Process for the prepolymerization of polyolefin catalysts, its use and polyolefin polymerization process

Abstract

The present application relates to the field of olefin polymerization, and discloses a method for pre-polymerization of a polyolefin catalyst, application of the method and a method for polyolefin polymerization. The method for pre-polymerization of a polyolefin catalyst comprises: (1) performing a first pre-polymerization reaction on a first polymerization monomer and a polyolefin catalyst composition to obtain a first pre-polymerization catalyst slurry; (2) performing a second pre-polymerization reaction on the first pre-polymerization catalyst slurry obtained in step (1) and a second polymerization monomer to obtain a second pre-polymerization catalyst slurry; the temperature of the second pre-polymerization reaction is 0.5-70 DEG C higher than that of the first pre-polymerization reaction. The method can significantly improve the problems of polymer crushing and large particle agglomeration.

Description

Technical Field

[0001] This invention relates to the field of olefin polymerization, and more specifically, to a method for prepolymerization of polyolefin catalysts, its application, and a method for polyolefin polymerization. Background Technology

[0002] With the advent of MgCl2 support technology and the development of internal / external electron donor technology, the polymerization activity and particle morphology of Ziegler-Natta (ZN) catalysts have been greatly improved, enabling the direct production of low-ash, high-stereoregularity polypropylene products through polymerization. This has also driven significant progress in polymerization processes, eliminating the need for deashing and atactic removal steps and simplifying the polymerization process. High catalyst activity is a crucial indicator pursued by catalyst technology developers. Currently, Ziegler-Natta (ZN) catalysts can achieve activities up to nearly 200,000 times higher, significantly reducing ash content in polymers and enabling the widespread application of such polypropylene products in lithium-ion battery separators, capacitor films, and other fields. However, when highly active catalysts enter the main reactor, violent reactions occur inside the catalyst particles, causing polymer particle breakage and excessive fine powder content. Simultaneously, localized high temperatures inside and outside the particles lead to polymer melting, easily resulting in problems such as flakes and agglomeration within the reactor.

[0003] Currently, a major control method is to perform prepolymerization before the catalyst enters the main reactor. This ensures catalyst activity while improving polymer morphology and enhancing plant stability. This method is applied in most polypropylene processes. For example, the Hypol and Horizone gas-phase polypropylene processes use intermittent prepolymerization, continuously feeding the prepolymerized slurry into the main reactor. The Spheripol and ST polypropylene processes use continuous prepolymerization. Compared to intermittent prepolymerization, continuous prepolymerization simplifies operation, avoids batch-to-batch catalyst quality instability caused by intermittent prepolymerization, and achieves stable plant production. CN111100227B and CN111100225B mention adding anti-crushing agents to the reaction system during the catalyst pre-complexation or prepolymerization stage to further improve polymer morphology and reduce fine powder generation.

[0004] While continuous or intermittent prepolymerization can significantly improve the stability of the unit's operation and reduce the workload of subsequent fine powder separation processes, prepolymerization cannot effectively solve the polymer particle breakage problem for some ultra-highly active catalysts, initially highly active catalysts, or catalysts with poor particle morphology, especially under high-hydrogen polymerization conditions. Summary of the Invention

[0005] The purpose of this invention is to overcome the problems existing in the prior art and provide a method for prepolymerization of polyolefin catalysts, its application, and a method for polyolefin polymerization. This method can significantly improve the problems of polymer breakage and large particle agglomeration.

[0006] To achieve the above objectives, the present invention provides a method for prepolymerization of polyolefin catalysts, the method comprising:

[0007] (1) The first polymerizing monomer is subjected to a first prepolymerization reaction with the polyolefin catalyst composition to obtain a first prepolymerization catalyst slurry;

[0008] (2) The first prepolymerization catalyst slurry obtained in step (1) is subjected to a second prepolymerization reaction with the second polymerizing monomer to obtain the second prepolymerization catalyst slurry;

[0009] The temperature of the second prepolymerization reaction is 0.5-70℃ higher than that of the first prepolymerization reaction.

[0010] Preferably, the temperature of the second prepolymerization reaction is 10-50°C higher than the temperature of the first prepolymerization reaction.

[0011] Preferably, the prepolymerization ratio of the second prepolymerization reaction is 1-150 times that of the first prepolymerization reaction, and more preferably 5-100 times.

[0012] The second aspect of this invention provides an application of the prepolymerization method of the polyolefin catalyst described in the first aspect in olefin polymerization.

[0013] A third aspect of the present invention provides an olefin polymerization method, the method comprising: reacting a second prepolymerization catalyst slurry obtained by the prepolymerization method of the polyolefin catalyst described in the first aspect with a third polymerization monomer to obtain an olefin polymer.

[0014] The beneficial effects of this invention include:

[0015] The method provided by this invention employs a first prepolymerization reaction carried out at a lower temperature and a second prepolymerization reaction carried out at a higher temperature, which can significantly improve the problems of polymer breakage and large particle agglomeration, narrow the polymer particle size distribution, and increase the flowability of polymer particles. Attached Figure Description

[0016] Figure 1 This is a schematic flowchart of the olefin polymerization method of Embodiment 1 of the present invention;

[0017] Figure 2 This is a schematic flowchart of the olefin polymerization method of Example 3 of the present invention;

[0018] Figure 3 This is a schematic flowchart of the olefin polymerization method of Example 4 of the present invention.

[0019] Explanation of reference numerals in the attached figures

[0020] Figure 1 In the diagram: 01, First prepolymerization reactor; 02, Second prepolymerization reactor; 03, Main reactor; 101, Polyolefin catalyst composition; 102, First material stream containing the first polymerizing monomer; 103, Coolant for the first prepolymerization reactor; 201, First prepolymerization catalyst slurry; 202, Second material stream containing the second polymerizing monomer; 203, Coolant for the second prepolymerization reactor; 301, Second prepolymerization catalyst slurry; 302, Main reactor discharge; 303, Main reactor feed containing the third polymerizing monomer;

[0021] Figure 2 In the middle: 11, First prepolymerization reactor; 12, Second prepolymerization reactor; 13, Main reactor; 111, Polyolefin catalyst composition; 112, First material stream containing the first polymerizing monomer; 113, Coolant of the first prepolymerization reactor; 211, First prepolymerization catalyst slurry; 212, Second material stream containing the second polymerizing monomer; 213, Coolant of the second prepolymerization reactor; 311, Second prepolymerization catalyst slurry; 312, Main reactor discharge; 313, Main reactor feed containing the third polymerizing monomer;

