Ethylene gas treatment method, polyolefin elastomer and preparation method thereof

Abstract

The invention provides an ethylene gas processing method, a polyolefin elastomer and a preparation method thereof, and belongs to the technical field of polymerization process. The ethylene gas processing method comprises: passing commercially available ethylene gas through a primary purification tank, a secondary purification tank and a tertiary purification tank in sequence to obtain activated ethylene gas; wherein the primary purification tank is loaded with a triglyceride solution of Cu(Qc)2 or a triglyceride solution of Zn(benzimidazole)2 or pure triglyceride, wherein Qc represents quinoline-5-carboxylate; the secondary purification tank is loaded with anhydrous ether; and the tertiary purification tank is loaded with an organic solvent containing trace amounts of water, wherein the organic solvent is selected from at least one of isobutane, n-pentane, isopentane, n-hexane, methylcyclopentane, n-heptane, methylcyclohexane, isooctane, and toluene and a C4-C8 isomeric saturated alkane mixture.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymerization process engineering, and in particular relates to a method for treating ethylene gas, a polyolefin elastomer and a preparation method thereof, and more specifically relates to a method for treating ethylene gas, a preparation method of a polyolefin elastomer by solution polymerization, and a polyolefin elastomer. Background Art

[0002] At present, when ethylene gas is used for homopolymerization or copolymerization, it is generally directly introduced into a reactor for solution polymerization to prepare ethylene homopolymer or ethylene-containing copolymer. However, the presence of some impurity gases in ethylene gas, such as ethane, can easily lead to a decrease in the activity of the solution polymerization reaction. Therefore, there is still room for further improvement in the activity of the solution polymerization reaction. Summary of the invention

[0003] In view of the above technical problems, the present invention provides a method for treating ethylene gas, a polyolefin elastomer and a preparation method thereof, in order to at least partially solve the above technical problems. In this regard, the technical solution provided by the present invention is as follows.

[0004] As a first aspect of the present invention, a method for treating ethylene gas is provided, comprising: passing commercially available ethylene gas through a primary purification tank, a secondary purification tank and a tertiary purification tank in sequence to obtain activated ethylene gas; wherein the primary purification tank is loaded with a triglyceride solution of Cu(Qc)2 or a triglyceride solution of Zn(benzimidazole)2 or pure triglyceride, wherein Qc represents quinoline-5-carboxylate; the secondary purification tank is loaded with anhydrous ether; and the tertiary purification tank is loaded with an organic solvent containing trace amounts of water, wherein the organic solvent is selected from at least one of isobutane, n-pentane, isopentane, n-hexane, methylcyclopentane, n-heptane, methylcyclohexane, isooctane, and toluene and a mixture of isomeric saturated alkanes of C4-C8.

[0005] As a second aspect of the present invention, a method for preparing a polyolefin elastomer is provided, comprising: using the activated ethylene gas obtained by the above-mentioned ethylene gas treatment method as a reaction raw material for solution polymerization.

[0006] As a third aspect of the present invention, there is provided a polyolefin elastomer prepared by the above-mentioned method for preparing a polyolefin elastomer, wherein the polyolefin elastomer is a homopolymer of activated ethylene gas, or a homopolymer of activated ethylene gas and C3-C 12 Copolymers of α-olefins.

[0007] In an embodiment of the present invention, commercially available ethylene gas is passed into a primary purification tank, and triglycerides have a higher adsorption selectivity for impurity gases (such as ethane) in ethylene gas, which can be dissolved or adsorbed into triglycerides without adsorbing ethylene, thereby achieving primary purification of ethylene gas. Subsequently, the ethylene gas treated in the primary purification tank is passed into a secondary purification tank. Since the ethylene gas will carry away part of the triglycerides during the process of being transported to the secondary purification tank, part of the triglycerides contained in the ethylene gas can be removed by using anhydrous ether in the secondary purification tank, thereby achieving secondary purification of the primary purified ethylene gas. Finally, the ethylene gas treated in the secondary purification tank is transported to a tertiary purification tank, and the ethylene gas treated in the secondary purification tank is purified and activated using an organic solvent containing trace amounts of water in the tertiary purification tank to obtain activated ethylene gas, thereby improving the purity and activity of the ethylene gas.

[0008] Furthermore, using activated ethylene gas as a raw material for preparing polyolefin elastomers through solution polymerization can improve the activity of the solution polymerization reaction, thereby obtaining polyolefin elastomers with excellent properties, such as a homopolymer of activated ethylene gas, or a copolymer of activated ethylene gas and C3-C 12 The copolymer of α-olefins helps to further reduce the cost of polyolefin elastomers and enable industrial production. DETAILED DESCRIPTION

[0009] Embodiments of the present invention will be described below, but it should be appreciated that these descriptions are exemplary only, and are not intended to limit the scope of the present invention. In the following detailed description, for ease of explanation, many specific details are set forth to provide a comprehensive understanding of embodiments of the present invention. However, it is apparent that one or more embodiments may also be implemented without these specific details. In addition, in the following description, the description of known structures and technologies is omitted to avoid unnecessarily confusing concepts of the present invention.

