WO2025232102A1 - 烯烃聚合催化剂及其制备方法、烯烃聚合的方法 - Google Patents

烯烃聚合催化剂及其制备方法、烯烃聚合的方法

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WO2025232102A1
WO2025232102A1 PCT/CN2024/126975 CN2024126975W WO2025232102A1 WO 2025232102 A1 WO2025232102 A1 WO 2025232102A1 CN 2024126975 W CN2024126975 W CN 2024126975W WO 2025232102 A1 WO2025232102 A1 WO 2025232102A1
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catalyst
sio2
olefin polymerization
formula
preparation
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French (fr)
Inventor
王玉如
任鹤
高宇新
曹婷婷
倪双阳
王伟众
张瑞
张明强
孙维
王磊
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Petrochina Co Ltd
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/08—Butenes
    • 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
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/643—Component covered by group C08F4/64 with a metal or compound covered by group C08F4/44 other than an organo-aluminium compound

Definitions

  • This invention relates to the field of chemical synthesis technology, specifically to an olefin polymerization catalyst and its preparation method, as well as a method for olefin polymerization.
  • Poly(4-methyl-1-pentene) is a crystalline resin with a stereoregular structure. This unique structure endows it with excellent properties, including superior chemical resistance, mechanical properties, and processability; excellent electrical insulation properties; low dielectric properties; optical properties; air permeability; and easy peeling properties. Therefore, this type of high-end thermoplastic resin has important applications in fiber materials, release materials, high-end medical materials, and electronic materials. It is particularly suitable for insulators for 5G and 6G communication high-frequency devices, pharmaceutical sustained-release membranes, ECMO membranes, and other advanced network communication, microporous materials, and high-end medical fields. The demand for PMP products is expected to grow rapidly.
  • 4-Methyl-1-pentene monomers have a unique structure with long side chains and an isopropyl group at the end, making them one of the most sterically hindered monomers among commonly used olefin monomers, exhibiting a strong steric hindrance effect. Therefore, conventionally used high-activity polyolefin catalysts show very low activity for the polymerization of 4-methyl-1-pentene, with slow coordination and insertion rates. For example, metallocene catalysts, due to their single metal center, result in a narrow molecular weight distribution of polymerized polyolefins (PMPs), typically below 3.
  • PMPs polymerized polyolefins
  • non-metallocene catalysts lack ring-fixing properties, have a more open steric environment, and can achieve chirality of the metal center through racemic mixing and selective optimization of skeletal substituents, balancing high activity and isotacticity. This has led to increasing interest in non-metallocene catalysts.
  • Pyridine-amine hafnium catalysts were discovered in 2003 by Dow Chemical and Symyx using high-throughput screening. These catalysts exhibit superior catalytic performance in olefin polymerization, demonstrating excellent stereoselectivity. They can catalyze the polymerization of propylene and other ⁇ -olefins at high temperatures to prepare highly isotactic polyolefin materials. Furthermore, these catalysts also possess good copolymerization properties, capable of catalyzing the copolymerization of ethylene, propylene, and ⁇ -olefins to prepare polyolefin materials with high ⁇ -olefin insertion rates. Therefore, pyridine-amine hafnium catalysts have received widespread attention in the polyolefin field.
  • pyridine-amine hafnium catalysts are mainly used for homogeneous solution polymerization, and can be used for the highly active solution polymerization of 4-methyl-1-pentene.
  • the production of PMP resin using pyridine-amine hafnium catalysts in solution polymerization processes faces a series of problems. For example, "explosive polymerization” is prone to occur, the morphology of the polymerization product is poor, the reactor is prone to scaling, the separation of product and catalyst is difficult, and continuous production is difficult to achieve.
  • the pyridine-amine hafnium catalyst can be supported to allow the monomers to be directionally polymerized into regular spherical particles.
  • the overall viscosity of the polymerization system can be controlled to ensure that the product performance meets the required specifications.
  • continuous gas-phase and slurry polymerization can be achieved by controlling the polymer morphology and preventing reactor contamination.
  • Professor Marks's research group at Northwestern University conducted research on the supported pyridine-amine hafnium catalyst (Marks et al. ACS Catal. 2021, 11, 3239-3250; Marks et al. ACS Catal. 2018, 8, 4893-4901.).
  • This invention addresses the problems of existing homogeneous pyridine-amine-based hafnium catalysts in the production of polyolefins, such as reactor scaling, difficulty in separating products and catalysts, difficulty in achieving continuous production, and poor product morphology, as well as the problem of existing supported pyridine-amine-based hafnium catalysts having low activity and failing to meet application requirements.
  • the invention provides an olefin polymerization catalyst, its preparation method, and a method for olefin polymerization.
  • a first aspect of the present invention provides an olefin polymerization catalyst comprising a cationic pyridineamine hafnium active component with the structure shown in formula (1) and a modified SiO2 support; wherein the modified SiO2 support comprises a SiO2 matrix and an anionic boron compound with the structure shown in formula (2); wherein the B in the anionic boron compound is connected to at least a portion of the O on the surface of the SiO2 matrix;
  • R1 , R2 , R3 , R4 , R5 , R6 , R7, R8 , R9 , R10 , R11 , R12 , R13 , R14 , and R15 are each independently selected from -H or C1 - C9 hydrocarbon groups; R16 and R17 are each independently selected from -H or C1 - C9 hydrocarbon groups, and when R16 and R17 are each independently C2 - C6 alkyl groups, they can close into a ring.
  • the catalyst Based on the total weight of the catalyst, the catalyst contains 1-5 wt% Hf, 0.2-0.8 wt% B, and 25-60 wt% Si.
  • a second aspect of the present invention provides a method for preparing an olefin polymerization catalyst, comprising:
  • the activated support is reacted with B( C6F5 ) 3 to obtain a first product; then the first product is reacted with an ionizing agent to obtain a SiO2- supported ion - paired boron compound.
  • R1 , R2 , R3 , R4 , R5 , R6 , R7 , R8 , R9, R10 , R11 , R12 , R13 , R14 , and R15 are each independently selected from -H or C1 - C9 hydrocarbon groups;
  • R16 and R17 are each independently selected from -H or C1 - C9 hydrocarbon groups, and when R16 and R17 are each independently C2 - C6 alkyl groups, they can close to form a ring;
  • the weight ratio of the activated support to B(C6F5)3 is 1 :(0.3-1); the molar ratio of the ionizing reagent to B( C6F5 ) 3 is ( 1-2 ):1; and the molar ratio of Hf: SiO2 -loaded ions in the pyridineamine hafnium complex to B in the boron compound is (0.6-1.6):1.
  • the third aspect of the present invention provides an olefin polymerization catalyst prepared by the preparation method described in the second aspect above.
  • a fourth aspect of the present invention provides a method for olefin polymerization, comprising: polymerizing an olefin monomer in the presence of a main catalyst and an optional co-catalyst to obtain a polymerization product;
  • the main catalyst is the olefin polymerization catalyst described in the first or third aspect above.
  • the olefin polymerization catalyst provided by the present invention has high catalytic polymerization activity. Compared with the existing reported pyridine-amine hafnium catalysts supported on alumina sulfate (AlS) or zirconium sulfate (ZrS), the catalyst provided by the present invention has significantly improved activity and has good industrialization prospects.
  • the components of the olefin polymerization catalyst provided by the present invention are bonded by chemical bonds (Si-O covalent bonds, B-O covalent bonds and Hf-B ionic bonds). Compared with the catalyst prepared by simple blend adsorption, it has better stability, and the olefin polymerization reaction is stable and efficient. It can effectively solve the problems of "explosive polymerization", poor morphology of polymerization products and difficulty in continuous production in homogeneous catalyst systems.
  • Figure 1 is a morphology diagram of poly(4-methyl-1-pentene) prepared using the catalyst prepared in Example 1 of the present invention.
  • Figure 2 shows the morphology of poly(4-methyl-1-pentene) prepared using the catalyst prepared in Comparative Example 4 of the present invention.
  • the first aspect of the present invention provides an olefin polymerization catalyst, the catalyst comprising a cationic pyridineamine hafnium active component with the structure shown in formula (1), and a modified SiO2 support; wherein the modified SiO2 support comprises a SiO2 matrix and an anionic boron compound with the structure shown in formula (2); the B in the anionic boron compound is connected to at least a portion of the O on the surface of the SiO2 matrix;
  • R1 , R2 , R3 , R4 , R5 , R6 , R7, R8 , R9 , R10 , R11 , R12 , R13 , R14 , and R15 are each independently selected from -H or C1 - C9 hydrocarbon groups; R16 and R17 are each independently selected from -H or C1 - C9 hydrocarbon groups, and when R16 and R17 are each independently C2 - C6 alkyl groups, they can close into a ring.
  • the catalyst Based on the total weight of the catalyst, the catalyst contains 1-5 wt% Hf, 0.2-0.8 wt% B, and 25-60 wt% Si.
  • the catalyst provided by this invention is a novel supported pyridine-amine hafnium olefin polymerization catalyst with a specific structure.
  • the bonding relationship between the cationic pyridine-amine hafnium active component and the modified SiO2 support is shown in Equation (7). It should be explained and emphasized by the inventor that Equation (7) is only used to illustrate the structure of the catalyst and the bonding relationship between the components, and does not represent the quantitative relationship between the components.
  • the cationic pyridineamine hafnium active component (hafnium metal center) in this catalyst is "free" outside the modified SiO2 support, which can effectively reduce the activity loss caused by loading and help maintain the high polymerization activity of the catalyst;
  • the matrix of the modified SiO2 support in this catalyst is connected to the anionic boron compound through chemical bonds, which has better stability and allows the modified SiO2 support to have a higher boron content, enabling it to load more hafnium metal centers.
  • the anionic boron compound can act on the hafnium metal center over a long distance through ionic bonds, ensuring that the polymerization can proceed smoothly and continuously without the "explosive polymerization" problem of the homogeneous catalyst system.