[0022] Figure 3 In the middle: 21, first prepolymerization reactor; 22, second prepolymerization reactor; 23, main reactor; 24, pump; 121, polyolefin catalyst composition; 122, first material flow containing the first polymerizing monomer; 123, coolant for the first prepolymerization reactor; 221, first prepolymerization catalyst slurry; 222, second material flow containing polymerizing monomer; 223, coolant for the second prepolymerization reactor; 321, second prepolymerization catalyst slurry; 322, discharge from the main reactor; 323, feed to the main reactor containing the third polymerizing monomer. Detailed Implementation

[0023] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0024] As used herein, "prepolymerization" refers to a polymerization reaction carried out to achieve a lower reaction rate and monomer conversion compared to the reaction rate and monomer conversion under normal polymerization conditions. "Prepolymerization ratio" refers to the ratio of the mass of polymer produced to the mass of catalyst in the prepolymerization reactor. "Residence time" refers to the average residence time of the polyolefin catalyst in the prepolymerization reactor, expressed by the formula: reactor volume / reactor outflow prepolymer slurry volume flow rate.

[0025] In this invention, the unit "ppm(wt)" refers to one part per million by mass, and the unit "ppm(v)" refers to one part per million by volume.

[0026] This invention provides a method for prepolymerizing polyolefin catalysts, the method comprising:

[0027] (1) The first polymerizing monomer is subjected to a first prepolymerization reaction with the polyolefin catalyst composition to obtain a first prepolymerization catalyst slurry;

[0028] (2) The first prepolymerization catalyst slurry obtained in step (1) is subjected to a second prepolymerization reaction with the second polymerizing monomer to obtain the second prepolymerization catalyst slurry;

[0029] The temperature of the second prepolymerization reaction is 0.5-70℃ higher than that of the first prepolymerization reaction.

[0030] The method provided by this invention carries out the first prepolymerization reaction at a lower temperature, which can effectively overcome the problem of polymer particle breakage caused by the violent reaction inside the catalyst particles when the catalyst is highly active in the early stage of the reaction. Then, the second prepolymerization reaction is carried out at a higher temperature, which can further improve the problems of polymer breakage and large particle agglomeration, narrow the polymer particle size distribution, and increase polymer flowability.

[0031] The prepolymerization described in this invention refers to the contact between a polyolefin catalyst composition and a polymeric monomer at a prepolymerization reaction temperature to form a catalyst encapsulating the polyolefin.

[0032] To further improve the problems of polymer breakage and large particle agglomeration, preferably, the temperature of the second prepolymerization reaction is 10-50°C higher than the temperature of the first prepolymerization reaction, for example, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, and any value within the range formed by any two of these values.

[0033] According to the present invention, preferably, the prepolymerization ratio of the second prepolymerization reaction is 1-150 times that of the first prepolymerization reaction, more preferably 5-100 times, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150 times, and any value within any two of these values. This preferred embodiment can further improve the problems of polymer breakage and large particle agglomeration, narrow the polymer particle size distribution, and increase polymer flowability.

[0034] The first prepolymerization reaction of the present invention can be either continuous prepolymerization or intermittent prepolymerization, as long as the second prepolymerization reaction can be continuously prepolymerized. Preferably, the first prepolymerization reaction is a continuous prepolymerization.

[0035] According to the present invention, preferably, the first prepolymerization reaction is a continuous prepolymerization, wherein the conditions of the first prepolymerization reaction include: an operating temperature of -50 to 30°C, preferably -30 to 20°C, for example -50°C, -45°C, -40°C, -35°C, -30°C, -25°C, -20°C, -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, and any value within any two of these values; and an operating pressure of 0.1-10 MPaG, preferably 0.5-5 MPaG, for example 0.1 MPaG, 0.5 MPaG, 1 MPaG, 1.5 MPaG, 2 MPaG. The concentrations are 2.5 MPaG, 3 MPaG, 3.5 MPaG, 4 MPaG, 4.5 MPaG, 5 MPaG, 5.5 MPaG, 6 MPaG, 6.5 MPaG, 7 MPaG, 75 MPaG, 8 MPaG, 85 MPaG, 9 MPaG, 95 MPaG, 10 MPaG, and any value within any range of any two of these values; the residence time is ≤6 h, preferably 1-120 min, for example 1 min, 30 min, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, and any value within any range of any two of these values.

[0036] When the first prepolymerization reaction is a continuous prepolymerization, preferably, the prepolymerization ratio of the first prepolymerization reaction is ≤1000 times, preferably 0.5-80 times, for example 0.5 times, 5 times, 10 times, 15 times, 20 times, 25 times, 30 times, 35 times, 40 times, 45 times, 50 times, 55 times, 60 times, 65 times, 70 times, 75 times, 80 times, and any value within the range formed by any two of these values.

[0037] According to the present invention, preferably, the first prepolymerization reaction is a batch prepolymerization, wherein the conditions of the first prepolymerization reaction include: an operating temperature of -50 to 70°C, preferably -30 to 50°C, more preferably -10 to 50°C, for example -50°C, -40°C, -30°C, -20°C, -10°C, 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, and any value within any range formed by any two of these values; and an operating pressure ≤1 MPaG, preferably 0.01-0.5 MPaG, for example... 0.01 MPaG, 0.05 MPaG, 0.1 MPaG, 0.15 MPaG, 2 MPaG, 0.25 MPaG, 0.3 MPaG, 0.4 MPaG, 0.45 MPaG, 0.5 MPaG, 0.55 MPaG, 0.6 MPaG, 0.65 MPaG, 0.7 MPaG, 0.75 MPaG, 0.8 MPaG, 0.85 MPaG, 0.9 MPaG, 0.95 MPaG, 1 MPaG, and any value within the range formed by any two of these values.

[0038] In this invention, the intermittent prepolymerization is achieved by controlling the reaction rate through controlling the operating pressure and operating temperature.

[0039] When the first prepolymerization reaction is a batch prepolymerization, preferably, the prepolymerization ratio of the first prepolymerization reaction is ≤1000 times, preferably 0.5-80 times, for example 0.5 times, 5 times, 10 times, 15 times, 20 times, 25 times, 30 times, 35 times, 40 times, 45 times, 50 times, 55 times, 60 times, 65 times, 70 times, 75 times, 80 times, and any value within the range formed by any two of these values.

