethylene, and cleaning the polymerization kettle. The catalyst has catalytic activity of 3934g PE/gcat, molecular weight distribution of 5.3 and molecular weight Mw 252520.
Example 9:
polymerization experiment: (2-methyl-4-phenyl-indene) (N-methyl-indene [2,1-b ] indole) dimethylsilyl ] hafnium dichloride complex (example 4 catalyst).
Pretreating a polymerization kettle, and vacuumizing the polymerization kettle at 80 ℃ for replacing nitrogen for three times; at room temperature, under the protection of nitrogen, 2.8Kg of hexane is injected into the polymerization kettle; according to the experimental plan, a quantitative 10% strength by mass solution of triethylaluminum in hexane was added. Then heating to 55 ℃, stirring the polymerization kettle for 15min, and then cooling to room temperature; adding 500mg of catalyst into a polymerization kettle, and washing with 0.2Kg of hexane to ensure that the catalyst is completely added into the polymerization kettle; introducing nitrogen in the polymerization kettle, replacing the nitrogen with ethylene, increasing the stirring speed to 900RPM, setting the polymerization pressure to be 2MPa, ensuring the pressure to control the feeding of ethylene, heating to the polymerization temperature of 60 ℃, starting polymerization, paying attention to the polymerization temperature change and the ethylene consumption rate change in the whole process, reacting for 60 minutes, cooling and discharging 950g of polyethylene, and cleaning the polymerization kettle. The catalyst has catalytic activity of 1900g PE/gcat, molecular weight distribution of 6.5 and molecular weight Mw 768520.
Example 10:
polymerization experiment: the catalyst was [ (2-methyl-4-phenyl-indene) (N-phenyl-indene [1,2-b ] indole) dimethylsilyl ] zirconium dichloride complex (example 5 catalyst).
Pretreating a polymerization kettle, and vacuumizing the polymerization kettle at 80 ℃ for replacing nitrogen for three times; at room temperature, under the protection of nitrogen, 2.8Kg of hexane is injected into the polymerization kettle; according to the experimental plan, a quantitative 10% strength by mass solution of triethylaluminum in hexane was added. Then heating to 55 ℃, stirring the polymerization kettle for 15min, and then cooling to room temperature; adding 450mg of catalyst into a polymerization kettle, and washing with 0.2Kg of hexane to ensure that the catalyst is completely added into the polymerization kettle; introducing nitrogen in the polymerization kettle, replacing the nitrogen with ethylene, increasing the stirring speed to 900RPM, setting the polymerization pressure to be 2MPa, ensuring the pressure to control the feeding of ethylene, heating to the polymerization temperature of 85 ℃, starting polymerization, paying attention to the polymerization temperature change and the ethylene consumption rate change in the whole process, reacting for 60 minutes, cooling and discharging 1100g of polyethylene, and cleaning the polymerization kettle. The catalytic activity of the catalyst is 2445g PE/gcat, the molecular weight distribution is 5.9, and the molecular weight Mw 515110.
Example 11:
polymerization experiment: [ (2-methyl-4-phenyl-indene) (N-methyl-indene [1,2-b ] indole) dimethylsilyl ] zirconium dichloride complex (example 5 catalyst).
Pretreating a polymerization kettle, and vacuumizing the polymerization kettle at 80 ℃ for replacing nitrogen for three times; at room temperature, under the protection of nitrogen, 2.8Kg of hexane is injected into the polymerization kettle; according to the experimental plan, a quantitative 10% strength by mass solution of triethylaluminum in hexane was added. Then heating to 55 ℃, stirring the polymerization kettle for 15min, and then cooling to room temperature; adding 430mg of catalyst into a polymerization kettle, and washing with 0.2Kg of hexane to ensure that the catalyst is completely added into the polymerization kettle; introducing nitrogen in the polymerization kettle, replacing the nitrogen with ethylene, increasing the stirring speed to 900RPM, setting the polymerization pressure to be 2MPa, ensuring the pressure to control the feeding of ethylene, heating to the polymerization temperature of 65 ℃, starting polymerization, paying attention to the polymerization temperature change and the ethylene consumption rate change in the whole process, reacting for 60 minutes, cooling and discharging 780g of polyethylene, and cleaning the polymerization kettle. Catalytic activity of catalyst 1814g PE/gcat, molecular weight distribution 6.1, molecular weight Mw 267800
Example 12:
polymerization experiment: [ (2-methyl-4-phenyl-indene) (N-methyl- [1,2-b ] indole) dimethylsilyl ] hafnium dichloride complex (example 6 catalyst).