  • the polymerization product has a good morphology and a narrow product particle size distribution.
  • This catalyst can be used for the homopolymerization or copolymerization of various olefin monomers, and can especially meet the requirements of solution polymerization process for PMP for catalyst activity and stability.
  • the cationic pyridineamine hafnium active component represented by formula (1) provides the hafnium metal center of the olefin polymerization catalyst.
  • R1 , R2 , R3 , R4, R5 , R6 , R7 , R8 , R9 , R10 , R11 , R12 , R13 , R14 , and R15 are each independently selected from -H or C1 - C4 hydrocarbon groups, which makes the cationic pyridineamine hafnium active component have less steric hindrance, which is more conducive to the insertion of comonomers during the polymerization reaction and obtains high catalytic activity.
  • the cationic pyridine-amine hafnium active component has the structure shown in formula (3) or formula (4), which can make the olefin polymerization catalyst have higher catalytic activity. More preferably, the cationic pyridine-amine hafnium active component has the structure shown in formula (4).
  • the Hf content, B content, and Si content are 4-5 wt% Hf content, 0.6-0.8 wt% B content, and 25-30 wt% Si content, respectively, thereby enabling the olefin polymerization catalyst to have further improved catalytic activity.
  • the elemental content in the catalyst is determined according to the method specified in GB/T 30902-2014 and using ICP (inductively coupled plasma spectrometry).
  • the olefin polymerization catalyst comprises a cationic pyridinamine hafnium active component with the structure shown in formula (4) and a modified SiO2 support; wherein the modified SiO2 support comprises a SiO2 matrix and an anionic boron compound with the structure shown in formula (2); the B in the anionic boron compound is connected to at least a portion of the O on the surface of the SiO2 matrix; based on the total weight of the catalyst, the catalyst contains 4.7-5 wt% Hf, 0.6-0.75 wt% B, and 25-27 wt% Si.
  • the catalyst of the above preferred embodiment has better overall performance by balancing high polymerization activity, excellent stability, and good morphology of the polymerization product.
  • a second aspect of the present invention provides a method for preparing an olefin polymerization catalyst, comprising:
  • the activated support is reacted with B( C6F5 ) 3 to obtain a first product; then the first product is reacted with an ionizing agent to obtain a SiO2- supported ion - paired boron compound.
  • R1 , R2 , R3 , R4 , R5 , R6 , R7 , R8 , R9, R10 , R11 , R12 , R13 , R14 , and R15 are each independently selected from -H or C1 - C9 hydrocarbon groups;
  • R16 and R17 are each independently selected from -H or C1 - C9 hydrocarbon groups, and when R16 and R17 are each independently C2 - C6 alkyl groups, they can close to form a ring;
  • the weight ratio of the activated support to B(C6F5)3 is 1 :(0.3-1); the molar ratio of the ionizing reagent to B( C6F5 ) 3 is ( 1-2 ):1; and the molar ratio of Hf: SiO2 -loaded ions in the pyridineamine hafnium complex to B in the boron compound is (0.6-1.6):1.
  • the SiO2 particles in the preparation method of the olefin polymerization catalyst, in step (1), can be any self-made or commercially available SiO2 particles that can be used as a catalyst support.
  • the average particle size of the SiO2 particles is 20-200 ⁇ m, which is beneficial to the olefin polymerization of the obtained catalyst.
  • the catalyst was used to prepare polymer products with low fine powder content and uniform particle size distribution in the catalytic polymerization of olefin monomers.
  • the average particle size refers to D50, which can be determined using a laser particle size analyzer according to the method specified in GB/T 41949-2022.
  • the activation treatment in the preparation method of the olefin polymerization catalyst, in step (1), can be carried out by heating the SiO2 particles.
  • the activation treatment conditions include: a temperature of 200-700°C and a time of 1-10h.
  • the activation treatment includes: placing the SiO2 particles in a heating device, heating them to 200-250°C at a heating rate of 1-5°C/min, holding the temperature for 0.5-2 hours, and then heating them to 500-700°C at a heating rate of 1-5°C/min, holding the temperature for 2-6 hours to obtain an activated carrier.
  • the SiO2 particles are activated to form isolated silanol groups on the surface of the SiO2 particles so that they can be chemically bonded to the boron atoms in B( C6F5 ) 3 in step (2).
  • the content of silanol groups in the activated support is 0.5-2 mmol/g, preferably 1-1.5 mmol/g, which is conducive to the forward reaction of the activated support and B( C6F5 ) 3 in step (2) and promotes the formation of BO bonds.
  • the content of silanol groups can be determined by nuclear magnetic resonance hydrogen spectroscopy.
  • step (2) has a relatively broad limitation on the first solvent, as long as it can dissolve B( C6F5 ) 3 .
  • the first solvent can be selected from at least one of toluene, n-pentane, n-hexane, cyclohexane, and n-heptane, which is beneficial to the dissolution of B( C6F5 ) 3 and the dispersion of the activated support.
  • the first solvent can be further preferably toluene and/or n-heptane.
  • the activated support is first mixed with the first solvent to obtain a mixed slurry, and then the mixed slurry is mixed with B( C6F5 ) 3 to undergo the first reaction.
  • the conditions for the first reaction include: a temperature of 0-50°C and a time of 1-12 h.
  • the amount of the first solvent used is relatively limited, as long as it can fully dissolve the above- mentioned amount of B( C6F5 ) 3.
  • the weight ratio of the activated support to the first solvent is 1:(15-25), which is more conducive to the dissolution of B( C6F5 ) 3 and the uniform dispersion of the activated support.
  • step (2) in the preparation method of the olefin polymerization catalyst, in step (2), for the second reaction, preferably, the product system (first product) obtained from the first reaction is mixed with the ionizing reagent and a second reaction occurs.
  • the conditions for the second reaction include: the reaction is carried out under light-protected conditions, the temperature is 0-50°C, and the time is 6-24 hours.
  • the ionizing agent in the preparation method of the olefin polymerization catalyst, in step (2), preferably, can be selected from CPh3Cl and/or NPhMe2 , which can promote the forward shift of the reversible reaction of BO bonding and form a more stable BO bond.
  • the ionizing agent is further preferably CPh3Cl .
  • the ionizing agent is added in the form of a solution.
  • the ionizing agent is pre-prepared with an organic solvent to form a solution with a concentration of 0.5-1 mol/L.
  • the organic solvent may be selected from at least one of toluene, xylene, and ethylbenzene.
  • step (2) a SiO2 -supported ion-pair boron compound (support) is prepared by sequentially performing the first reaction and the second reaction.
  • the ionizing agent is CPh3Cl
  • the main reaction process in step (2) is illustrated as follows:
  • step (2) When the ionizing reagent is NPhMe2 , the main reaction process in step (2) is shown below:
  • the preparation method of the SiO2- supported ion -pair boron compound differs from the direct mixing method.
  • the direct mixing method involves simply dissolving and mixing the raw materials in solution, with the SiO2 support and B( C6F5 ) 3 primarily undergoing physical adsorption. This results in a low boron content in the prepared support, significantly reducing the loading of the active component and decreasing the catalyst activity.
  • this invention prepares the SiO2 -supported ion -pair boron compound through a chemical reaction.
  • the SiO2 support and B( C6F5 ) 3 are bonded by chemical bonds, which significantly increases the boron content in the support and also improves the stability of the O and B atom bond, making it more favorable for the subsequent loading of pyridine-amine hafnium complexes onto the support.
  • the content of B in the SiO2- supported ion-pair boron compound is 0.2-0.8 mmol/g, which is more conducive to the loading of the pyridine-amine hafnium complex on the support in step (3).
  • the content of B in the carrier is determined according to the method specified in GB/T 30902-2014 and using ICP (inductively coupled plasma spectrometry).
  • the second solvent is an aromatic hydrocarbon solvent, preferably at least one of benzene, toluene and ethylbenzene.
  • the pyridine-amine hafnium complex is first mixed with the second solvent, and then the SiO2 -supported ion-paired boron compound is added to mix and undergo an ion exchange reaction to obtain a solid.
  • the solid is then purified to obtain the olefin polymerization catalyst.
  • the conditions for the ion exchange reaction include: a temperature of 0-50°C and a time of 0.5-5 h.
  • the amount of the second agent used in step (3) is relatively limited, as long as it can fully dissolve the pyridine-amine hafnium complex.
  • the weight ratio of the pyridine-amine hafnium complex to the second solvent is 1:(20-60).
  • step (3) a cationic pyridine amino-based hafnium active component and a boron compound supported on SiO2 to counteract the anion (containing anionic boron compound) are generated through the ion exchange reaction.
  • the main reaction process is illustrated below:
  • the cationic pyridine-amine hafnium active component (hafnium metal center) is "free" outside the modified SiO2 support, which can effectively reduce the activity loss caused by loading and help maintain the high polymerization activity of the catalyst.
  • the anionic boron compound can act on the hafnium metal center over a long distance through ionic bonds, ensuring that the polymerization can proceed smoothly and continuously without the "explosive polymerization" problem of the homogeneous catalyst system.
  • the polymerization product has good morphology and a narrow product particle size distribution.
  • the pyridine-amine hafnium complex in the preparation method of the olefin polymerization catalyst, in step (3), preferably, has the structure shown in formula (5) or formula (6), which enables the prepared olefin polymerization catalyst to have higher catalytic activity. More preferably, the pyridine-amine hafnium complex has the structure shown in formula (6).
  • the feed amounts of each raw material while satisfying the above-mentioned limitations, preferably have the following characteristics: the weight ratio of the activated support to B( C6F5 ) 3 is 1:(0.6-1); the molar ratio of the ionizing reagent to B( C6F5 ) 3 is ( 1.1-1.5 ):1; and the molar ratio of Hf in the pyridine-amine hafnium complex to B in the boron compound supported by SiO2 is (1-1.6):1.