[0040] According to the present invention, preferably, the second prepolymerization reaction is a continuous prepolymerization, wherein the conditions of the second prepolymerization reaction include: an operating temperature of -30 to 100°C, preferably -10 to 70°C; an operating pressure of 0.1-10 MPaG, preferably 0.5-5 MPaG; and a residence time ≤2h, preferably 1-90min.

[0041] According to the present invention, preferably, the prepolymerization ratio of the second prepolymerization reaction is 1-3000 times, more preferably 10-1000 times, and more preferably 50-800 times, for example 50 times, 100 times, 150 times, 200 times, 250 times, 300 times, 350 times, 400 times, 450 times, 500 times, 550 times, 600 times, 650 times, 700 times, 750 times, 800 times, and any value within the range formed by any two of these values.

[0042] The present invention does not have a particular limitation on the amount of the second polymerizing monomer, as long as the prepolymerization ratio of the second prepolymerization reaction is achieved.

[0043] Preferably, the first prepolymerization reaction is carried out in a first prepolymerization reactor.

[0044] Preferably, the second prepolymerization reaction is carried out in a second prepolymerization reactor.

[0045] This invention does not specifically limit the first prepolymerization reactor and the second prepolymerization reactor. Any container that meets the above-described operating conditions for the first prepolymerization reaction can be defined as the first prepolymerization reactor, and any container that meets the above-described operating conditions for the second prepolymerization reaction can be defined as the second prepolymerization reactor. The first and second prepolymerization reactors of this invention can take various forms, including batch reactors, tubular reactors, and even pipeline reactors. These reactor types are well known to those skilled in the art.

[0046] A batch reactor can be a conventional batch reactor or a more specialized batch reactor, such as a pre-complexation batch reactor.

[0047] The first prepolymerization reactor and the second prepolymerization reactor may be the same or different, and the present invention does not limit this.

[0048] This invention does not impose any particular limitation on the feeding method of each material in the first and second prepolymerization reactions. Materials can be added individually to the prepolymerization reactor or mixed in the feed pipe before being added together. To ensure a sufficient flow rate of the catalyst composition in the pipe, it is preferable to mix them in the feed pipe before adding them together to the prepolymerization reactor.

[0049] According to the present invention, preferably, the polyolefin catalyst composition comprises a main catalyst, a first co-catalyst, an optional impurity remover, and an optional first external electron donor.

[0050] In this invention, the amounts of the main catalyst, the first co-catalyst, the impurity remover, and the first external electron donor in the polyolefin catalyst composition can be conventionally selected in the art.

[0051] The present invention does not particularly limit the amount of the first polymerizing monomer and the polyolefin catalyst composition, as long as the prepolymerization ratio of the first prepolymerization reaction is achieved. Preferably, the ratio of the mass of the first polymerizing monomer to the mass of the main catalyst in the polyolefin catalyst composition is not less than the prepolymerization ratio of the first prepolymerization reaction.

[0052] The present invention allows for a wide range of choices for the main catalyst, which can be conventional choices in the art. Preferably, the main catalyst is selected from at least one of Ziegler-Natta catalysts, chromium-based catalysts, and vanadium-based catalysts, and is preferably a Ziegler-Natta catalyst (ZN catalyst for short).

[0053] The specific types of Ziegler-Natta catalysts, chromium-based catalysts, and vanadium-based catalysts described in this invention are not particularly limited. Various Ziegler-Natta catalysts, chromium-based catalysts, and vanadium-based catalysts commonly used in the art can be used, and this invention does not make any requirements in this regard.

[0054] The present invention allows for a wide range of choices for the type of the first cocatalyst, which can be a conventional choice in the art. Preferably, the first cocatalyst is a Group IIIA metal compound, more preferably an aluminum compound.

[0055] More preferably, the aluminum compound is selected from at least one of alkyl aluminum compounds, alkyl aluminum halides, alkoxy aluminum compounds, alkyl alkoxy aluminum compounds, and alkoxy aluminum halides.

[0056] The present invention does not particularly limit the amount of the first co-catalyst, and can use a conventional selection in the art. Preferably, the mass ratio of the main catalyst to the first co-catalyst is 1:0.05-100.

[0057] In this invention, the "optional impurity remover and optional first external electron donor" means that the impurity remover and the first external electron donor may or may not be introduced into the polyolefin catalyst composition.

[0058] The impurity removal agent described in this invention can be any of the various impurity removal agents conventionally used in the art.

[0059] The present invention does not impose any particular limitation on the amount of the impurity removal agent, and can be a conventional choice in the field, which will not be elaborated further here.

[0060] It should be noted that when the first co-catalyst is an aluminum compound, it can also be used as a purification agent, in which case no purification agent is added separately.

[0061] The present invention allows for a wide range of selections for the first external electron donor, which can be various commonly used external electron donors in the art. According to the present invention, preferably, the first external electron donor is selected from at least one of organic amine external electron donors, aromatic carboxylic acid ester external electron donors, siloxane external electron donors, calixarene external electron donors, ether external electron donors, aminosilane external electron donors, and carbonate external electron donors.

[0062] The present invention does not particularly limit the specific types of the above-mentioned organic amine electron donors, aromatic carboxylic acid ester electron donors, siloxane electron donors, calixarene electron donors, ether electron donors, aminosilane electron donors, and carbonate electron donors, and can be conventional choices in the art.

[0063] The present invention does not particularly limit the amount of the first external electron donor, and can use conventional choices in the art. Preferably, the mass ratio of the first co-catalyst to the first external electron donor is 1:0.1-100.

[0064] According to the present invention, the main catalyst, the first co-catalyst, the impurity remover and the first external electron donor of the polyolefin catalyst composition can be added to the first prepolymerization reactor separately, or they can be mixed and added together to the first prepolymerization reactor.

[0065] According to the present invention, preferably, the first polymerizing monomer and the second polymerizing monomer are each independently C2-C containing carbon-carbon double bonds and carbon-carbon triple bonds. 16 Hydrocarbon compounds, preferably C2-C 16 The olefins, more preferably selected from ethylene, propylene, 1-butene, 1-hexene, 1-octene, propadiene, 1,3-butadiene, 1,4-butadiene, 1,2-pentadiene, 1,3-pentadiene, 1,4-pentadiene, vinylcyclopentane, vinylcyclohexane, and C3-C 12 At least one of the cyclic olefins.