Pretreating a polymerization kettle, and vacuumizing the polymerization kettle at 80 ℃ for replacing nitrogen for three times; at room temperature, under the protection of nitrogen, 2.8Kg of hexane is injected into the polymerization kettle; according to the experimental plan, a quantitative 10% strength by mass solution of triethylaluminum in hexane was added. Then heating to 55 ℃, stirring and treating the polymerization kettle for 15min, and then cooling to room temperature; adding 700mg of catalyst into a polymerization kettle, and washing with 0.2Kg of hexane to ensure that the catalyst is completely added into the polymerization kettle; introducing nitrogen in the polymerization kettle, replacing the nitrogen with ethylene, increasing the stirring speed to 900RPM, setting the polymerization pressure to be 2MPa, ensuring the pressure to control the feeding of ethylene, heating to the polymerization temperature of 85 ℃, starting polymerization, paying attention to the polymerization temperature change and the ethylene consumption rate change in the whole process, reacting for 60 minutes, cooling and discharging 800g of polyethylene, and cleaning the polymerization kettle. The catalytic activity of the catalyst is 1143g PE/gcat, the molecular weight distribution is 6.3, and the molecular weight Mw 568800
The polymerization characterization results of examples 7-12 are shown in Table 1 below.
TABLE 1 characterization results for polymerization of examples 7-12
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. An ethylene polymerization method is characterized in that the catalyst is a supported metallocene catalyst, the supported metallocene catalyst comprises a carrier and a metallocene compound, the metallocene compound is supported on the carrier, the metallocene compound has a cis structure and a trans structure in a spatial structure, and the metallocene compound has a structure shown as the following formula I or formula II:
wherein M is zirconium, hafnium or titanium; t is C or Si; x is independently selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, mercapto, carboxyl, amino, phosphino and OSO 2 CF 3 (ii) a Q is independently selected from hydrogen, halogen, alkyl, alkoxy, haloalkyl; e is a group VA element; r 1 ，R 2 ，R 3 ，R 4 The same or different from each other, and are independently hydrogen, methyl or phenyl.
2. The ethylene polymerization process according to claim 1, characterized in that said xs, equal to or different from each other, are independently selected from halogens; said Q's are the same or different from each other and are independently selected from alkyl groups.
3. The ethylene polymerization process of claim 2, wherein X is chlorine or bromine.
4. The ethylene polymerization process of claim 1, wherein the preparation of the metallocene compound comprises:
step 1, ligands A1 and Q 2 TA 2 Reacting to prepare intermediate 1, lithiating ligand A2 with alkyl lithium reagent to prepare intermediate 2, and preparingThe intermediate product 1 and the intermediate product 2 are subjected to a salt elimination reaction to obtain an intermediate product 3, which is shown as a formula III below;
step 2, intermediate 3 with MX 4 The metallocene compound is obtained by salt elimination reaction, and comprises a cis structure and a trans structure, which are shown in the following formula IV;
wherein A is halogen.
5. The process for polymerization of ethylene according to claim 4, wherein Q is an alkyl group, and the ligand A1 is lithiated with an alkyllithium reagent and then with Q 2 TA 2 The salt elimination reaction takes place to give intermediate 1.
6. The ethylene polymerization process of claim 4, wherein X is a halogen, and the intermediate product 3 is lithiated with an alkyllithium reagent and then with MX 4 The salt elimination reaction occurs to obtain the metallocene compound.
7. The ethylene polymerization process according to claim 4, wherein the supported metallocene catalyst is obtained by directly supporting the metallocene compounds having cis-structure and trans-structure on a carrier without separation.