  • the prepared catalyst to have better comprehensive performance in terms of high polymerization activity, excellent stability, and good morphology of the polymerization product.
  • the third aspect of the present invention provides an olefin polymerization catalyst prepared by the preparation method described in the second aspect above.
  • the catalyst prepared by the method described in the second aspect above has the same structure, composition and performance as the olefin polymerization catalyst described in the first aspect above, and will not be repeated here.
  • a fourth aspect of the present invention provides a method for olefin polymerization, comprising: polymerizing an olefin monomer in the presence of a main catalyst and an optional co-catalyst to obtain a polymerization product;
  • the main catalyst is the olefin polymerization catalyst described in the first or third aspect above.
  • the method for olefin polymerization has a broad definition of the olefin monomer, and preferably can be selected from at least one of 4-methyl-1-pentene, ethylene, propylene, 1-butene, 1-hexene and 1-octene.
  • the olefin polymerization catalyst in the method for olefin polymerization, can catalyze olefin polymerization with or without a co-catalyst, exhibiting high activity.
  • the co-catalyst can be an organoaluminum compound, including but not limited to triisobutylaluminum, triethylaluminum, tri-n-hexylaluminum, trimethylaluminum, diethylaluminum chloride, etc., preferably triisobutylaluminum.
  • the molar ratio of Al in the organoaluminum compound to Hf in the olefin polymerization catalyst is (0-200):1.
  • the polymerization reaction is preferably carried out by gas-phase polymerization or slurry polymerization.
  • the olefin polymerization method provided by this invention can catalyze olefin polymerization with high activity, the reaction process is stable, which is conducive to continuous production, and the polymerization product has good morphology and a narrow particle size distribution.
  • this method can solve the problems of insufficient reactivity, unstable reaction, and difficulty in continuous production in the preparation of PMP by existing solution polymerization processes.
  • the molar ratio of the initiator G and the structural units contained in the polymer was calculated by the amount of raw materials fed.
  • This preparation example illustrates the preparation of pyridineamine-based hafnium complexes.
  • Hf-1 The pyridine-amine hafnium complex (denoted as Hf-1) was prepared according to the method described in the literature (Gregory J Domski, James M Eagan, Claudio De Rosa, et al. Combined Experimental and Theoretical Approach for Living and Isoselective Propylene Polymerization[J].ACS Catal.2017,7,6930-6937).
  • Hf-1 has the structure shown in formula (4).
  • This preparation example illustrates the preparation of pyridineamine-based hafnium complexes.
  • Hf-2 The pyridine-amine hafnium complex (denoted as Hf-2) was prepared according to the method in the literature (Gregory J Domski, James M Eagan, Claudio De Rosa, et al. Combined Experimental and Theoretical Approach for Living and Isoselective Propylene Polymerization[J].ACS Catal.2017,7,6930-6937).
  • Hf-2 has the structure shown in formula (3).
  • This preparation example illustrates the preparation of the activated support.
  • This preparation example illustrates the preparation of SiO2 -supported ion-pair boron compounds.
  • the activated support Z-1 (1 g) prepared in Preparation Example 3 was dispersed in 20 mL of anhydrous toluene solvent to obtain a mixed slurry; then B( C6F5 ) 3 (0.6 g, 1.17 mmol) was added, and the mixture was stirred at 25 °C for 4 h to carry out the first reaction, obtaining the first product; the ionizing reagent CPh3Cl (0.42 g, 1.52 mmol) was dissolved in 2 mL of toluene and added to the first product, and the mixture was stirred at 25 °C in the dark for 12 h to carry out the second reaction.
  • ICP-AES Inductively coupled plasma atomic emission spectrometry
  • This preparation example illustrates the preparation of SiO2 -supported ion-pair boron compounds.
  • Preparation Example 5 The method of Preparation Example 5 was followed, except that in Preparation Example 6, the activated support Z-1 (1g) obtained in Preparation Example 3 was dispersed in 20mL of anhydrous n-pentane solvent to obtain a mixed slurry.
  • the conditions of the first reaction were adjusted (temperature was 0°C, reaction time was 12h), and the conditions of the second reaction were adjusted (temperature was 0°C, reaction time was 24h). All other steps and conditions were the same as in Preparation 5, and SiO2 -supported ion-pair boron compound (denoted as S-2) was obtained.
  • Preparation Example 5 The method of Preparation Example 5 was followed, except that in Preparation Example 7, the activated support Z-2 (1g) obtained in Preparation Example 4 was dispersed in 20mL of anhydrous n-heptane solvent to obtain a mixed slurry, and the conditions of the first reaction were adjusted (temperature 50°C, reaction time 1h), and the conditions of the second reaction were adjusted.
  • the conditions (temperature 50°C, reaction time 6h) were the same as those in preparation 5, and other steps and conditions were the same to obtain the SiO2 -supported ion-pair boron compound (denoted as S-3).
  • This preparation example illustrates the preparation of SiO2 -supported ion-pair boron compounds.
  • Preparation Example 5 The method of Preparation Example 5 was followed, except that in Preparation Example 8 , the weight ratio of B( C6F5 ) 3 to the activated support was 0.3:1, and the other steps and conditions were the same as in Preparation 5, to obtain the SiO2 -supported ion-pair boron compound (denoted as S-4).
  • Preparation Example 5 The method of Preparation Example 5 was followed, except that in Preparation Example 9 , the weight ratio of B( C6F5 ) 3 to the activated support was 1:1, and the other steps and conditions were the same as in Preparation 5, to obtain the SiO2 -supported ion-pair boron compound (denoted as S-5).
  • This preparation example illustrates the preparation of SiO2 -supported ion-pair boron compounds.
  • This preparation example illustrates the preparation of SiO2 -supported ion-pair boron compounds.
  • Preparation Example 5 The method of Preparation Example 5 was followed, except that in Preparation Example 12, the molar ratio of the ionizing reagent to B( C6F5 ) 3 was 2:1, and the other steps and conditions were the same as in Preparation 5, to obtain the SiO2 -supported ion -pair boron compound (denoted as S-8).
  • This example illustrates the preparation of the catalyst.
  • the pyridine-amine hafnium complex Hf-2 (0.46 g, 0.64 mmol) and dry toluene solvent (20 mL) were mixed together in a 100 mL Schlenk reaction flask. Then, the SiO2- supported ion-pair boron compound S-1 (1 g) prepared above was added, and the reaction was stirred at 25 °C for 2 h. After the reaction was completed, the mixture was filtered through a sintered glass filter, washed three times with anhydrous toluene (3 ⁇ 10 mL), and dried under vacuum for 6 h. The resulting solid was the olefin polymerization catalyst (denoted as Cat-1).
  • This example illustrates the preparation of the catalyst.
  • Example 2 The method of Example 1 was followed, except that the pyridine-amine hafnium complex Hf-2 was replaced with an equimolar amount of Hf-1, and all other steps and conditions were the same as in Example 1, to obtain the olefin polymerization catalyst (denoted as Cat-2).
  • This example illustrates the preparation of the catalyst.
  • Example 1 The method of Example 1 was followed, except that the SiO2 -supported ion-pair boron compound S-1 was replaced with equimolar amounts of S-2, S-3, S-4, S-5, S-6, S-7, and S-8, respectively. All other steps and conditions were the same as in Example 1, to obtain olefin polymerization catalysts (denoted as Cat-3, Cat-4, Cat-5, Cat-6, Cat-7, Cat-8, and Cat-9, respectively).
  • This example illustrates the preparation of the catalyst.
  • Example 1 The method of Example 1 was followed, except that the molar ratio of Hf:B of the pyridine-amine hafnium complex Hf- 2 and the SiO2-supported ion-pair boron compound S-1 was 0.6:1. All other steps and conditions were the same as in Example 1, and an olefin polymerization catalyst (denoted as Cat-10) was obtained.
  • the ICP-AES test was performed on Cat-10, and the Hf content, B content, and Si content (in elemental terms) were obtained, as shown in Table 2.
  • This example illustrates the preparation of the catalyst.
  • Example 1 The method of Example 1 was followed, except that the molar ratio of Hf:B of the pyridineamine hafnium complex Hf-2 and the SiO2- supported ion-pair boron compound S-1 was 1.6:1. All other steps and conditions were the same as in Example 1, and an olefin polymerization catalyst (denoted as Cat-11) was obtained.
  • the ICP-AES test was performed on Cat-11, and the Hf content, B content, and Si content (in elemental terms) were obtained, as shown in Table 2.
  • This example illustrates the preparation of the catalyst.
  • Example 2 Following the method of Example 1, the only difference being that the reaction temperature was 0°C and the reaction time was 0.5 h, while all other steps and conditions were the same as in Example 1, to obtain an olefin polymerization catalyst (denoted as Cat-12).
  • This example illustrates the preparation of the catalyst.
  • Example 13 Following the method of Example 1, the only difference being that the reaction temperature was 50°C and the reaction time was 5 hours, while all other steps and conditions were the same as in Example 1, to obtain an olefin polymerization catalyst (denoted as Cat-13).
  • the ICP-AES test was performed on Cat-13, and the Hf content, B content, and Si content (in elemental terms) were obtained, as shown in Table 2.
  • This comparative example illustrates the preparation of catalysts.
  • This comparative example illustrates the preparation of catalysts.
  • the boron compound supported on SiO2 was prepared by direct mixing method: Under a nitrogen atmosphere, the above-mentioned activated support (1g) was dispersed in 20mL of anhydrous toluene solvent and mixed into a slurry. Then, 1.17mmol of [ Ph3C ][ B ( C6F5 ) 4 ] was added, and the mixture was directly stirred at 25°C for 12h. The mixture was filtered through a sand filter ball, washed three times with anhydrous toluene (3 ⁇ 10mL), and vacuum dried for 6h to obtain the boron compound supported on SiO2 prepared by direct mixing method.
  • This comparative example illustrates the preparation of catalysts.