[0010] At present, commercially available ethylene gas is generally used to directly carry out solution polymerization to prepare polyolefin elastomers, such as ethylene homopolymers or ethylene-containing copolymers. However, impurity gases (such as ethane) contained in the ethylene gas will reduce the activity of the ethylene polymerization reaction, and thus higher performance polyolefin elastomers cannot be obtained. In this regard, the present invention proposes a method for treating ethylene gas, and uses activated ethylene gas as a raw material to carry out solution polymerization reaction, and the activated ethylene gas makes the polymerization reaction have higher activity, thereby being able to prepare higher performance polyolefin elastomers.

[0011] Specifically, as a first aspect of the present invention, a method for treating ethylene gas is provided, comprising: passing commercially available ethylene gas through a primary purification tank, a secondary purification tank and a tertiary purification tank in sequence to obtain activated ethylene gas; wherein the primary purification tank is loaded with a triglyceride solution of Cu(Qc)2 or a triglyceride solution of Zn(benzimidazole)2 or pure triglyceride, wherein Qc represents quinoline-5-carboxylate; the secondary purification tank is loaded with anhydrous ether; and the tertiary purification tank is loaded with an organic solvent containing trace amounts of water, wherein the organic solvent is selected from at least one of isobutane, n-pentane, isopentane, n-hexane, methylcyclopentane, n-heptane, methylcyclohexane, isooctane, and toluene and a mixture of isomeric saturated alkanes of C4-C8.

[0012] In an embodiment of the present invention, commercially available ethylene gas is introduced into a primary purification tank, and the triglyceride in the primary purification tank has a higher adsorption selectivity for impurity gases (such as ethane) in the ethylene gas, and the impurity gases can be dissolved or adsorbed into the triglyceride without adsorbing ethylene at the same time, thereby achieving primary purification of the ethylene gas. Subsequently, the ethylene gas treated in the primary purification tank is introduced into a secondary purification tank, and in this process, the primary purified ethylene gas will carry away part of the triglyceride, and the anhydrous ether in the secondary purification tank can remove part of the triglyceride contained in the primary purified ethylene gas, thereby achieving secondary purification of the primary purified ethylene gas. Finally, the secondary purified ethylene gas treated in the secondary purification tank is transported to a tertiary purification tank, and a small amount of anhydrous ether in the secondary purified ethylene gas can be removed by using an organic solvent containing trace water in the tertiary purification tank, so as to achieve purification and activation of the ethylene gas, so as to obtain activated ethylene gas. The present invention improves the purity and activity of the ethylene gas through a specific purification and activation sequence, and the purification and activation reagents used.

[0013] For example: the ethylene gas in the commercially available ethylene cylinder is sequentially passed into a primary purification tank (referred to as "purification tank 1"), a secondary purification tank (referred to as "purification tank 2"), and a tertiary purification tank (referred to as "purification tank 3") for purification and activation to obtain activated ethylene gas.

[0014] According to an embodiment of the present invention, in the primary purification tank, the concentration of Cu(Qc)2 or Zn(benzimidazole)2 is 1 μmol / L-100 μmol / L. Within this concentration range, it helps to improve the selective adsorption of impurity gases in ethylene gas and improve the activation efficiency and purity of ethylene gas.

[0015] According to an embodiment of the present invention, Cu(Qc)2 is obtained by ball milling copper hydroxide (Cu(OH)2) and quinoline-5-carboxylic acid (HQc) in the presence of N,N-dimethylformamide and ethanol. For example, Cu(OH)2 and HQc are added to a steel tank containing N,N-dimethylformamide (DMF) and ethanol (EtOH), and after ball milling at 25Hz for 15 minutes, they are dissolved in triglycerides and stirred evenly to obtain a triglyceride solution of Cu(Qc)2.

[0016] According to an embodiment of the present invention, Zn (benzimidazole) 2 is obtained by dissolving benzimidazole and zinc in acetic acid in proportion, refluxing and rotary evaporation, wherein the molar ratio of benzimidazole to zinc is 2: 1. For example: benzimidazole and zinc are dissolved in acetic acid solution in a molar ratio of 2: 1, and refluxed at 65 ° C for 4 hours. Subsequently, the solvent is rotary evaporated, and the remaining liquid is transferred to a beaker, and after cooling to room temperature, the beaker is sealed. After standing for several days, it is dissolved in triglycerides to obtain a triglyceride solution of Zn (benzimidazole) 2.

[0017] As a second aspect of the present invention, a method for preparing a polyolefin elastomer is provided. The method uses the activated ethylene gas obtained by the method for treating ethylene gas in the above embodiment as a reaction raw material for solution polymerization.

[0018] In the embodiments of the present invention, the purity and activity of the ethylene raw material are improved by activating the ethylene gas, so that the solution polymerization reaction has a higher activity, thereby being able to prepare a homopolymer of ethylene with higher performance, such as vinyl polyolefin elastomer (EPOE), or a copolymer of ethylene and α-olefin (such as C3-C 12 Copolymers of α-olefins).