8. Ethylene polymerization process according to claim 1, characterized in that it is carried out in a single reactor.
9. Polyethylene produced by the ethylene polymerization process according to any one of claims 1-8, characterized in that the polyethylene has a bimodal distribution and/or a molecular weight distribution breadth of 5-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110035707.6A CN112940158B (en) | 2021-01-12 | 2021-01-12 | Supported metallocene catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110035707.6A CN112940158B (en) | 2021-01-12 | 2021-01-12 | Supported metallocene catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112940158A CN112940158A (en) | 2021-06-11 |
| CN112940158B true CN112940158B (en) | 2023-04-07 |
Family
ID=76235262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110035707.6A Active CN112940158B (en) | 2021-01-12 | 2021-01-12 | Supported metallocene catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112940158B (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6756455B2 (en) * | 2002-05-31 | 2004-06-29 | Equistar Chemicals, Lp | High-temperature solution process for polyolefin manufacture |
| KR20150066344A (en) * | 2013-12-06 | 2015-06-16 | 주식회사 엘지화학 | Metallocene compound, catalyst composition comprising the same, and method for preparation of olefin-based polymer using the same |
| EP3173429B1 (en) * | 2014-12-15 | 2019-03-20 | LG Chem, Ltd. | Metallocene compound, metallocene supported catalyst, and method for preparing polyolefin using same |
| CN105985383B (en) * | 2015-02-06 | 2019-09-03 | 中国石油天然气股份有限公司 | The application of metallocene complex containing heteroatomic π-ligand and preparation method thereof, its catalyst system and catalyst system |
-
2021
- 2021-01-12 CN CN202110035707.6A patent/CN112940158B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112940158A (en) | 2021-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114127129A (en) | Improved preparation of catalyst systems | |
| CN106661142B (en) | Ligand compound, transistion metal compound and the carbon monoxide-olefin polymeric comprising the compound | |
| CN105452268B (en) | Metallocene compound, the carbon monoxide-olefin polymeric comprising it and the method for preparing olefin polymer using it | |
| CN1139604C (en) | Supported olefin polymerization catalyst | |
| JP6420911B2 (en) | Hybrid supported catalyst and method for producing olefin polymer using the same | |
| CN106488923B (en) | Ligand compound, transistion metal compound and the carbon monoxide-olefin polymeric comprising the transistion metal compound | |
| CN105473601B (en) | Metallocene compound, comprising its carbon monoxide-olefin polymeric and using it prepare the method for olefin polymer | |
| EP3312201B1 (en) | Supported hybrid catalyst and method for preparing olefin polymer using the same | |
| JP6511151B2 (en) | Method of producing polyolefin | |
| CN112088173B (en) | Polyethylene and chlorinated polyethylene thereof | |
| CN107075008A (en) | The method of Metallocenic compound, the catalyst of carried metal cyclopentadienyl and the catalyst preparation polyolefin using carried metal cyclopentadienyl | |
| CN101885791B (en) | Broad/multimodal distributed polyolefin catalyst, preparation and application thereof | |
| WO2016093678A1 (en) | Supported metallocene catalyst and polyolefin preparation method using same | |
| CN105111336A (en) | Electron donor of ethylene polymerization catalyst, ball-like catalyst and preparation method | |
| KR101725351B1 (en) | Method for preparing supported hybrid metallocene catalyst, and supported hybrid metallocene catalyst using the same | |
| CN112940158B (en) | Supported metallocene catalyst and preparation method and application thereof | |
| EP2623522B1 (en) | Preparation method of hybrid supported metallocene catalyst | |
| KR20180040405A (en) | Process for preparing polypropylene | |
| CN107459592A (en) | Modified silica gel carrier and supported metallocene catalyst and preparation method and metallocene catalyst system | |
| CN117050215A (en) | Polyethylene and chlorinated polyethylene thereof | |
| JP3731196B2 (en) | Method for producing copolymer | |
| CN112759679B (en) | Supported non-metallocene catalyst and preparation and application thereof | |
| KR20140015666A (en) | Tandem catalyst system comprising transition metal compound for alpha-olefin synthesis, and preparation method for polyethylene using the system | |
| EP0965600A1 (en) | Process for preparing polymer by using copper compound | |
| CN112778441B (en) | Supported metallocene catalyst and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230720 Address after: 100011 Beijing city Dongcheng District No. 16 Andrew Patentee after: PETROCHINA Co.,Ltd. Patentee after: China Petroleum (Shanghai) New Materials Research Institute Co.,Ltd. Address before: 100007 Oil Mansion, 9 North Avenue, Dongcheng District, Beijing, Dongzhimen Patentee before: PETROCHINA Co.,Ltd. |
|
| TR01 | Transfer of patent right |