  • This example illustrates the preparation of the catalyst.
  • the molar ratio of Al:Hf refers to the molar ratio of Hf in the catalyst to Al in triisobutylaluminum; the polymer products prepared by tests 1-13, 15-16 and 18-19 are spherical particles in appearance.
  • the catalyst activity in the above reaction was tested, as well as the melting temperature, weight-average molecular weight, molecular weight distribution and particle size (D50) of the obtained polybutene product. The results are shown in Table 4.
  • the catalyst activity in the above reaction was tested, as well as the melting temperature, weight-average molecular weight, molecular weight distribution and particle size (D50) of the obtained polyethylene product. The results are shown in Table 4.
  • the olefin polymerization catalyst provided by this invention can catalyze the polymerization reaction of various olefin monomers with high activity.
  • the product D50 is between 22-31 ⁇ m (under the condition that the molar ratio of Al:Hf is 100), and the molecular weight distribution of the product is relatively narrow.
  • this catalyst has a larger loading of active centers and higher catalytic activity, and can prepare polyolefin products with higher molecular weight.
  • this catalyst can produce spherical polyolefin powders with better morphology ( Figure 1 shows the morphology of poly4-methyl-1-pentene obtained in Test 1 above, the product is spherical and the particle size is relatively uniform; Figure 2 shows the morphology of poly4-methyl-1-pentene obtained in Test 17 above, the product after reaction is a viscous liquid, and after drying, the product is in blocks of different sizes). It can effectively solve the problems of polymer sticking and clogging, meet the needs of continuous production of polyolefins, and is especially suitable for gas phase process and slurry polymerization process.

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Abstract

本发明涉及化工合成技术领域，具体涉及一种烯烃聚合催化剂及其制备方法、烯烃聚合的方法。所述催化剂包括式(1)所示结构的阳离子吡啶胺基铪活性组分，以及改性SiO2载体；其中，所述改性SiO2载体包括SiO2基体，以及式(2)所示结构的阴离子硼化合物；所述阴离子硼化合物中的B与所述SiO2基体表面的至少部分O连接；基于所述催化剂的总重量，所述催化剂中，以元素计的Hf含量为1-5wt％，以元素计的B含量为0.2-0.8mmol/g，以元素计Si含量为25-60wt％。催化聚合活性高，稳定性好，能够有效解决均相催化剂体系存在的"爆聚"、聚合产物形貌差以及难以连续化生产的问题。

Description

烯烃聚合催化剂及其制备方法、烯烃聚合的方法
相关申请的交叉引用
本申请要求2024年05月09日提交的发明名称为“烯烃聚合催化剂及其制备方法、烯烃聚合的方法”的中国专利申请202410570737.0的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及化工合成技术领域，具体涉及一种烯烃聚合催化剂及其制备方法、烯烃聚合的方法。
背景技术
聚(4-甲基-1-戊烯)(PMP)是一种具有立体规整结构的结晶型树脂，独特的结构赋予其优异的性能，包括优良的耐化学性能、机械性能及可加工性能，优异的电气绝缘性能、低介电特性能、光学性能、透气性能和易剥离性能。因此，这类高端的热塑性树脂在纤维材料、离型材料，高端医疗材料以及电子材料领域有着重要的用途，特别适用于5G、6G通信高射频器绝缘子、医药缓释膜、人工肺(ECMO)肺膜等先进网络通信、微孔材料、高端医疗等领域，PMP产品的需求量必将迅猛增长。
4-甲基-1-戊烯单体结构特殊，具有较长的侧链、末端为异丙基结构，是目前常用的烯烃单体中空间位阻最大的单体之一，位阻效应较强。因此，常规通用的高活性聚烯烃催化剂对于4-甲基-1-戊烯的聚合活性很低，配位和插入速率都比较慢，例如茂金属催化剂，由于单金属中心，聚合得到的PMP分子量分布比较窄，一般低于3。茂金属催化剂空间位阻大，大位阻的4-甲基-1-戊烯单体难以插入，茂金属催化剂催化4-甲基-1-戊烯的活性较低，相比齐格勒-纳塔催化剂活性低10倍以上。而非茂金属催化剂无茂环，空间比较开放，可通过外消旋和骨架取代基的优选使金属中心具有手性，兼顾高活性和等规度，使得非茂金属催化剂越来越受到关注。
吡啶胺基铪催化剂是2003年由美国陶氏化学公司和美国Symyx公司利用高通量筛选法发现的，该催化剂显示出优越的催化烯烃聚合性能，也具有良好的立构选择性，能在高温下催化丙烯和其他α-烯烃聚合，制备得到高等规的聚烯烃材料。同时该催化剂也具有良好的共聚性能，能够催化乙烯、丙烯和α-烯烃共聚，制备得到高α-烯烃插入率的聚烯烃材料。因此吡啶胺基铪催化剂在聚烯烃领域受到了广泛的重视。
当前，吡啶胺基铪催化剂主要用于均相溶液聚合，可以用于4-甲基-1-戊烯的高活性溶液聚合，然而吡啶胺基铪催化剂用溶液聚合工艺生产PMP树脂会面临一系列问题。例如，容易发生“爆聚”，聚合产物形貌差，反应器易结垢、产物和催化剂分离困难、难以实现连续化生产。
对于上述问题，可通过对吡啶胺基铪催化剂进行负载化，使单体定向聚合为规整的球形颗粒，通过催化剂和聚合工艺条件联动调控聚合体系的综合粘度使产品性能达到指标要求，同时通过控制聚合物形貌和防止反应器污染来实现连续的气相和淤浆聚合。美国西北大学的Marks教授课题组开展了吡啶胺基铪催化剂负载化研究(Marks et al.ACS Catal.2021,11,3239-3250；Marks et al.ACS Catal.2018,8,4893-4901.)，他们将吡啶胺基铪配合物负载在硫酸化氧化铝(AlS)和硫酸化氧化锆(ZrS)上来研究乙烯的均聚以及乙烯和1-辛烯的共聚合，然而该负载型吡啶胺基铪催化剂的活性大大降低，在催化烯烃聚合时催化活性最高仅有4.8×104gpolymer/(mol Hf·h)，这无法满足工业上对催化剂的活性要求。
因此，开发一种活性高、反应平稳性优异、产物形貌好，并能够实现连续化生产的烯烃聚合催化剂，对于聚烯烃工业化的发展具有重要的意义和推动作用。
发明内容
本发明针对现有的均相吡啶胺基铪催化剂在生产聚烯烃过程中易出现反应器易结垢、产物和催化剂分离困难、难以实现连续化生产以及产品形貌较差的的问题，以及现有的负载型吡啶胺基铪催化剂存在活性低难以满足使用需求的问题，提供一种烯烃聚合催化剂及其制备方法、烯烃聚合的方法。
为了实现上述目的，本发明第一方面提供一种烯烃聚合催化剂，所述催化剂包括式(1)所示结构的阳离子吡啶胺基铪活性组分，以及改性SiO2载体；其中，所述改性SiO2载体包括SiO2基体，以及式(2)所示结构的阴离子硼化合物；所述阴离子硼化合物中的B与所述SiO2基体表面的至少部分O连接；
式(1)中，R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15各自独立地选自-H或C1-C9的烃基；R16、R17各自独立地选自-H或C1-C9的烃基，且在R16、R17各自独立地为C2-C6的烷基时，二者可以闭合成环；
基于所述催化剂的总重量，所述催化剂中，以元素计的Hf含量为1-5wt％，以元素计的B含量为0.2-0.8wt％，以元素计Si含量为25-60wt％。