[0019] According to an embodiment of the present invention, the preparation method of polyolefin elastomer solution polymerization includes: passing a main catalyst, a co-catalyst and an activated ethylene gas into a reactor containing a polymerization solvent, performing a solution polymerization reaction, and obtaining a polyolefin elastomer, which is a homopolymer of activated ethylene gas; wherein the polymerization solvent is the same as the organic solvent loaded in the three-stage purification tank, and the molar ratio of trace water to the co-catalyst in the polymerization solvent is 1:2-1:6. In other words, the polymerization solvent is an organic solvent containing trace water, selected from at least one of isobutane, n-pentane, isopentane, n-hexane, methylcyclopentane, n-heptane, methylcyclohexane, isooctane, and toluene and C4-C8 isomerized saturated alkane mixtures. The content of trace water in the organic solvent in the three-stage purification tank is less than 5wt% of the organic solvent, preferably 0.5-5wt%. In the three-stage purification tank, ethylene gas will carry water away and enter the reactor, and react with the co-catalyst in the solution polymerization reaction in the reactor to generate active substances, thereby improving the polymerization activity of the activated ethylene gas.

[0020] In an embodiment of the present invention, in the presence of a main catalyst and a co-catalyst, a solution polymerization reaction (such as a homopolymerization reaction) of activated ethylene gas is carried out in a reactor to obtain a homopolymer of activated ethylene gas (hereinafter referred to as a homopolymer of ethylene), namely, a vinyl polyolefin elastomer (EPOE). The present invention provides a relatively simple method for preparing a polyolefin elastomer, and the preparation of EPOE by activated ethylene greatly improves the polymerization activity, thereby improving the performance of EPOE, such as physical and mechanical properties, aging resistance, UV resistance, low temperature performance (-40°C~-4°C), flow properties, affinity, etc.

[0021] According to an embodiment of the present invention, the organic solvent loaded in the tertiary purification tank is the same as the polymerization solvent, preferably at least one of n-hexane, methylcyclopentane, n-heptane and a mixture of isomeric saturated alkanes of C4-C8, more preferably n-heptane.

[0022] According to an embodiment of the present invention, the main catalyst is a nickel diimide catalyst, and the nickel diimide catalyst has a structure as shown in the following formula (1):

[0023] Formula (1), wherein R is selected from at least one of isobutyl, phenyl, and hydrogen. More specifically, the main catalyst used in the present invention is a nickel diimide catalyst produced by Hefei Zhongke Kele New Materials Co., Ltd., which has a large steric hindrance. The preparation method of the nickel diimide catalyst can refer to the published Chinese patent application documents, such as the Chinese patent application documents with publication numbers CN118084719A, CN117865847A, CN117659237A, CN117645552A, CN117902999A, CN117658851A, etc.

[0024] According to an embodiment of the present invention, the co-catalyst is selected from at least one of triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, sesquiethylaluminum chloride, monoisobutylaluminum monochloride, and diisobutylaluminum dichloride. The molar ratio of trace water in the polymerization solvent to the co-catalyst is 1:2-1:6. Wherein, when the co-catalyst is diethylaluminum monochloride (DEAC), the molar ratio of trace water in the polymerization solvent to diethylaluminum monochloride is 1:3; when the co-catalyst is triethylaluminum, the molar ratio of trace water in the polymerization solvent to triethylaluminum is 1:2; when the co-catalyst is ethylaluminum dichloride (EADC), the molar ratio of trace water in the polymerization solvent to ethylaluminum dichloride is 1:6. The trace water contained in the polymerization solvent can react with the co-catalyst to form ethylaluminoxane (EAO) to increase the activity of the polymerization reaction. For example: ; .

[0025] According to an embodiment of the present invention, in the solution polymerization reaction, the polymerization temperature of the solution polymerization reaction is 25° C.-45° C., and the polymerization pressure is 0.6 MPa-2.0 MPa.

[0026] For example, a method for preparing a vinyl polyolefin elastomer through a solution polymerization reaction may include: introducing a polymerization solvent (such as n-heptane) into a reactor, using nitrogen to vacuum replace the air in the reactor, and repeating multiple times (such as 3 times). Subsequently, the ethylene gas in the commercially available ethylene gas cylinder is directly introduced into purification tank 1, purification tank 2, and purification tank 3 in sequence for purification and activation to obtain activated ethylene gas. The obtained activated ethylene gas is introduced into the reactor to replace the nitrogen in the reactor, and the process is repeated multiple times. Furthermore, after introducing a co-catalyst (such as DEAC) into the reactor and stirring for 25 minutes, the main catalyst (such as a nickel diimide catalyst shown in formula (1), wherein R is selected from H) is introduced into the reactor and stirred for 1 minute, and the activated ethylene gas is introduced into the reactor for solution polymerization. During the polymerization reaction, the polymerization temperature is controlled at 25-45° C. and the polymerization pressure is controlled at 0.6 MPa-2.0 MPa, thereby obtaining a vinyl polyolefin elastomer (i.e., a homopolymer of ethylene). The activated ethylene gas flow rate is 4L / min-8L / min, preferably 6L / min; the concentration of the main catalyst in a single reactor is 2μmol / L-50μmol / L; the molar number of aluminum (Al) in the co-catalyst is 300-500 times the molar number of nickel (Ni) in the main catalyst.