[0066] According to the present invention, preferably, the C3-C 12 The cycloolefin is selected from at least one of cyclobutadiene, cyclopentadiene, cyclobutene, cyclopentene, and norbornene.

[0067] In this invention, the first polymeric monomer and the second polymeric monomer can be of the same type or different types.

[0068] To further improve the problems of polymer breakage and large particle agglomeration, preferably, the first polymerizing monomer and the second polymerizing monomer are of different types.

[0069] When the first polymeric monomer and the second polymeric monomer are of different types, preferably, the first polymeric monomer includes a portion of the same type as the second polymeric monomer and a portion of different type.

[0070] Preferably, in the first polymeric monomer, the mass ratio of the portion that is the same type as the second polymeric monomer and the portion that is different type from the second polymeric monomer is 1-99:99-1.

[0071] Preferably, the C3-C 12 The cycloolefin is selected from at least one of cyclobutadiene, cyclopentadiene, cyclobutene, cyclopentene, and norbornene.

[0072] In the method of the present invention, one or more of the polyolefin catalyst composition may be added to the second prepolymerization reaction, or one or more of the polyolefin catalyst composition may not be added. That is, at least one of the main catalyst, the second cocatalyst, the impurity remover, and the second external electron donor may be added to the second prepolymerization reaction, or at least one of the main catalyst, the second cocatalyst, the impurity remover, and the second external electron donor may not be added. Preferably, the method further includes adding at least one of the main catalyst, the second cocatalyst, the impurity remover, and the second external electron donor to the second prepolymerization reaction.

[0073] More preferably, the method further includes adding a second co-catalyst and a second external electron donor to the second prepolymerization reaction. This preferred embodiment can further improve the problems of polymer breakage and large particle agglomeration.

[0074] Preferably, the mass ratio of the first cocatalyst to the second cocatalyst is 1:99-99:1, and more preferably 5:95-60:40.

[0075] Preferably, the mass ratio of the second external electron donor to the first external electron donor is 1:99-99:1, and more preferably 10:90-90:10.

[0076] The present invention allows for a wide range of choices for the type of the second cocatalyst, which can be conventional choices in the art. Preferably, the second cocatalyst is a Group IIIA metal compound, more preferably an aluminum compound.

[0077] More preferably, the aluminum compound is selected from at least one of alkyl aluminum compounds, alkyl aluminum halides, alkoxy aluminum compounds, alkyl alkoxy aluminum compounds, and alkoxy aluminum halides.

[0078] The present invention allows for a wide range of choices for the second external electron donor, which can be conventional choices in the art. According to the present invention, preferably, the second external electron donor is selected from at least one of organic amine external electron donors, aromatic carboxylic acid ester external electron donors, siloxane external electron donors, calixarene external electron donors, ether external electron donors, aminosilane external electron donors, and carbonate external electron donors.

[0079] The present invention does not particularly limit the specific types of the above-mentioned organic amine electron donors, aromatic carboxylic acid ester electron donors, siloxane electron donors, calixarene electron donors, ether electron donors, aminosilane electron donors, and carbonate electron donors, and can be conventional choices in the art.

[0080] In this invention, the second cocatalyst and the first cocatalyst may be of the same or different types. Similarly, the second external electron donor and the first external electron donor may be of the same or different types.

[0081] According to the present invention, preferably, the method includes:

[0082] (1) The first polymerization monomer, the main catalyst, the first co-catalyst, the first external electron donor and the optional impurity removal agent are subjected to a first prepolymerization reaction to obtain a first prepolymerization catalyst slurry;

[0083] (2) In the presence of the second co-catalyst and the second external electron donor, the first prepolymerization catalyst slurry obtained in step (1) is subjected to a second prepolymerization reaction with the second polymerizing monomer to obtain the second prepolymerization catalyst slurry.

[0084] The first external electron donor and the second external electron donor are of different types.

[0085] The inventors have discovered that when different types of first and second external electron donors are used, the synergistic effect of the first and second external electron donors can significantly improve the problem of polymer breakage.

[0086] Further research by the inventors revealed that the synergistic effect of a first external electron donor with weak Lewis basicity and a second external electron donor with strong Lewis basicity can significantly improve the problem of polymer breakage.

[0087] The orbital with the highest energy level where an electron donor has occupied an electron is called the highest occupied orbital (HOMO), and the orbital with the lowest energy level where an electron donor has not occupied an electron is called the lowest unoccupied orbital (LUMO). HOMO and LUMO are collectively referred to as frontier orbitals. HOMO orbitals have relatively loose electron binding and possess electron donor properties; therefore, the higher the energy level of a HOMO orbital, the stronger its electron donor ability and the stronger its basicity.

[0088] Preferably, the HOMO orbital energy level of the first external electron donor is 0.001-1 eV weaker than the HOMO orbital energy level of the second external electron donor.

[0089] In this invention, the HOMO orbital energy levels of the external electron body are calculated using the Fukui function method (see reference: Chattaraj PK. Chemical Reactivity and Selectivity: Local HSAB Principle versus Frontier Orbital Theory[J]. Journal of Physical Chemistry A,2001,105(2):511-513).

[0090] This invention provides exemplary examples of HOMO orbital energy levels for common external electron donors in the art, as detailed in Table 1. The basicity of other external electron donors can be determined by calculating the HOMO orbital energy levels.

[0091] Table 1

[0092] Dicyclopentyldimethoxysilane -6.513 Dicyclohexyldimethoxysilane -6.476 Cyclohexylmethyldimethoxysilane -6.633 Diisopropyldimethoxysilane -6.637 diisobutyldimethoxysilane -6.815 Tetramethoxysilane -7.417

[0093] The addition of an inert solvent can, to some extent, reduce the concentration of monomers near the active site of the catalyst and inhibit the diffusion rate of monomers, thereby controlling the reaction rate. This invention can make appropriate selections according to the reaction requirements. Preferably, an inert solvent may also be added to the first prepolymerization reaction and / or the second prepolymerization reaction.