本发明第二方面提供一种烯烃聚合催化剂的制备方法，包括：
(1)将SiO2颗粒进行活化处理，得到活化载体；
(2)在第一溶剂存在下，将所述活化载体与B(C6F5)3进行第一反应，得到第一产物；之后将所述第一产物与离子化试剂进行第二反应，得到SiO2负载的离子对硼化合物；
(3)在第二溶剂存在下，将式(1’)所示结构的吡啶胺基铪配合物与所述SiO2负载的离子对硼化合物进行离子交换反应，得到烯烃聚合催化剂；
其中，R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15各自独立地选自-H或C1-C9的烃基；R16、R17各自独立地选自-H或C1-C9的烃基，且在R16、R17各自独立地为C2-C6的烷基时，二者可以闭合成环；
所述活化载体：B(C6F5)3的重量比为1：(0.3-1)；所述离子化试剂：B(C6F5)3的摩尔比为(1-2)：1；所述吡啶胺基铪配合物中的Hf：SiO2负载的离子对硼化合物中的B的摩尔比为(0.6-1.6)：1。
本发明第三方面提供前述第二方面所述的制备方法制得的烯烃聚合催化剂。
本发明第四方面提供一种烯烃聚合的方法，包括：在主催化剂和可选的助催化剂存在下，将烯烃单体进行聚合反应，得到聚合产物；
其中，所述主催化剂为前述第一方面或第三方面所述的烯烃聚合催化剂。
本发明提供的烯烃聚合催化剂具有如下有益效果：
(1)本发明提供的烯烃聚合催化剂的催化聚合活性高，相较于现有报道的硫酸化氧化铝(AlS)或硫酸化氧化锆(ZrS)负载的吡啶胺基铪催化剂，本发明提供的催化剂的活性显著提高，具有良好的工业化前景；
(2)本发明提供的烯烃聚合催化剂的组分之间通过化学键结合(Si-O共价键、B-O共价键以及Hf与B的离子键)，相较于采用简单的共混吸附方式制得的催化剂，具有更好的稳定性，催化烯烃聚合反应平稳且高效，能够有效解决均相催化剂体系存在的“爆聚”、聚合产物形貌差以及难以连续化生产的问题；
(3)制备工艺简单，制备成本低廉，经济效益好。
附图说明
图1为利用本发明的实施例1制备的催化剂制得的聚4-甲基-1-戊烯形貌图。
图2为利用本发明的对比例4制备的催化剂制得的聚4-甲基-1-戊烯形貌图。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
本发明第一方面提供一种烯烃聚合催化剂，所述催化剂包括式(1)所示结构的阳离子吡啶胺基铪活性组分，以及改性SiO2载体；其中，所述改性SiO2载体包括SiO2基体，以及式(2)所示结构的阴离子硼化合物；所述阴离子硼化合物中的B与所述SiO2基体表面的至少部分O连接；
式(1)中，R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15各自独立地选自-H或C1-C9的烃基；R16、R17各自独立地选自-H或C1-C9的烃基，且在R16、R17各自独立地为C2-C6的烷基时，二者可以闭合成环；
基于所述催化剂的总重量，所述催化剂中，以元素计的Hf含量为1-5wt％，以元素计的B含量为0.2-0.8wt％，以元素计Si含量为25-60wt％。
本发明提供的催化剂为一种新型的负载型吡啶胺基铪烯烃聚合催化剂，具有特定的结构，其中的阳离子吡啶胺基铪活性组分与改性SiO2载体之间的结合关系如下式(7)所示。发明人需要解释和强调的是，式(7)仅用于示意性的阐述该催化剂的结构及组分之间的结合关系，并不代表组分之间的数量关系。由式(7)可见，一方面，该催化剂中的阳离子吡啶胺基铪活性组分(铪金属中心)“游离于”改性SiO2载体之外，能够有效降低负载化带来的活性损失，利于保持催化剂的高聚合活性；另一方面，该催化剂中的改性SiO2载体的基体通过化学键与阴离子硼化合物连接，稳定性更好，可使得所述改性SiO2载体具有较高的硼含量，能够负载更多的铪金属中心，且所述阴离子硼化合物能够通过离子键远距离的作用于所述铪金属中心，保证了聚合能够平稳、连续进行，不会出现均相催化剂体系的“爆聚”问题，聚合产物形貌良好，具有窄的产品粒径分布。该催化剂可用于多种烯烃单体的均聚或共聚，尤其能够满足溶液聚合工艺制备PMP对催化剂活性及稳定性的要求。
根据本发明，式(1)所示的阳离子吡啶胺基铪活性组分提供所述烯烃聚合催化剂的铪金属中心。在式(1)中，优选地，R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15各自独立地选自-H或C1-C4的烃基，可使得所述阳离子吡啶胺基铪活性组分具有更小的空间位阻，在聚合反应过程中更利于共聚单体的插入，获得高催化活性。
根据本发明的一种优选实施方式，所述烯烃聚合催化剂中，所述阳离子吡啶胺基铪活性组分具有式(3)或式(4)所示的结构，进而可使得所述烯烃聚合催化剂具有更高的催化活性，进一步优选地，所述阳离子吡啶胺基铪活性组分具有式式(4)所示的结构。
根据本发明，所述烯烃聚合催化剂中，式(2)中，表示所述阴离子硼化合物与所述SiO2基体表面的至少部分O的连接位置。
根据本发明，所述烯烃聚合催化剂中，所述以元素计的Hf含量、以元素计的B含量和以元素计Si含量在满足上述限定的基础上，优选地，基于所述催化剂的总重量，所述催化剂中，以元素计的Hf含量为4-5wt％，以元素计的B含量为0.6-0.8wt％，以元素计Si含量为25-30wt％，可使得所述烯烃聚合催化剂具有进一步提高的催化活性。
在本发明中，催化剂中元素的含量根据GB/T 30902-2014中规定的方法并利用ICP(电感耦合等离子体光谱仪)测定。
根据本发明的一种最优选实施方式，所述烯烃聚合催化剂包括式(4)所示结构的阳离子吡啶胺基铪活性组分，以及改性SiO2载体；其中，所述改性SiO2载体包括SiO2基体，以及式(2)所示结构的阴离子硼化合物；所述阴离子硼化合物中的B与所述SiO2基体表面的至少部分O连接；基于所述催化剂的总重量，所述催化剂中，以元素计的Hf含量为4.7-5wt％，以元素计的B含量为0.6-0.75wt％，以元素计Si含量为25-27wt％。上述最优选实施方式的催化剂，具有更好的兼顾高聚合活性、优异的稳定性及聚合产物形貌好的综合性能。
本发明第二方面提供一种烯烃聚合催化剂的制备方法，包括：
(1)将SiO2颗粒进行活化处理，得到活化载体；
(2)在第一溶剂存在下，将所述活化载体与B(C6F5)3进行第一反应，得到第一产物；之后将所述第一产物与离子化试剂进行第二反应，得到SiO2负载的离子对硼化合物；
(3)在第二溶剂存在下，将式(1’)所示结构的吡啶胺基铪配合物与所述SiO2负载的离子对硼化合物进行离子交换反应，得到烯烃聚合催化剂；
其中，R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15各自独立地选自-H或C1-C9的烃基；R16、R17各自独立地选自-H或C1-C9的烃基，且在R16、R17各自独立地为C2-C6的烷基时，二者可以闭合成环；
所述活化载体：B(C6F5)3的重量比为1：(0.3-1)；所述离子化试剂：B(C6F5)3的摩尔比为(1-2)：1；所述吡啶胺基铪配合物中的Hf：SiO2负载的离子对硼化合物中的B的摩尔比为(0.6-1.6)：1。
根据本发明，所述烯烃聚合催化剂的制备方法中，步骤(1)中，所述SiO2颗粒可以为任何能够用作催化剂载体的自制或市售SiO2颗粒。优选地，所述SiO2颗粒的平均粒径为20-200μm，利于所制得的烯烃聚 合催化剂在催化烯烃单体聚合中制得细粉含量少、粒径分布均匀的聚合产物。
在本发明中，平均粒径是指D50，可根据GB/T 41949-2022中规定的方法并利用激光粒度仪测定。
根据本发明，所述烯烃聚合催化剂的制备方法中，步骤(1)中，所述活化处理可以采用对所述SiO2颗粒进行加热的方式进行。优选地，所述活化处理的条件包括：温度为200-700℃，时间为1-10h。
根据本发明的一种优选实施方式，所述活化处理包括：将所述SiO2颗粒置于加热装置中，以1-5℃/min的升温速率升温至200-250℃，恒温0.5-2h，之后以1-5℃/min的升温速率升温至500-700℃，恒温2-6h，得到活化载体。
根据本发明，所述烯烃聚合催化剂的制备方法中，通过对所述SiO2颗粒进行活化处理，在所述SiO2颗粒的表面形成孤立的硅羟基，以在步骤(2)中能够与B(C6F5)3中的硼原子通过化学键键合。
根据本发明，所述烯烃聚合催化剂的制备方法中，步骤(1)中，所述活化载体中硅羟基的含量为0.5-2mmol/g，优选为1-1.5mmol/g，利于在步骤(2)中所述活化载体与B(C6F5)3的键合反应正向进行，促进B-O键的形成。
在本发明中，硅羟基的含量可通过核磁共振氢谱测定。
根据本发明，所述烯烃聚合催化剂的制备方法中，步骤(2)中，对所述第一溶剂的限定较宽，只要能够溶解B(C6F5)3即可。优选地，所述第一溶剂可以选自甲苯、正戊烷、正己烷、环己烷和正庚烷中的至少一种，利于B(C6F5)3的溶解及所述活化载体的分散。所述第一溶剂可以进一步优选为甲苯和/或正庚烷。
根据本发明，所述烯烃聚合催化剂的制备方法中，步骤(2)中，对于所述第一反应，优选地，在保护气氛下，先将所述活化载体与所述第一溶剂进行混合，得到混合浆液，之后将所述混合浆液与B(C6F5)3进行混合并发生第一反应。优选地，所述第一反应的条件包括：温度为0-50℃，时间为1-12h。
根据本发明，所述烯烃聚合催化剂的制备方法中，步骤(2)中，对所述第一溶剂的使用量限定较宽，只要能够充分溶解上述用量的B(C6F5)3即可，优选地，所述活化载体：第一溶剂的重量比为1：(15-25)，更利于B(C6F5)3的溶解及所述活化载体的均匀分散。