[0027] According to an embodiment of the present invention, another method for preparing a polyolefin elastomer by solution polymerization is provided, comprising: introducing C3-C 12 α-olefin and activated ethylene gas are subjected to solution polymerization to obtain a polyolefin elastomer. The polyolefin elastomer is C3-C 12 Copolymers of alpha-olefins and activated ethylene gas.

[0028] In an embodiment of the present invention, in the presence of a primary catalyst and a co-catalyst, activated ethylene gas and C3-C 12 The α-olefins can be copolymerized to obtain polyolefin elastomer (POE), which is a polyolefin elastomer composed of activated ethylene gas and C3-C 12α-olefin copolymers, for example, can be: copolymers of ethylene and propylene, copolymers of ethylene and 1-octene. Polyolefin elastomer (POE) is a random copolymer of ethylene and α-olefin with a high α-olefin comonomer content. It is a thermoplastic elastomer that has elasticity without vulcanization. The molecular weight distribution index (PDI=2-4) of polyolefin elastomer (POE) is relatively narrow and the comonomer content is relatively high (10%-30%), so that polyolefin elastomer (POE) has excellent low temperature resistance (-24℃~-4℃), aging resistance, good mechanical properties and processing properties. It can replace part of EPDM rubber and can also be widely used as an impact modifier for polyolefin materials to prepare instrument panels, bumpers, connectors and plugs, pipes, instrument parts, sheets, gardening tools and building materials. It can also be directly made into molded products and extruded products. It is an elastomeric material with excellent performance and higher added value.

[0029] According to an embodiment of the present invention, activated ethylene gas and C3-C 12 The main catalyst, co-catalyst and polymerization solvent involved in preparing polyolefin elastomer (POE) from α-olefin are the same as the main catalyst, co-catalyst and polymerization solvent used in preparing vinyl polyolefin elastomer (EPOE) from activated ethylene gas in the above embodiment, and will not be described in detail here.

[0030] According to an embodiment of the present invention, the comonomer for solution polymerization with ethylene gas is preferably C3-C8 α-olefin, such as any one of 1-propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene.

[0031] For example, a method for preparing a polyolefin elastomer by solution polymerization based on activated ethylene and 1-octene comonomers comprises: introducing a polymerization solvent (such as n-heptane) into a reactor, and replacing the air in the reactor with nitrogen vacuum, and repeating the process multiple times. Subsequently, the ethylene gas in a commercially available ethylene gas cylinder is directly introduced into purification tank 1, purification tank 2, and purification tank 3 in sequence for purification and activation to obtain activated ethylene gas. The activated ethylene gas is introduced into the reactor to replace the nitrogen in the reactor, and the process is repeated multiple times. Furthermore, after the DEAC co-catalyst is introduced into the reactor and stirred for 25 minutes, the main catalyst (such as the diimine nickel catalyst shown in formula (1), wherein R is selected from H) is introduced into the reactor and stirred for 1 minute, and activated ethylene gas and 1-octene (comonomer) are introduced into the reactor for solution polymerization. During the polymerization reaction, the polymerization temperature is controlled at 25-45° C. and the polymerization pressure is controlled at 0.6 MPa-2.0 MPa to obtain a polyolefin elastomer (i.e., a copolymer of ethylene and 1-octene). The flow rate of the activated ethylene gas is 4 L / min-8 L / min, preferably 6 L / min; the concentration of the main catalyst in the single reactor is 2 μmol / L-50 μmol / L; and the molar number of aluminum (Al) in the co-catalyst is 300-500 times the molar number of nickel (Ni) in the main catalyst.

[0032] As a third aspect of the present invention, there is provided a polyolefin elastomer prepared by the method for preparing a polyolefin elastomer according to the above embodiment, wherein the polyolefin elastomer is a homopolymer of activated ethylene gas, or a homopolymer of activated ethylene gas and C3-C 12 Copolymers of α-olefins.

[0033] The technical solution of the present invention will be further explained below in conjunction with specific embodiments. Unless otherwise specified, the reagents used in the following embodiments are all common commercially available reagents.

[0034] Example 1

[0035] Preparation of vinyl polyolefin elastomers

[0036] Raw materials: commercially available ethylene gas stored in ethylene gas cylinders, which is polymerization grade ethylene (purity is 99.95%); the organic solvent or polymerization solvent is n-heptane containing trace amounts of water (the water content is 0.5wt% of n-heptane); the co-catalyst is diethylaluminum chloride; the main catalyst is , where R is isobutyl, named Cat-1.