[0094] This invention allows for a wide range of choices for the inert solvent; any inert solvent that does not react with the materials involved in the first and second prepolymerization reactions can be used. Preferably, the inert solvent for the first and second prepolymerization reactions are each independently C2-C. 40 Hydrocarbon compounds, preferably C3-C 10 The hydrocarbon compound is more preferably at least one of propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, octane, heptane, decane, and aromatic hydrocarbon compounds.

[0095] The present invention does not have a particular limitation on the amount of inert solvent used, as long as the prepolymerization ratio of the first prepolymerization reaction and / or the second prepolymerization reaction is obtained.

[0096] Hydrogen can be used as a molecular weight regulator and can be selected appropriately according to the reaction requirements. Preferably, hydrogen can also be added to the first prepolymerization reaction and / or the second prepolymerization reaction.

[0097] This invention does not impose any particular limitation on the amount of hydrogen used; it can be carried out in accordance with conventional methods in the field.

[0098] The second aspect of the present invention provides an application of the prepolymerization method of the polyolefin catalyst described in the first aspect in olefin polymerization, preferably in propylene polymerization.

[0099] A third aspect of the present invention provides an olefin polymerization method, the method comprising: reacting a second prepolymerization catalyst slurry obtained by the prepolymerization method of the polyolefin catalyst described in the first aspect with a third polymerization monomer to obtain an olefin polymer.

[0100] The polymerization conditions described in this invention are conventional polymerization conditions in the art, and are not limited herein.

[0101] The polymerization reaction described in this invention may also incorporate an inert solvent as needed. The types of inert solvents are as described in the first aspect.

[0102] The present invention does not have a particular limitation on the amount of the inert solvent used, but rather on obtaining the prepolymerization ratio of the polymerization reaction.

[0103] The polymerization reaction described in this invention may also incorporate hydrogen gas as needed. The amount of hydrogen gas used is as described in the first aspect.

[0104] According to the present invention, preferably, the third polymerizing monomer is a C2-C monomer containing carbon-carbon double bonds and carbon-carbon triple bonds. 16 Hydrocarbon compounds, preferably C2-C 16 The olefin is more preferably selected from at least one of ethylene, propylene, 1-butene, 1-hexene, 1-octene, propadiene, 1,3-butadiene, 1,4-butadiene, 1,2-pentadiene, 1,3-pentadiene, 1,4-pentadiene, vinylcyclopentane, and vinylcyclohexane.

[0105] According to the present invention, preferably, the olefin polymer is C2-C. 16 The polyolefin preferably includes at least one of polypropylene, polyethylene, polybutene, poly(butene-hexene), poly(ethylene-butene), and poly(ethylene-hexene).

[0106] Preferably, the polymerization reaction is carried out in the main reactor.

[0107] Preferably, the main reactor is a reactor with a reaction mass load exceeding 80%. That is, the polymerization reaction occurring in the main reactor is the main reaction for olefin polymerization, and the prepolymerization reaction is an auxiliary reaction.

[0108] This invention does not specifically limit the type of the main reactor; any container that meets the above-described polymerization reaction operating conditions can be defined as the main reactor. For example, it can be a fluidized bed reactor, a tubular reactor, a batch reactor, or a multiphase multi-zone reactor.

[0109] The reaction phases in the main reactor described in this invention are various phases such as gas-solid phase, solid-liquid phase, solid-liquid-gas phase, and liquid-liquid phase.

[0110] According to a specific embodiment of the present invention, such as Figure 1 As shown, the polyolefin catalyst composition 101 and the first material stream 102 containing the first polymerizing monomer are continuously injected into the first prepolymerization reactor 01 via pipelines; the second material stream 202 containing the second polymerizing monomer is mixed with the first prepolymerization catalyst slurry 201 and then continuously injected into the second prepolymerization reactor 02; the second prepolymerization catalyst slurry 301 is continuously injected into the main reactor 03; the main reactor feed 303 containing the third polymerizing monomer is injected into the main reactor 03; the main reactor discharge 302 is sent to subsequent reactors or other equipment. The coolant 103 in the first prepolymerization reactor and the coolant 203 in the second prepolymerization reactor continuously enter and exit, providing heat for the prepolymerization reaction.

[0111] According to a specific embodiment of the present invention, such as Figure 2 As shown, the polyolefin catalyst composition 111 is mixed with a first material stream 112 containing a first polymerizing monomer and then continuously injected into the first prepolymerization reactor 11 via a pipeline; a second material stream 212 containing a second polymerizing monomer and the first prepolymerization catalyst slurry 211 are respectively injected into the second prepolymerization reactor 12 via pipelines; the second prepolymerization catalyst slurry 311 is continuously injected into the main reactor 13; the main reactor feed 313 containing a third polymerizing monomer is injected into the main reactor 13; the main reactor discharge 312 is sent to subsequent reactors or other equipment. The coolant 113 in the first prepolymerization reactor and the coolant 213 in the second prepolymerization reactor continuously flow in and out, providing heat for the prepolymerization reaction.

[0112] According to a specific embodiment of the present invention, such as Figure 3 As shown, the polyolefin catalyst composition 121 and the first material stream 122 containing the first polymerizing monomer are injected into the first prepolymerization reactor 21 via pipelines; the first prepolymerization catalyst slurry 221 is pressurized by pump 24 and mixed with the second material stream 222 containing the second polymerizing monomer, and then continuously injected into the second prepolymerization reactor 22; the second prepolymerization catalyst slurry 321 is continuously injected into the main reactor 23; the main reactor feed 323 containing the third polymerizing monomer is injected into the main reactor 23; the main reactor discharge 322 is sent to subsequent reactors or other equipment. The coolant 123 of the first prepolymerization reactor and the coolant 223 of the second prepolymerization reactor continuously enter and exit, providing heat for the prepolymerization reaction.

[0113] In this invention, the terms "first," "second," and "third" do not limit the substances and operations, but are only used to distinguish the substances introduced in different steps and the operations performed in different stages.

[0114] The present invention will be described in detail below through embodiments.

[0115] In the following embodiments,

[0116] Polymer sieving test method: 100g sample was placed in a Frisch vibrating sieve (model: Analysette 3) with a vibration amplitude of 2.0mm and a vibration time of 15min. The weight of the sample on sieves with different aperture sizes was weighed, and the proportion of the sample in different fractions was calculated.