根据本发明，所述烯烃聚合催化剂的制备方法中，步骤(2)中，对于所述第二反应，优选地，将所述第一反应得到的产物体系(第一产物)与所述离子化试剂进行混合并发生第二反应。优选地，所述第二反应的条件包括：在避光条件下进行反应，温度为0-50℃，时间为6-24h。
根据本发明，所述烯烃聚合催化剂的制备方法中，步骤(2)中，优选地，所述离子化试剂可以选自CPh3Cl和/或NPhMe2，能够促进B-O键合的可逆反应正向移动，形成更加稳定的B-O键。所述离子化试剂进一步优选为CPh3Cl。
根据本发明，优选地，所述离子化试剂以溶液的形式投料。例如，预先将所述离子化试剂与有机溶剂配制成浓度为0.5-1mol/L的溶液。优选地，所述有机溶剂可以选自甲苯、二甲苯和乙苯中的至少一种。
根据本发明，所述烯烃聚合催化剂的制备方法中，步骤(2)中，通过依次进行的所述第一反应和第二反应，制备得到SiO2负载的离子对硼化合物(载体)。具体地，当离子化试剂为CPh3Cl时，步骤(2)中的主要反应过程示意如下：
当离子化试剂为NPhMe2时，步骤(2)中的主要反应过程示意如下：
在本发明中，所述SiO2负载的离子对硼化合物的制备方法不同于直接混合法，直接混合法是在溶液中简单地进行原料溶解混合，SiO2载体和B(C6F5)3之间主要是物理吸附，制得的载体中硼含量较低，导致活性组分的负载量大大降低，催化剂的活性降低。而本发明通过化学反应的方式制备得到SiO2负载的离子对硼化合物，SiO2载体和B(C6F5)3以化学键的形式结合，能够显著提高载体中硼含量，同时也提高了O原子和B原子结合的稳定性，更有利于后续吡啶胺基铪配合物在载体上的负载。
根据本发明，所述烯烃聚合催化剂的制备方法中，优选地，所述SiO2负载的离子对硼化合物中B的含量为0.2-0.8mmol/g，更利于步骤(3)中吡啶胺基铪配合物在载体上的负载。
在本发明中，载体中B的含量根据GB/T 30902-2014中规定的方法并利用ICP(电感耦合等离子体光谱仪)测定。
根据本发明，所述烯烃聚合催化剂的制备方法中，步骤(3)中，所述第二溶剂为芳香烃类溶剂，优选为苯、甲苯和乙苯中的至少一种。
根据本发明，所述烯烃聚合催化剂的制备方法中，步骤(3)中，对于所述离子交换反应，优选地，在保护气氛下，先将所述吡啶胺基铪配合物与所述第二溶剂进行混合，之后加入所述SiO2负载的离子对硼化合物进行混合并发生离子交换反应，得到固体，所述固体经纯化后得到烯烃聚合催化剂。优选地，所述离子交换反应的条件包括：温度为0-50℃，时间为0.5-5h。
根据本发明，所述烯烃聚合催化剂的制备方法中，步骤(3)中，对所述第二剂的使用量限定较宽，只要能够充分溶解所述吡啶胺基铪配合物即可，优选地，所述吡啶胺基铪配合物：第二溶剂的重量比为1：(20-60)。
根据本发明，所述烯烃聚合催化剂的制备方法中，步骤(3)中，通过所述离子交换反应，生成阳离子吡啶胺基铪活性组分和SiO2负载的硼化合物抗衡阴离子(含阴离子硼化合物)，主要反应过程示意如下：
使所制得的催化剂中，阳离子吡啶胺基铪活性组分(铪金属中心)“游离于”改性SiO2载体之外，能够有效降低负载化带来的活性损失，利于保持催化剂的高聚合活性，且阴离子硼化合物能够通过离子键远距离的作用于所述铪金属中心，保证了聚合能够平稳、连续进行，不会出现均相催化剂体系的“爆聚”问题，聚合产物形貌良好，具有窄的产品粒径分布。
根据本发明，所述烯烃聚合催化剂的制备方法中，步骤(3)中，优选地，所述吡啶胺基铪配合物具有式(5)或式(6)所示的结构，能够使所制得的烯烃聚合催化剂具有更高的催化活性。进一步优选地，所述吡啶胺基铪配合物具有式(6)所示的结构。
根据本发明，所述烯烃聚合催化剂的制备方法中，各原料的投料量在满足上述限定的基础上，优选地，所述活化载体：B(C6F5)3的重量比为1：(0.6-1)；所述离子化试剂：B(C6F5)3的摩尔比为(1.1-1.5)：1；所述吡啶胺基铪配合物中的Hf：SiO2负载的离子对硼化合物中的B的摩尔比为(1-1.6)：1，可使所制得的催化剂具有更好的兼顾高聚合活性、优异的稳定性及聚合产物形貌好的综合性能。
本发明第三方面提供前述第二方面所述的制备方法制得的烯烃聚合催化剂。
根据本发明，由前述第二方面所述方法制得的催化剂，其结构、组成及性能均同本发明前述第一方面所述的烯烃聚合催化剂，此处不再赘述。
本发明第四方面提供一种烯烃聚合的方法，包括：在主催化剂和可选的助催化剂存在下，将烯烃单体进行聚合反应，得到聚合产物；
其中，所述主催化剂为前述第一方面或第三方面所述的烯烃聚合催化剂。
根据本发明，所述烯烃聚合的方法中，对所述烯烃单体的限定较宽，优选可以选自4-甲基-1-戊烯、乙烯、丙烯、1-丁烯、1-己烯和1-辛烯中的至少一种。
根据本发明，所述烯烃聚合的方法中，所述烯烃聚合催化剂可以在有或者没有助催化剂的情况下高活性催化烯烃聚合。在本发明中，所述助催化剂可以为有机铝化合物，包括但不限于三异丁基铝、三乙基铝、三正己基铝、三甲基铝、一氯二乙基铝等，优选为三异丁基铝。优选地，所述有机铝化合物中的Al：烯烃聚合催化剂中的Hf的摩尔比为(0-200)：1。
根据本发明，所述烯烃聚合的方法中，所述聚合反应优选采用气相聚合法或淤浆聚合法。
本发明提供的烯烃聚合的方法能够高活性催化烯烃聚合，反应过程平稳，利于连续化生产，聚合产物形貌良好，具有窄的产品粒径分布。该方尤其能够解决现有的溶液聚合工艺制备PMP中出现的反应活性不足、反应不稳定、难以连续化生产的问题。
以下将通过实施例对本发明进行详细描述。下述制备例、实施例和对比例中，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。
以下制备例、实施例中，所制得的引发剂G、聚合物中含有的结构单元的摩尔比通过原料的投料量计算得到。
制备例1
通过本制备例阐述吡啶胺基铪配合物的制备
按照文献(Gregory J Domski,James M Eagan,Claudio De Rosa,et al.Combined Experimental and Theoretical Approach for Living and Isoselective Propylene Polymerization[J].ACS Catal.2017,7,6930-6937)中的方法制备吡啶胺基铪配合物(记为Hf-1)，Hf-1具有式(4)所示结构，
对HF-1进行核磁共振氢谱测试，所得核磁氢谱：1H NMR(C6D6,400MHz):δ(ppm)δ8.42(d,1H,Ar-H),7.46-7.40(m,2H,Ar-H),7.23-6.72(m,10H,Ar-H),6.36(d,1H,Ar-H),5.92(s,1H,NCH),3.80(sept,1H,CH(CH3)2),3.22(sept,1H,CH(CH3)2),2.91(sept,1H,CH(CH3)2),1.38(d,6H,CH(CH3)2),1.13-1.15(d,6H,CH(CH3)2),0.94(s,3H,Hf-CH3),0.71(d,3H,CH(CH3)2),0.63(s,3H,Hf-CH3),0.38(d,3H,CH(CH3)2)。
制备例2
通过本制备例阐述吡啶胺基铪配合物的制备
按照文献(Gregory J Domski,James M Eagan,Claudio De Rosa,et al.Combined Experimental and Theoretical Approach for Living and Isoselective Propylene Polymerization[J].ACS Catal.2017,7,6930-6937)中的方法制备吡啶胺基铪配合物(记为Hf-2)，Hf-2具有式(3)所示结构，
对HF-2进行核磁共振氢谱测试，所得核磁氢谱：1H NMR(C6D6,400MHz):δ(ppm)8.59(d,1H,Nap-H),8.25(d,1H,Nap-H),7.82(d,1H,Nap-H),7.71(d,1H,Nap-H),7.50(d,1H,Py-H),7.35-7.00(m,9H,Ar-H),6.83(d,1H,Py-H),6.56(s,1H,NCH),6.55(d,1H,Py-H),3.84(sept,1H,CH(CH3)2),3.34(sept,1H,CH(CH3)2),2.90(sept,1H,CH(CH3)2),1.38(d,3H,CH(CH3)2),1.36(d,3H,CH(CH3)2),1.18(d,3H,CH(CH3)2),1.15(d,3H,CH(CH3)2),0.95(s,3H,Hf-CH3),0.70(d,3H,CH(CH3)2),0.68(s,3H,Hf-CH3),0.39(d,3H,CH(CH3)2)。
制备例3
通过本制备例阐述活化载体的制备
将10g的SiO2颗粒(平均粒径为50μm)置于管式炉中，从25℃开始，以2.9℃/min的升温速率升温至200℃，恒温1h，之后以4.4℃/min的升温速率升温至600℃，恒温4h，得到活化载体(记为Z-1)。
活化载体Z-1的表面Si-OH含量测定：在氮气保护的密封核磁管中称取100mg的上述活化载体，加入0.5mL C6D6(不含TMS)，之后加入20mg二茂铁作为内标，最后加入10mg LiCH2SiMe3在25℃下反应1h后进行1H NMR测试，根据生成的四甲基硅烷的相对积分面积，计算得到活化载体Z-1的表面硅羟基含量为2.0mmol/g。
制备例4
将10g的SiO2颗粒(平均粒径为50μm)置于管式炉中，从25℃开始，以2.3℃/min的升温速率升温至210℃，恒温1.5h，之后以5℃/min的升温速率升温至500℃，恒温2h，得到活化载体(记为Z-2)。
活化载体Z-2的表面Si-OH含量测定：在氮气保护的密封核磁管中称取100mg的上述活化载体，加入0.5mL C6D6(不含TMS)，之后加入20mg二茂铁作为内标，最后加入10mg LiCH2SiMe3在25℃下反应1h后进行1H NMR测试，根据生成的四甲基硅烷的相对积分面积，计算得到活化载体Z-2的表面硅羟基含量为0.5mmol/g。