[0037] Treatment of ethylene gas: The ethylene gas in the commercially available ethylene gas cylinder is directly passed into purification tank 1, purification tank 2, and purification tank 3 in sequence for purification and activation to obtain activated ethylene gas; wherein purification tank 1 is loaded with a triglyceride solution of Cu(Qc)2, purification tank 2 is loaded with anhydrous ether, and purification tank 3 is loaded with n-heptane containing trace amounts of water.

[0038] Preparation of vinyl polyolefin elastomer (EPOE) by homopolymerization of ethylene: n-heptane (i.e., polymerization solvent) containing trace amounts of water is introduced into the reactor, and the air in the reactor is replaced by nitrogen vacuum, which is repeated multiple times (e.g., 3 times). Subsequently, the obtained activated ethylene gas is introduced into the reactor to replace the nitrogen in the reactor, and this is repeated 3 times. Furthermore, after the co-catalyst is introduced into the reactor and stirred for 25 minutes, the main catalyst is introduced into the reactor and stirred for 1 minute, and activated ethylene gas is introduced into the reactor for solution polymerization. During the polymerization reaction, the polymerization temperature is controlled at 25°C and the polymerization pressure is controlled at 0.6MPa, thereby obtaining vinyl polyolefin elastomer (i.e., homopolymer of ethylene), and the activated ethylene gas flow rate is 6L / min; the concentration of the main catalyst in a single reactor is 4μmol / L; the molar number of aluminum (Al) in the co-catalyst is 300 times the molar number of nickel (Ni) in the main catalyst.

[0039] Example 2

[0040] The vinyl polyolefin elastomer was prepared by the same method as in Example 1, except that R in the main catalyst was selected from phenyl, and was named Cat-2.

[0041] Example 3

[0042] The vinyl polyolefin elastomer was prepared in the same manner as in Example 1, except that R in the main catalyst was selected from hydrogen and was named Cat-3.

[0043] Example 4

[0044] The vinyl polyolefin elastomer was prepared in the same manner as in Example 1, except that the polymerization temperature was 35°C.

[0045] Example 5

[0046] The vinyl polyolefin elastomer was prepared in the same manner as in Example 1, except that the polymerization temperature was 45°C.

[0047] Example 6

[0048] The vinyl polyolefin elastomer was prepared in the same manner as in Example 1, except that the polymerization pressure was 1.0 MPa.

[0049] Example 7

[0050] The vinyl polyolefin elastomer was prepared in the same manner as in Example 1, except that the polymerization pressure was 2.0 MPa.

[0051] Comparative Example 1

[0052] The vinyl polyolefin elastomer was prepared by the same method as in Example 1, except that the ethylene gas was not treated in sequence by purification tank 1, purification tank 2, and purification tank 3. In other words, the vinyl polyolefin elastomer was prepared by directly using commercially available ethylene gas through solution polymerization.

[0053] Comparative Example 2

[0054] The vinyl polyolefin elastomer was prepared by the same method as in Example 2, except that the ethylene gas was not treated in sequence by purification tank 1, purification tank 2, and purification tank 3. In other words, the vinyl polyolefin elastomer was prepared by directly using commercially available ethylene gas through solution polymerization.

[0055] Comparative Example 3

[0056] The vinyl polyolefin elastomer was prepared by the same method as in Example 3, except that the ethylene gas was not treated in sequence by purification tank 1, purification tank 2, and purification tank 3. In other words, the vinyl polyolefin elastomer was prepared by directly using commercially available ethylene gas through solution polymerization.

[0057] Comparative Example 4

[0058] The vinyl polyolefin elastomer was prepared by the same method as in Example 4, except that the ethylene gas was not sequentially treated by purification tank 1, purification tank 2, and purification tank 3. In other words, the vinyl polyolefin elastomer was prepared by directly using commercially available ethylene gas for solution polymerization.

[0059] Comparative Example 5

[0060] The vinyl polyolefin elastomer was prepared by the same method as in Example 5, except that the ethylene gas was not treated in the purification tank 1, the purification tank 2, and the purification tank 3 in sequence. In other words, the vinyl polyolefin elastomer was prepared by directly using commercially available ethylene gas through solution polymerization.

[0061] Comparative Example 6

[0062] The vinyl polyolefin elastomer was prepared by the same method as in Example 6, except that the ethylene gas was not treated in sequence by purification tank 1, purification tank 2, and purification tank 3. In other words, the vinyl polyolefin elastomer was prepared by directly using commercially available ethylene gas through solution polymerization.

[0063] Comparative Example 7

[0064] The vinyl polyolefin elastomer was prepared by the same method as in Example 7, except that the ethylene gas was not treated in sequence by purification tank 1, purification tank 2, and purification tank 3. In other words, the vinyl polyolefin elastomer was prepared by directly using commercially available ethylene gas through solution polymerization.

[0065] Furthermore, the activities of the vinyl polyolefin elastomers prepared in Examples 1 to 7 and Comparative Examples 1 to 7 were tested, and the specific test results are shown in Table 1.

[0066] Table 1

[0067]

[0068] Note: The activity is the mass of the product after drying and divided by the mass of the catalyst used (including the main catalyst and the co-catalyst).