[0117] Fall time test method: 100g sample is completely poured out of a stainless steel conical funnel (cone angle 60±0.5°, outflow diameter 10mm), and the time taken is measured.

[0118] The ZN catalyst used in Examples 1, 3, and 4 was a product of Sinopec Aoda Catalyst Branch with the grade DQC602.

[0119] The ZN catalyst used in Example 2 is a product of Sinopec Aoda Catalyst Branch with the brand name BCL.

[0120] Example 1

[0121] Propylene polymerization according to Figure 1 The process proceeds as follows:

[0122] The propylene polymerization reaction is carried out on a bulk propylene polymerization unit, which mainly includes a first prepolymerization reactor (1L), a second prepolymerization reactor (5L), and a loop reactor (75L).

[0123] (1) First prepolymerization reaction

[0124] The Zn catalyst (main catalyst) was mixed at a flow rate of 0.2 g / hr, triethylaluminum (co-catalyst) at a flow rate of 8 g / hr, and the external electron donor (cyclohexylmethyldimethoxysilane) at a flow rate of 1 g / hr to form a polyolefin catalyst composition, which was continuously injected into the first prepolymerization reactor. The liquid propylene feed stream was also continuously injected into the first prepolymerization reactor at a flow rate of 0.5 kg / hr. The prepolymerization temperature of the first prepolymerization reaction was -5°C, the operating pressure was 4 MPaG, and the residence time was approximately 50 min.

[0125] (2) Second prepolymerization reaction

[0126] The first prepolymerization catalyst slurry is mixed with the liquid propylene feed at a total flow rate of 15 kg / hr and then injected into the second prepolymerization reactor. The prepolymerization temperature of the second prepolymerization reaction is 30°C, the operating pressure is 4 MPaG, and the residence time is about 10 min.

[0127] (3) Polymerization reaction

[0128] The second prepolymerization catalyst slurry is continuously injected into the loop reactor. The polymerization reaction temperature is 70℃, the reaction pressure is 4MPaG, and 40 kg / h of propylene and hydrogen enter the main reactor. The hydrogen concentration in the reactor is approximately 6000 ppmv. The residence time is approximately 0.7 h.

[0129] The obtained polypropylene granules were sieved and their falling time was tested. The results are shown in Table 2.

[0130] Example 2

[0131] Ethylene polymerization according to Figure 1 The process proceeds as follows:

[0132] The ethylene polymerization reaction was carried out on a 25 kg / hr slurry polymerization unit, which mainly consisted of a first prepolymerization reactor (1 L), a second prepolymerization reactor (5 L), and a loop reactor (75 L).

[0133] (1) First prepolymerization reaction

[0134] The main catalyst (ZN catalyst) flow rate is 0.66 g / hr, the triethylaluminum flow rate is 7.6 g / hr, and the polyolefin catalyst composition is mixed together with isobutane (inert solvent) at a flow rate of 0.5 kg / hr and continuously injected into the first prepolymerization reactor; the ethylene feed flow rate is 0.2 kg / hr and is continuously injected into the first prepolymerization reactor; the prepolymerization temperature of the first prepolymerization reaction is -5℃, the operating pressure is 5 MPaG, and the residence time is approximately 55 min.

[0135] (2) Second prepolymerization reaction

[0136] The first prepolymerization catalyst slurry is mixed with isobutane containing ethylene (2 kg / hr) at a total flow rate of 15 kg / hr and then injected into the second prepolymerization reactor. The prepolymerization temperature of the second prepolymerization reaction is 40°C, the operating pressure is 5 MPaG, and the residence time is about 11 min.

[0137] (3) Polymerization reaction

[0138] The second prepolymerization catalyst slurry is continuously injected into the main reactor. The polymerization reaction temperature is 70℃, the reaction pressure is 5MPaG, and the hydrogen and ethylene feed is 26kg / hr. It enters the main reactor along with 50kg / h of isobutane. The hydrogen concentration in the reactor is about 4000ppm(v).

[0139] The obtained polypropylene granules were sieved and their falling time was tested. The results are shown in Table 2.

[0140] Example 3

[0141] Propylene polymerization according to Figure 2 The process proceeds as follows:

[0142] The propylene polymerization reaction is carried out on a gas-phase propylene polymerization unit, which mainly includes a first prepolymerization reactor (1L), a second prepolymerization reactor (5L), and a gas-phase fluidized bed reactor (500L).

[0143] (1) First prepolymerization reaction

[0144] The main catalyst (ZN catalyst) flow rate is 0.36 g / hr, the triethylaluminum (co-catalyst) flow rate is 4 g / hr, and the external electron donor (cyclohexylmethyldimethoxysilane) flow rate is 0.4 g / hr. They are mixed to form a polyolefin catalyst composition, which is then mixed with a liquid propylene feed flow rate of 0.5 kg / hr and continuously injected into the first prepolymerization reactor. The prepolymerization temperature of the first prepolymerization reaction is 5 °C, the operating pressure is 2.6 MPaG, and the residence time is approximately 47 min.

[0145] (2) Second prepolymerization reaction

[0146] The first prepolymerization catalyst slurry is directly injected into the second prepolymerization reactor, and the liquid propylene feed flow rate is 15 kg / hr. The prepolymerization temperature of the second prepolymerization reaction is 30°C, the operating pressure is 2.6 MPaG, and the residence time is about 10 min.

[0147] (3) Polymerization reaction

[0148] The second prepolymerization catalyst slurry is continuously injected into the gas-phase fluidized bed reactor. The polymerization reaction temperature is 70℃, the reaction pressure is 2.6MPaG, and propylene at a rate of 17kg / h and hydrogen enter the main reactor. The hydrogen concentration in the reactor is approximately 12000ppm(v).

[0149] The obtained polypropylene granules were sieved and their falling time was tested. The results are shown in Table 2.

[0150] Example 4

[0151] Propylene polymerization according to Figure 3 The process proceeds as follows:

[0152] The propylene polymerization reaction is carried out on a bulk propylene polymerization unit, which mainly includes a first prepolymerization reactor (1L), a second prepolymerization reactor (5L), and a loop reactor (75L).