制备例5
通过本制备例阐述SiO2负载的离子对硼化合物的制备
在氮气氛围下，将上述制备例3制得的活化载体Z-1(1g)分散到20mL无水甲苯溶剂中混合得到混合浆液；之后加入B(C6F5)3(0.6g，1.17mmol)，25℃下混合搅拌进行第一反应4h，得到第一产物；将离子化试剂CPh3Cl(0.42g，1.52mmol)溶解于2mL甲苯，加入上述第一产物中，25℃下避光搅拌进行第二反应12h，反应完毕砂芯滤球过滤，用无水甲苯洗涤三次(3×10mL)，真空干燥6h，得到SiO2负载的离子对硼化合物(记为S-1)。
对S-1进行电感耦合等离子体原子发射光谱测试(ICP-AES)，测得S-1中B含量为0.64mmol/g。
制备例6-7
通过本制备例阐述SiO2负载的离子对硼化合物的制备
按照制备例5的方法，区别仅在于，在制备例6中，将制备例3制得的活化载体Z-1(1g)分散到20mL无水正戊烷溶剂中混合得到混合浆液，调整第一反应的条件(温度为0℃，反应时间为12h)，调整第二反应的条件(温度为0℃，反应时间为24h)，其他步骤及条件均同制备5，得到SiO2负载的离子对硼化合物(记为S-2)；
按照制备例5的方法，区别仅在于，在制备例7中，将制备例4制得的活化载体Z-2(1g)分散到20mL无水正庚烷溶剂中混合得到混合浆液，调整第一反应的条件(温度为50℃，反应时间为1h)，调整第二反 应的条件(温度为50℃，反应时间为6h)，其他步骤及条件均同制备5，得到SiO2负载的离子对硼化合物(记为S-3)。
S-2、S-3的主要制备条件及S-2、S-3的B含量(ICP-AES)见表1。
制备例8-9
通过本制备例阐述SiO2负载的离子对硼化合物的制备
按照制备例5的方法，区别仅在于，在制备例8中，B(C6F5)3与活化载体的重量比为0.3：1，其他步骤及条件均同制备5，得到SiO2负载的离子对硼化合物(记为S-4)；
按照制备例5的方法，区别仅在于，在制备例9中，B(C6F5)3与活化载体的重量比为1：1，其他步骤及条件均同制备5，得到SiO2负载的离子对硼化合物(记为S-5)。
S-4、S-5的主要制备条件及S-4、S-5的B含量(ICP-AES)见表1。
制备例10
通过本制备例阐述SiO2负载的离子对硼化合物的制备
按照制备例5的方法，区别仅在于，将离子化试剂CPh3Cl替换为等摩尔量的NPhMe2，其他步骤及条件均同制备5，得到SiO2负载的离子对硼化合物(记为S-6)。
S-6的主要制备条件及S-6的B含量(ICP-AES)见表1。
制备例11-12
通过本制备例阐述SiO2负载的离子对硼化合物的制备
按照制备例5的方法，区别仅在于，在制备例11中，离子化试剂与B(C6F5)3的摩尔比为1：1，其他步骤及条件均同制备5，得到SiO2负载的离子对硼化合物(记为S-7)；
按照制备例5的方法，区别仅在于，在制备例12中，离子化试剂与B(C6F5)3的摩尔比为2：1，其他步骤及条件均同制备5，得到SiO2负载的离子对硼化合物(记为S-8)。
S-7、S-8的主要制备条件及S-7、S-8的B含量(ICP-AES)见表1。
表1
实施例1
通过本实施例阐述催化剂的制备
在氮气氛围下，将吡啶胺基铪配合物Hf-2(0.46g，0.64mmol)和干燥的甲苯溶剂(20mL)一起混合到100mL Schlenk反应瓶中，之后加入上述制备的SiO2负载的离子对硼化合物S-1(1g)，在25℃下搅拌反应2h，反应完毕砂芯滤球过滤，用无水甲苯洗涤三次(3×10mL)，真空干燥6h，所得固体即为烯烃聚合催化剂(记为Cat-1)。
对Cat-1进行ICP-AES测试，测得Cat-1中以元素计的Hf含量、以元素计的B含量和以元素计的Si含量见表2。
实施例2
通过本实施例阐述催化剂的制备
按照实施例1的方法，区别仅在于，将吡啶胺基铪配合物Hf-2替换为等摩尔量的Hf-1，其他步骤及条件均同实施例1，得到烯烃聚合催化剂(记为Cat-2)。
对Cat-2进行ICP-AES测试，测得Cat-2中以元素计的Hf含量、以元素计的B含量和以元素计的Si含量见表2。
实施例3-9
通过本实施例阐述催化剂的制备
按照实施例1的方法，区别仅在于，将分别将SiO2负载的离子对硼化合物S-1替换为等摩尔量的S-2、S-3、S-4、S-5、S-6、S-7、S-8，其他步骤及条件均同实施例1，得到烯烃聚合催化剂(分别记为Cat-3、Cat-4、Cat-5、Cat-6、Cat-7、Cat-8、Cat-9)。
对Cat-3、Cat-4、Cat-5、Cat-6、Cat-7、Cat-8、Cat-9进行ICP-AES测试，测得其中以元素计的Hf含量、以元素计的B含量和以元素计的Si含量见表2。
实施例10
通过本实施例阐述催化剂的制备
按照实施例1的方法，区别仅在于，吡啶胺基铪配合物Hf-2与SiO2负载的离子对硼化合物S-1的Hf：B摩尔比例为0.6：1，其他步骤及条件均同实施例1，得到烯烃聚合催化剂(记为Cat-10)。
对Cat-10进行ICP-AES测试，测得其中以元素计的Hf含量、以元素计的B含量和以元素计的Si含量见表2。
实施例11
通过本实施例阐述催化剂的制备
按照实施例1的方法，区别仅在于，吡啶胺基铪配合物Hf-2与SiO2负载的离子对硼化合物S-1的Hf：B摩尔比例为1.6：1，其他步骤及条件均同实施例1，得到烯烃聚合催化剂(记为Cat-11)。
对Cat-11进行ICP-AES测试，测得其中以元素计的Hf含量、以元素计的B含量和以元素计的Si含量见表2。
实施例12
通过本实施例阐述催化剂的制备
按照实施例1的方法，区别仅在于，反应温度为0℃，反应时间为0.5h，其他步骤及条件均同实施例1，得到烯烃聚合催化剂(记为Cat-12)。
对Cat-12进行ICP-AES测试，测得其中以元素计的Hf含量、以元素计的B含量和以元素计的Si含量见表2。
实施例13
通过本实施例阐述催化剂的制备
按照实施例1的方法，区别仅在于，反应温度为50℃，反应时间为5h，其他步骤及条件均同实施例1，得到烯烃聚合催化剂(记为Cat-13)。
对Cat-13进行ICP-AES测试，测得其中以元素计的Hf含量、以元素计的B含量和以元素计的Si含量见表2。
对比例1
通过本对比例阐述催化剂的制备
将上述吡啶胺基铪配合物Hf-2直接作为烯烃聚合催化剂(记为D-Cat-1)。
对比例2
通过本对比例阐述催化剂的制备
采用直接混合法制备SiO2负载的硼化合物：在氮气氛围下，将上述活化载体(1g)分散到20mL无水甲苯溶剂中混合成浆液，之后加入1.17mmol[Ph3C][B(C6F5)4]，并在25℃下直接混合搅拌12h，混合产物砂芯滤球过滤，用无水甲苯洗涤三次(3×10mL)，真空干燥6h，得到直接混合法制备的SiO2负载的硼化合物；
取上述制备的SiO2负载的硼化合物(1g)，上述吡啶胺基铪配合物Hf-2(0.46g，0.64mmol)和干燥 的甲苯溶剂(20mL)一起混合到100mL Schlenk反应瓶中，25℃下直接混合搅拌反应2h，反应完毕砂芯滤球过滤，用无水甲苯洗涤三次(3×10mL)，真空干燥6h，得直接混合法制备的SiO2负载型铪催化剂(记为D-Cat-2)。
对D-Cat-2进行ICP-AES测试，测得其中以元素计的Hf含量、以元素计的B含量见表2。
对比例3
通过本对比例阐述催化剂的制备
在氮气氛围下，将吡啶胺基铪配合物Hf-2(0.46g，0.64mmol)和干燥的甲苯溶剂(20mL)一起混合到100mL Schlenk反应瓶中，之后加入上述制备的SiO2负载的离子对硼化合物S-1(1g)，在25℃下搅拌反应0.2h，反应完毕砂芯滤球过滤，用无水甲苯洗涤三次(3×10mL)，真空干燥6h，得到烯烃聚合催化剂(记为D-Cat-3)。
对D-Cat-3进行ICP-AES测试，测得其中以元素计的Hf含量、以元素计的B含量见表2。
对比例4
通过本实施例阐述催化剂的制备
将2μmol的吡啶胺基铪化合物Hf-2与2.4μmol的三苯碳鎓四(五氟苯基)硼酸盐(Hf：B的摩尔比为1：1.2)在2mL甲苯中混合并反应，得到烯烃聚合催化剂(记为D-Cat-4)。
对D-Cat-4进行ICP-AES测试，测得其中以元素计的Hf含量、以元素计的B含量见表2。
表2
测试例
1、催化4-甲基-1-戊烯均聚测试
分别利用上述催化剂Cat-1、Cat-2、Cat-3、Cat-4、Cat-5、Cat-6、Cat-7、Cat-8、Cat-9、Cat-10、Cat-11、Cat-12、Cat-13、D-Cat-1、D-Cat-2、D-Cat-3和D-Cat-4对4-甲基-1-戊烯进行均聚反应，测试过程及条件如下：
在无水无氧的条件下，向反应瓶中加入6mL干燥的甲苯、3mL的4-甲基-1-戊烯和0.2mmol三异丁基铝，将8mg上述催化剂(Al：Hf的摩尔比见表3)分散在1mL甲苯中，用注射器加入反应瓶中，50℃下反 应20min；用质量分数为10％盐酸酸化的乙醇溶液终止聚合，搅拌2h后过滤，用乙醇洗涤三次，在60℃下真空干燥箱中干燥12h，得到PMP聚合产物。
分别测试上述反应中的催化剂活性，以及制得的PMP聚合产物的分子量分布、重均分子量和粒径(D50)，结果见表3。
表3
注：表3中，Al：Hf的摩尔比是指催化剂中的Hf与三异丁基铝中Al的摩尔比；测试1-13、测试15-16和测试18-19制备得到的聚合物产品在外观上呈球形颗粒状。
2、催化其它烯烃单体均聚测试
(2-1)催化丙烯单体均聚测试
分别利用上述催化剂Cat-1、D-Cat-1、D-Cat-2、D-Cat-3和D-Cat-4对丙烯进行均聚反应，测试过程及条件如下：