[0069] As shown in Table 1, by comparing Example 1-Example 3 and Reference Example 1-Reference Example 3, it can be found that the activated ethylene gas obtained by activating ethylene gas using a purification tank provided by the present invention is applied to the ethylene solution polymerization reaction, and has a certain activation effect on different catalysts, and the activity of the polymerization reaction in the embodiment is higher than the activity of the polymerization reaction in the reference example. By comparing Example 1, Example 4-Example 5 and corresponding Reference Example 1, Reference Example 4-Reference Example 5, it can be found that with the increase of the polymerization temperature, the activation effect of the purification tank is more significant, which is manifested as a significant increase in the activity of the polymerization reaction, and the activity of the polymerization reaction in the embodiment is higher than the activity of the polymerization reaction in the reference example. By comparing Example 1, Example 6-Example 7 and corresponding Reference Example 1, Reference Example 6-Reference Example 7, it can be found that with the increase of the polymerization pressure, the activation effect of the purification tank is more significant, which is manifested as a significant increase in the activity of the polymerization reaction, and the activity of the polymerization reaction in the embodiment is higher than the activity of the polymerization reaction in the reference example.

[0070] Furthermore, by removing the purification tank 1 and keeping other conditions the same as those in Example 1 to Example 7, the effect of the purification tank 1 on the activity of the ethylene solution polymerization reaction was investigated.

[0071] Comparative Example A1

[0072] The vinyl polyolefin elastomer was prepared in the same manner as in Example 1, except that purification tank 1 was removed and purification tanks 2 and 3 were retained.

[0073] Comparative Example A2

[0074] The vinyl polyolefin elastomer was prepared in the same manner as in Example 2, except that purification tank 1 was removed and purification tanks 2 and 3 were retained.

[0075] Comparative Example A3

[0076] The vinyl polyolefin elastomer was prepared in the same manner as in Example 3, except that purification tank 1 was removed and purification tanks 2 and 3 were retained.

[0077] Comparative Example A4

[0078] The vinyl polyolefin elastomer was prepared in the same manner as in Example 4, except that purification tank 1 was removed and purification tanks 2 and 3 were retained.

[0079] Comparative Example A5

[0080] The vinyl polyolefin elastomer was prepared in the same manner as in Example 5, except that purification tank 1 was removed and purification tanks 2 and 3 were retained.

[0081] Comparative Example A6

[0082] The vinyl polyolefin elastomer was prepared in the same manner as in Example 6, except that purification tank 1 was removed and purification tanks 2 and 3 were retained.

[0083] Comparative Example A7

[0084] The vinyl polyolefin elastomer was prepared in the same manner as in Example 7, except that purification tank 1 was removed and purification tanks 2 and 3 were retained.

[0085] The activity of the vinyl polyolefin elastomers prepared by the above-mentioned Control Examples A1 to A7 was tested. The specific test results are shown in Table 2.

[0086] Table 2

[0087]

[0088] As shown in Table 2, by comparing Examples 1 to 7 and Control Examples A1 to A7, it can be found that after the purification tank 1 is removed, the activation effect of the purification tanks 2 and 3 on the ethylene gas decreases, which is manifested in that the activity of the polymerization reaction in Examples 1 to 7 is higher than that in Control Examples A1 to A7, which shows that the purification tank 1 is indispensable.

[0089] Furthermore, by removing the purification tank 2 and keeping other conditions the same as those in Example 1 to Example 7, the effect of the purification tank 2 on the activity of the ethylene solution polymerization reaction was investigated.

[0090] Comparative Example B1

[0091] The vinyl polyolefin elastomer was prepared in the same manner as in Example 1, except that purification tank 2 was removed and purification tanks 1 and 3 were retained.

[0092] Comparative Example B2

[0093] The vinyl polyolefin elastomer was prepared by the same method as in Example 2, except that purification tank 2 was removed and purification tanks 1 and 3 were retained.

[0094] Comparative Example B3

[0095] The vinyl polyolefin elastomer was prepared in the same manner as in Example 3, except that purification tank 2 was removed and purification tanks 1 and 3 were retained.

[0096] Comparative Example B4

[0097] The vinyl polyolefin elastomer was prepared in the same manner as in Example 4, except that purification tank 2 was removed and purification tanks 1 and 3 were retained.

[0098] Comparative Example B5

[0099] The vinyl polyolefin elastomer was prepared in the same manner as in Example 5, except that purification tank 2 was removed and purification tanks 1 and 3 were retained.

[0100] Comparative Example B6

[0101] The vinyl polyolefin elastomer was prepared in the same manner as in Example 6, except that purification tank 2 was removed and purification tanks 1 and 3 were retained.

[0102] Comparative Example B7

[0103] The vinyl polyolefin elastomer was prepared in the same manner as in Example 7, except that purification tank 2 was removed and purification tanks 1 and 3 were retained.

[0104] The activity of the vinyl polyolefin elastomers prepared by the above-mentioned Control Examples B1 to B7 was tested. The specific test results are shown in Table 3.