[0153] (1) First prepolymerization reaction

[0154] 0.5 L of hexane (inert solvent), 12 g of triethylaluminum (co-catalyst), and 3 g of external electron donor (cyclohexylmethyldimethoxysilane) were added to the first prepolymerization reactor in one batch. 200 g of the main catalyst (Zn catalyst) was also added to the first prepolymerization reactor in one batch. A 1 kg liquid propylene feed stream was continuously and slowly injected into the first prepolymerization reactor. The prepolymerization temperature of the first prepolymerization reaction was 20 °C, the operating pressure was 0.15 MPaG, and the prepolymerization ratio was approximately 5 times.

[0155] The prepolymerized catalyst was dispersed in an inert solvent (white oil and petroleum jelly in a mass ratio of 1:1) and then injected into the second prepolymerization reactor by a pump with increased pressure. The flow rate of the prepolymerized catalyst was 1 g / hr.

[0156] (1) Second prepolymerization reaction

[0157] Same as Example 1. The difference is that the flow rate of triethylaluminum (co-catalyst) is 8 g / hr, and the flow rate of the external electron donor (cyclohexylmethyldimethoxysilane) is 1 g / hr, which is injected together with the liquid propylene feed.

[0158] (3) Polymerization reaction

[0159] Same as Example 1.

[0160] The obtained polypropylene granules were sieved and their falling time was tested. The results are shown in Table 2.

[0161] Example 5

[0162] Similar to Example 1, except that the prepolymerization temperature of the first prepolymerization reaction is 27°C, the flow rate of the liquid propylene feed is 8.0 kg / hr, and it is continuously injected into the first prepolymerization reactor with a residence time of about 4 min.

[0163] The obtained polypropylene granules were sieved and their falling time was tested. The results are shown in Table 2.

[0164] Example 6

[0165] Similar to Example 1, except that 3.0 kg / hr of inert solvent (hexane) and 0.2 kg / hr of propylene are combined and continuously injected into the first prepolymerization reactor, with a prepolymerization ratio of approximately 2 times and a residence time of approximately 12 min.

[0166] The obtained polypropylene granules were sieved and their falling time was tested. The results are shown in Table 2.

[0167] Example 7

[0168] Same as Example 1, except that the first external electron donor (tetramethoxysilane) is injected into the first prepolymerization reactor at a flow rate of 0.3 g / hr. The second external electron donor (cyclohexylmethyldimethoxysilane) is injected into the second prepolymerization reactor at a flow rate of 0.7 g / hr.

[0169] The obtained polypropylene granules were sieved and their falling time was tested. The results are shown in Table 2.

[0170] Example 8

[0171] Same as Example 1, except that the first external electron donor (cyclohexylmethyldimethoxysilane) is injected into the first prepolymerization reactor at a flow rate of 0.3 g / hr. The second external electron donor is injected into the second prepolymerization reactor at a flow rate of 0.7 g / hr, the same as the first external electron donor (cyclohexylmethyldimethoxysilane).

[0172] The obtained polypropylene granules were sieved and their falling time was tested. The results are shown in Table 2.

[0173] Example 9

[0174] Similar to Example 1, except that the first monomer is composed of a liquid propylene flow rate of 0.4 kg / hr and an ethylene flow rate of 0.1 kg / hr, and is continuously injected into the first prepolymerization reactor.

[0175] The obtained polypropylene granules were sieved and their falling time was tested. The results are shown in Table 2.

[0176] Comparative Example 1

[0177] Similar to Example 1, except that the first prepolymerization reaction is not carried out, and the liquid propylene feed stream of 15 kg / hr is mixed with the polyolefin catalyst composition and then injected into the second prepolymerization reactor.

[0178] The obtained polypropylene granules were sieved and their falling time was tested. The results are shown in Table 2.

[0179] Comparative Example 2

[0180] Similar to Example 2, except that the first prepolymerization reaction is not carried out, and the isobutane feed containing ethylene (2 kg / hr) is mixed with the polyolefin catalyst composition at a flow rate of 15 kg / hr and then injected into the second prepolymerization reactor.

[0181] The obtained polypropylene granules were sieved and their falling time was tested. The results are shown in Table 2.

[0182] Comparative Example 3

[0183] Similar to Example 3, except that the first prepolymerization reaction is not carried out, and the liquid propylene feed stream of 15 kg / hr and the polyolefin catalyst composition are separately injected into the second prepolymerization reactor.

[0184] The obtained polypropylene granules were sieved and their falling time was tested. The results are shown in Table 2.

[0185]

[0186] As shown in Table 2, the method of this invention can reduce the proportion of fine polymer powder (part with a sieve particle size < 0.071 mm) and large agglomerated particles (part with a sieve particle size > 2 mm), resulting in a narrower polymer particle size distribution. Furthermore, the falling time indicates that the method of this invention improves the flowability of polymer particles.

[0187] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for prepolymerizing polyolefin catalysts, characterized in that, The method includes: (1) The first polymerizing monomer and the polyolefin catalyst composition are subjected to a first prepolymerization reaction to obtain a first prepolymerization catalyst slurry; (2) The first prepolymerization catalyst slurry obtained in step (1) is subjected to a second prepolymerization reaction with the second polymerizing monomer to obtain the second prepolymerization catalyst slurry; The temperature of the second prepolymerization reaction is 10-50°C higher than that of the first prepolymerization reaction. The prepolymerization ratio of the second prepolymerization reaction is 5-100 times that of the first prepolymerization reaction.

2. The method according to claim 1, wherein, The first prepolymerization reaction is a continuous prepolymerization, wherein the conditions of the first prepolymerization reaction include: operating temperature of -50 to 30°C; operating pressure of 0.1-10 MPaG; and residence time ≤ 6 h.

3. The method according to claim 2, wherein, The first prepolymerization reaction is a continuous prepolymerization, wherein the conditions of the first prepolymerization reaction include: an operating temperature of -30 to 20°C; an operating pressure of 0.5 to 5 MPaG; and a residence time of 1 to 120 min.

4. The method according to claim 1, wherein, The prepolymerization ratio of the first prepolymerization reaction is ≤1000 times.

5. The method according to claim 4, wherein, The prepolymerization ratio of the first prepolymerization reaction is 0.5-80 times.

6. The method according to claim 1, wherein, The first prepolymerization reaction is a batch prepolymerization reaction, wherein the conditions for the first prepolymerization reaction include: an operating temperature of -50 to 70°C; and an operating pressure ≤1 MPaG.