在无水无氧的条件下，向反应釜内加入98mL干燥的甲苯和0.5mmol三异丁基铝，将20mg上述催化剂分散在2mL甲苯中，用注射器加入反应釜内，通入10atm的丙烯，在50℃下进行丙烯均聚反应20min，用质量分数10％盐酸酸化的乙醇溶液终止聚合，搅拌2h后过滤，用乙醇洗涤三次，在60℃下真空干燥箱中干燥12h，得到线性聚乙烯产物；
分别测试上述反应中的催化剂活性，以及制得的线性聚乙烯产物的熔融温度、重均分子量、分子量分布和粒径(D50)，结果见表4。
(2-2)催化1-丁烯单体均聚测试
按照上述(2-1)催化丙烯单体均聚测试中的方法和参数条件，区别在于，聚合单体为1-丁烯，得到聚丁烯产物；
分别测试上述反应中的催化剂活性，以及制得的聚丁烯产物的熔融温度、重均分子量、分子量分布和粒径(D50)，结果见表4。
(2-3)催化乙烯单体均聚测试
按照上述(2-1)催化丙烯单体均聚测试中的方法和参数条件，区别在于，聚合单体为乙烯，得到聚乙烯产物；
分别测试上述反应中的催化剂活性，以及制得的聚乙烯产物的熔融温度、重均分子量、分子量分布和粒径(D50)，结果见表4。
(2-4)催化1-己烯单体均聚测试
在无水无氧的条件下，向反应瓶中加入6mL干燥的甲苯、3mL的1-己烯和0.2mmol三异丁基铝，将8mg催化剂Cat-1(Cat-1中的Hf与三异丁基铝中Al的摩尔比为100：1)分散在1mL甲苯中，用注射器加入反应瓶中，50℃下反应20min；用质量分数为10％盐酸酸化的乙醇溶液终止聚合，搅拌2h后过滤，用乙醇洗涤三次，在60℃下真空干燥箱中干燥12h，得到聚已烯产物。
分别测试上述反应中的催化剂活性，以及制得的聚已烯产物的熔融温度、重均分子量、分子量分布和粒径(D50)，结果见表4。
(2-5)催化1-辛烯单体均聚测试
在无水无氧的条件下，向反应瓶中加入6mL干燥的甲苯、3mL的1-辛烯和0.2mmol三异丁基铝，将8mg催化剂Cat-1(Cat-1中的Hf与三异丁基铝中Al的摩尔比为100：1)分散在1mL甲苯中，用注射器加入反应瓶中，50℃下反应20min；用质量分数为10％盐酸酸化的乙醇溶液终止聚合，搅拌2h后过滤，用乙醇洗涤三次，在60℃下真空干燥箱中干燥12h，得到聚辛烯产物。
分别测试上述反应中的催化剂活性，以及制得的聚辛烯产物的熔融温度、重均分子量、分子量分布和粒径(D50)，结果见表4。
表4
由表3和表4可见，本发明提供烯烃聚合催化剂能够高活性催化多种烯烃单体聚合反应，产品D50在22-31μm之间(在Al：Hf的摩尔比为100条件下)，且产品的分子量分布较窄；该催化剂与常规混合法制备的负载型催化剂相比，活性中心的负载量更大，具有更高的催化活性，能够制备分子量更高的聚烯烃产品；该催化剂与均相非负载型催化剂相比，可生产形貌更好的球形聚烯烃粉料(如图1为上述测试1制得的聚4-甲基-1-戊烯形貌图，产品呈球形颗粒状，且粒径较均匀；图2为上述测试17制得的聚4-甲基-1-戊烯形貌图，反应后产物呈粘稠液状，经干燥后产品呈大小不同尺寸的块状)，能够有效解决聚合物粘釜、堵塞问题，满足聚烯烃连续化生产的需求，尤其适用于气相工艺及淤浆聚合工艺。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (21)

  1. 一种烯烃聚合催化剂，其特征在于，所述催化剂包括式(1)所示结构的阳离子吡啶胺基铪活性组分，以及改性SiO2载体；其中，所述改性SiO2载体包括SiO2基体，以及式(2)所示结构的阴离子硼化合物；所述阴离子硼化合物中的B与所述SiO2基体表面的至少部分O连接；
    式(1)中，R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15各自独立地选自-H或C1-C9的烃基；R16、R17各自独立地选自-H或C1-C9的烃基，且在R16、R17各自独立地为C2-C6的烷基时，二者可以闭合成环；
    基于所述催化剂的总重量，所述催化剂中，以元素计的Hf含量为1-5wt％，以元素计的B含量为0.2-0.8mmol/g，以元素计Si含量为25-60wt％。
  2. 根据权利要求1所述的催化剂，其中，式(1)中，R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15各自独立地选自-H或C1-C4的烃基。
  3. 根据权利要求2所述的催化剂，其中，所述阳离子吡啶胺基铪活性组分具有式(3)或式(4)所示的结构；
  4. 根据权利要求1-3中任意一项所述的方法，其中，基于所述催化剂的总重量，所述催化剂中，以元素计的Hf含量为4-5wt％，以元素计的B含量为0.6-0.8mmol/g，以元素计Si含量为25-30wt％。
  5. 一种烯烃聚合催化剂的制备方法，包括：
    (1)将SiO2颗粒进行活化处理，得到活化载体；
    (2)在第一溶剂存在下，将所述活化载体与B(C6F5)3进行第一反应，得到第一产物；之后将所述第一产物与离子化试剂进行第二反应，得到SiO2负载的离子对硼化合物；
    (3)在第二溶剂存在下，将式(1’)所示结构的吡啶胺基铪配合物与所述SiO2负载的离子对硼化合物进行离子交换反应，得到烯烃聚合催化剂；
    其中，R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15各自独立地选自-H或C1-C9的烃基；R16、R17各自独立地选自-H或C1-C9的烃基，且在R16、R17各自独立地为C2-C6的烷基时，二者可以闭合成环；
    所述活化载体：B(C6F5)3的重量比为1：(0.3-1)；所述离子化试剂：B(C6F5)3的摩尔比为(1-2)：1；所述吡啶胺基铪配合物中的Hf：SiO2负载的离子对硼化合物中的B的摩尔比为(0.6-1.6)：1。
  6. 根据权利要求5所述的方法，其中，步骤(1)中，所述SiO2颗粒的平均粒径为20-200μm。
  7. 根据权利要求5或6所述的方法，其中，步骤(1)中，所述活化处理的条件包括：温度为200-700℃，时间为1-10h。
  8. 根据权利要求7所述的方法，其中，步骤(1)中，所述活化载体中硅羟基的含量为0.5-2mmol/g。
  9. 根据权利要求5或6所述的方法，其中，步骤(2)中，所述第一溶剂选自甲苯、正戊烷、正己烷、环己烷和正庚烷中的至少一种。
  10. 根据权利要求5或6所述的方法，其中，步骤(2)中，所述第一反应的条件包括：温度为0-50℃，时间为1-12h。
  11. 根据权利要求5或6所述的方法，其中，步骤(2)中，所述离子化试剂选自CPh3Cl和/或NPhMe。
  12. 根据权利要求5或6所述的方法，其中，步骤(2)中，所述第二反应的条件包括：在避光条件下进行反应，温度为0-50℃，时间为6-24h。
  13. 根据权利要求12所述的方法，其中，步骤(2)中，所述SiO2负载的离子对硼化合物中B的含量为0.2-0.8mmol/g。
  14. 根据权利要求5或6所述的方法，其中，步骤(3)中，所述第二溶剂为芳香烃类溶剂.
  15. 根据权利要求5或6所述的方法，其中，步骤(3)中，所述离子交换反应的条件包括：温度为0-50℃，时间为0.5-5h。
  16. 根据权利要求15所述的方法，其中，步骤(3)中，所述吡啶胺基铪配合物具有式(5)或式(6)所示的结构；
  17. 权利要求5-16中任意一项所述的制备方法制得的烯烃聚合催化剂。
  18. 一种烯烃聚合的方法，包括：在主催化剂和可选的助催化剂存在下，将烯烃单体进行聚合反应，得到聚合产物；
    其中，所述主催化剂为权利要求1-4和17中任意一项所述的烯烃聚合催化剂。
  19. 根据权利要求18所述的方法，其中，所述烯烃单体选自4-甲基-1-戊烯、乙烯、丙烯、1-丁烯、1-己烯和1-辛烯中的至少一种。
  20. 根据权利要求18所述的方法，其中，所述助催化剂为有机铝化合物。
  21. 根据权利要求18-20中任意一项所述的方法，其中，所述聚合反应采用气相聚合法或淤浆聚合法。
PCT/CN2024/126975 2024-05-09 2024-10-24 烯烃聚合催化剂及其制备方法、烯烃聚合的方法 Pending WO2025232102A1 (zh)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101981064A (zh) * 2008-03-28 2011-02-23 Sk能源株式会社 茂金属负载催化剂组合物以及使用其制备聚烯烃的方法
KR101498814B1 (ko) * 2013-09-17 2015-03-05 한화케미칼 주식회사 메탈로센 담지 촉매의 제조 방법
CN113527352A (zh) * 2020-04-17 2021-10-22 中国石油天然气股份有限公司 一种吡啶胺基铪化合物及其制备方法与应用
CN113527351A (zh) * 2020-04-16 2021-10-22 中国石油天然气股份有限公司 一种吡啶胺基铪化合物及其制备方法和应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101981064A (zh) * 2008-03-28 2011-02-23 Sk能源株式会社 茂金属负载催化剂组合物以及使用其制备聚烯烃的方法
KR101498814B1 (ko) * 2013-09-17 2015-03-05 한화케미칼 주식회사 메탈로센 담지 촉매의 제조 방법
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CN113527352A (zh) * 2020-04-17 2021-10-22 中国石油天然气股份有限公司 一种吡啶胺基铪化合物及其制备方法与应用

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