[0105] Table 3

[0106]

[0107] As shown in Table 3, by comparing Examples 1 to 7 and Control Examples B1 to B7, it can be found that after the purification tank 2 is removed, the activation effect of the purification tank 1 and the purification tank 3 on the ethylene gas decreases, which is manifested in that the activity of the polymerization reaction in Examples 1 to 7 is higher than that in Control Examples B1 to B7, which shows that the purification tank 2 is indispensable.

[0108] Furthermore, by removing the purification tank 3 and keeping other conditions the same as those in Example 1-7, the effect of the purification tank 3 on the activity of the ethylene solution polymerization reaction was investigated.

[0109] Comparative Example C1

[0110] The vinyl polyolefin elastomer was prepared in the same manner as in Example 1, except that purification tank 3 was removed and purification tanks 1 and 2 were retained.

[0111] Comparative Example C2

[0112] The vinyl polyolefin elastomer was prepared in the same manner as in Example 2, except that purification tank 3 was removed and purification tanks 1 and 2 were retained.

[0113] Comparative Example C3

[0114] The vinyl polyolefin elastomer was prepared in the same manner as in Example 3, except that purification tank 3 was removed and purification tanks 1 and 2 were retained.

[0115] Comparative Example C4

[0116] The vinyl polyolefin elastomer was prepared in the same manner as in Example 4, except that purification tank 3 was removed and purification tanks 1 and 2 were retained.

[0117] Comparative Example C5

[0118] The vinyl polyolefin elastomer was prepared in the same manner as in Example 5, except that purification tank 3 was removed and purification tanks 1 and 2 were retained.

[0119] Comparative Example C6

[0120] The vinyl polyolefin elastomer was prepared in the same manner as in Example 6, except that purification tank 3 was removed and purification tanks 1 and 2 were retained.

[0121] Comparative Example C7

[0122] The vinyl polyolefin elastomer was prepared in the same manner as in Example 7, except that purification tank 3 was removed and purification tanks 1 and 2 were retained.

[0123] The activity of the vinyl polyolefin elastomers prepared by the above-mentioned Reference Examples C1 to C7 was tested. The specific test results are shown in Table 4.

[0124] Table 4

[0125]

[0126] As shown in Table 4, by comparing Examples 1 to 7 and Control Examples C1 to C7, it can be found that after removing purification tank 3, the activation effect of purification tank 1 and purification tank 2 on ethylene gas is significantly reduced, which is manifested in that the activity of the polymerization reaction in Examples 1 to 7 is higher than that in Control Examples C1 to C7, which shows that purification tank 3 is indispensable.

[0127] Furthermore, by removing purification tank 1 and purification tank 2, other conditions were the same as those in Example 1 to Example 7, and the effects of purification tank 1 and purification tank 2 on the activity of ethylene solution polymerization reaction were investigated.

[0128] Comparative Example D1

[0129] The vinyl polyolefin elastomer was prepared in the same manner as in Example 1, except that purification tank 1 and purification tank 2 were removed and purification tank 3 was retained.

[0130] Comparative Example D2

[0131] The vinyl polyolefin elastomer was prepared in the same manner as in Example 2, except that purification tank 1 and purification tank 2 were removed and purification tank 3 was retained.

[0132] Comparative Example D3

[0133] The vinyl polyolefin elastomer was prepared in the same manner as in Example 3, except that purification tank 1 and purification tank 2 were removed and purification tank 3 was retained.

[0134] Comparative Example D4

[0135] The vinyl polyolefin elastomer was prepared in the same manner as in Example 4, except that purification tank 1 and purification tank 2 were removed and purification tank 3 was retained.

[0136] Comparative Example D5

[0137] The vinyl polyolefin elastomer was prepared in the same manner as in Example 5, except that purification tank 1 and purification tank 2 were removed and purification tank 3 was retained.

[0138] Comparative Example D6

[0139] The vinyl polyolefin elastomer was prepared in the same manner as in Example 6, except that purification tank 1 and purification tank 2 were removed and purification tank 3 was retained.

[0140] Comparative Example D7

[0141] The vinyl polyolefin elastomer was prepared in the same manner as in Example 7, except that purification tank 1 and purification tank 2 were removed and purification tank 3 was retained.

[0142] The activity of the vinyl polyolefin elastomers prepared by the above-mentioned control examples D1 to D7 was tested. The specific test results are shown in Table 5.

[0143] Table 5

[0144]

[0145] As shown in Table 5, by comparing Examples 1 to 7 and Control Examples D1 to D7, it can be found that after removing purification tank 1 and purification tank 2, the activation effect of ethylene gas using only purification tank 3 is not significant, which is manifested in that the activity of the polymerization reaction in Examples 1 to 7 is higher than that in Control Examples D1 to D7, which indicates that purification tank 3 cannot be used alone, that is, purification tank 1 and purification tank 2 are indispensable.