7. The method according to claim 6, wherein, The first prepolymerization reaction is a batch prepolymerization reaction, wherein the conditions of the first prepolymerization reaction include: an operating temperature of -30 to 50°C; and an operating pressure of 0.01 to 0.5 MPaG.

8. The method according to claim 6, wherein, The prepolymerization ratio of the first prepolymerization reaction is ≤1000 times.

9. The method according to claim 8, wherein, The prepolymerization ratio of the first prepolymerization reaction is 0.5-80 times.

10. The method according to claim 1, wherein, The second prepolymerization reaction is a continuous prepolymerization reaction, wherein the conditions for the second prepolymerization reaction include: operating temperature of -30 to 100°C; operating pressure of 0.1-10 MPaG; and residence time ≤2h.

11. The method according to claim 10, wherein, The second prepolymerization reaction is a continuous prepolymerization reaction, wherein the conditions of the second prepolymerization reaction include: operating temperature of -10 to 70°C; operating pressure of 0.5-5 MPaG; and residence time of 1-90 min.

12. The method according to claim 1, wherein, The prepolymerization ratio of the second prepolymerization reaction is 1-3000 times.

13. The method according to claim 12, wherein, The prepolymerization ratio of the second prepolymerization reaction is 10-1000 times.

14. The method according to claim 13, wherein, The prepolymerization ratio of the second prepolymerization reaction is 50-800 times.

15. The method according to any one of claims 1-14, wherein, The polyolefin catalyst composition comprises a main catalyst, a first co-catalyst, an optional impurity remover, and an optional first external electron donor.

16. The method according to claim 15, wherein, The main catalyst is selected from at least one of Ziegler-Natta catalysts, chromium-based catalysts, and vanadium-based catalysts.

17. The method according to claim 16, wherein, The main catalyst is a Ziegler-Natta catalyst.

18. The method according to claim 15, wherein, The first cocatalyst is a Group IIIA metal compound.

19. The method according to claim 18, wherein, The first cocatalyst is an aluminum compound.

20. The method according to claim 19, wherein, The aluminum compound is selected from at least one of alkylaluminum compounds, alkylaluminum halides, alkoxyaluminum compounds, alkylalkoxyaluminum compounds, and alkoxyaluminum halides.

21. The method according to claim 15, wherein, The first external electron donor is selected from at least one of organic amine external electron donors, aromatic carboxylic acid ester external electron donors, siloxane external electron donors, calixarene external electron donors, ether external electron donors, aminosilane external electron donors, and carbonate external electron donors.

22. The method according to any one of claims 1-14, wherein, The first and second monomers are each independently C2-C containing carbon-carbon double bonds and carbon-carbon triple bonds. 16 At least one of the hydrocarbon compounds.

23. The method according to claim 22, wherein, The first and second monomers are C2-C 16 At least one of the olefins.

24. The method according to claim 23, wherein, The first and second polymerization monomers are ethylene, propylene, 1-butene, 1-hexene, 1-octene, propadiene, 1,3-butadiene, 1,4-butadiene, 1,2-pentadiene, 1,3-pentadiene, 1,4-pentadiene, vinylcyclopentane, vinylcyclohexane, and C3-C 12 At least one of the cyclic olefins.

25. The method according to claim 15, wherein, The method further includes adding a second cocatalyst and a second external electron donor to the second prepolymerization reaction.

26. The method according to claim 25, wherein, The mass ratio of the first cocatalyst to the second cocatalyst is 1:99-99:

1.

27. The method according to claim 26, wherein, The mass ratio of the first cocatalyst to the second cocatalyst is 5:95-60:

40.

28. The method according to claim 25, wherein, The mass ratio of the second external electron donor to the first external electron donor is 1:99-99:

1.

29. The method according to claim 28, wherein, The mass ratio of the second external electron donor to the first external electron donor is 10:90-90:

10.

30. The method according to claim 25, wherein, The second cocatalyst is a Group IIIA metal compound.

31. The method according to claim 30, wherein, The second cocatalyst is an aluminum compound.

32. The method according to claim 31, wherein, The aluminum compound is selected from at least one of alkylaluminum compounds, alkylaluminum halides, alkoxyaluminum compounds, alkylalkoxyaluminum compounds, and alkoxyaluminum halides.

33. The method according to claim 25, wherein, The second external electron donor is selected from at least one of organic amine external electron donors, aromatic carboxylic acid ester external electron donors, siloxane external electron donors, calixarene external electron donors, ether external electron donors, aminosilane external electron donors, and carbonate external electron donors.

34. The method according to claim 25, wherein, The method includes: (1) The first polymerization monomer, the main catalyst, the first co-catalyst, the first external electron donor and the optional impurity removal agent are subjected to a first prepolymerization reaction to obtain a first prepolymerization catalyst slurry; (2) In the presence of the second co-catalyst and the second external electron donor, the first prepolymerization catalyst slurry obtained in step (1) is subjected to a second prepolymerization reaction with the second polymerizing monomer to obtain the second prepolymerization catalyst slurry; The first external electron donor and the second external electron donor are of different types.

35. The application of the prepolymerization method of the polyolefin catalyst according to any one of claims 1-34 in olefin polymerization.

36. The application according to claim 35, wherein, Application of the prepolymerization method of the polyolefin catalyst in propylene polymerization.

37. A method for olefin polymerization, characterized in that, The method includes: reacting a second prepolymerized catalyst slurry obtained by the prepolymerization method of the polyolefin catalyst according to any one of claims 1-34 with a third polymerizing monomer to obtain an olefin polymer.

38. The method according to claim 37, wherein, The third monomer is a C2-C monomer containing carbon-carbon double and triple bonds. 16 At least one of the hydrocarbon compounds.

39. The method according to claim 38, wherein, The third monomer is C2-C. 16 At least one of the olefins.

40. The method according to claim 39, wherein, The third polymerization monomer is at least one of ethylene, propylene, 1-butene, 1-hexene, 1-octene, propadiene, 1,3-butadiene, 1,4-butadiene, 1,2-pentadiene, 1,3-pentadiene, 1,4-pentadiene, vinylcyclopentane, and vinylcyclohexane.

41. The method according to claim 37, wherein, The olefin polymer is C2-C. 16 At least one of the polyolefins.

42. The method according to claim 37, wherein, The olefin polymer includes at least one of polypropylene, polyethylene, polybutene, poly(butene-hexene), poly(ethylene-butene), and poly(ethylene-hexene).

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