[0146] Furthermore, by removing purification tank 2 and purification tank 3, other conditions were the same as those in Example 1 to Example 7, and the effects of purification tank 2 and purification tank 3 on the activity of ethylene solution polymerization reaction were investigated.

[0147] Comparative Example E1

[0148] The vinyl polyolefin elastomer was prepared in the same manner as in Example 1, except that purification tank 2 and purification tank 3 were removed and purification tank 1 was retained.

[0149] Comparative Example E2

[0150] The vinyl polyolefin elastomer was prepared in the same manner as in Example 2, except that purification tank 2 and purification tank 3 were removed and purification tank 1 was retained.

[0151] Comparative Example E3

[0152] The vinyl polyolefin elastomer was prepared in the same manner as in Example 3, except that purification tank 2 and purification tank 3 were removed and purification tank 1 was retained.

[0153] Comparative Example E4

[0154] The vinyl polyolefin elastomer was prepared in the same manner as in Example 4, except that purification tank 2 and purification tank 3 were removed and purification tank 1 was retained.

[0155] Comparative Example E5

[0156] The vinyl polyolefin elastomer was prepared in the same manner as in Example 5, except that purification tank 2 and purification tank 3 were removed and purification tank 1 was retained.

[0157] Comparative Example E6

[0158] The vinyl polyolefin elastomer was prepared in the same manner as in Example 6, except that purification tank 2 and purification tank 3 were removed and purification tank 1 was retained.

[0159] Comparative Example E7

[0160] The vinyl polyolefin elastomer was prepared in the same manner as in Example 7, except that purification tank 2 and purification tank 3 were removed and purification tank 1 was retained.

[0161] The activity of the vinyl polyolefin elastomers prepared by the above-mentioned Control Examples E1 to E7 was tested. The specific test results are shown in Table 6.

[0162] Table 6

[0163]

[0164] As shown in Table 6, by comparing Examples 1 to 7 and Control Examples E1 to E7, it can be found that after removing purification tanks 2 and 3, the activation effect of ethylene gas using only purification tank 1 is not significant, as shown by the higher polymerization reaction activity in Examples 1 to 7 than in Control Examples E1 to E7, which indicates that purification tank 1 cannot be used alone, that is, purification tank 2 and purification tank 3 are indispensable.

[0165] Furthermore, by removing purification tank 1 and purification tank 3, other conditions were the same as those in Example 1 to Example 7, and the effects of purification tank 1 and purification tank 3 on the activity of ethylene solution polymerization reaction were investigated.

[0166] Control Example F1

[0167] The vinyl polyolefin elastomer was prepared in the same manner as in Example 1, except that purification tank 1 and purification tank 3 were removed and purification tank 2 was retained.

[0168] Control Example F2

[0169] The vinyl polyolefin elastomer was prepared in the same manner as in Example 2, except that purification tank 1 and purification tank 3 were removed and purification tank 2 was retained.

[0170] Control Example F3

[0171] The vinyl polyolefin elastomer was prepared in the same manner as in Example 3, except that purification tank 1 and purification tank 3 were removed and purification tank 2 was retained.

[0172] Comparative Example F4

[0173] The vinyl polyolefin elastomer was prepared in the same manner as in Example 4, except that purification tank 1 and purification tank 3 were removed and purification tank 2 was retained.

[0174] Comparative Example F5

[0175] The vinyl polyolefin elastomer was prepared in the same manner as in Example 5, except that purification tank 1 and purification tank 3 were removed and purification tank 2 was retained.

[0176] Comparative Example F6

[0177] The vinyl polyolefin elastomer was prepared in the same manner as in Example 6, except that purification tank 1 and purification tank 3 were removed and purification tank 2 was retained.

[0178] Comparative Example F7

[0179] The vinyl polyolefin elastomer was prepared in the same manner as in Example 7, except that purification tank 1 and purification tank 3 were removed and purification tank 2 was retained.

[0180] The activity of the vinyl polyolefin elastomers prepared by the above-mentioned Control Examples F1 to F7 was tested. The specific test results are shown in Table 7.

[0181] Table 7

[0182]

[0183] As shown in Table 7, by comparing Examples 1 to 7 and Control Examples F1 to F7, it can be found that after removing purification tank 1 and purification tank 3, the activation effect of ethylene gas using only purification tank 2 is not significant, as shown by the polymerization reaction activity in Examples 1 to 7 being higher than that in Control Examples F1 to F7, which indicates that purification tank 2 cannot be used alone, that is, purification tank 1 and purification tank 3 are indispensable.

[0184] By comparing the above embodiment and the control example, it is shown that the highest activity can be obtained only when all three purification tanks are present and the ethylene gas is activated in a specific order, thereby proving the interdependent relationship between purification tank 1, purification tank 2 and purification tank 3.

[0185] Furthermore, the same method as in Example 1 was used to investigate the effect of activated ethylene gas on the polymerization reaction of ethylene and α-olefin to form a copolymer of ethylene and α-olefin.

[0186] Example 8

[0187] The copolymer of ethylene and propylene was prepared in the same manner as in Example 1, except that the mass ratio of activated ethylene gas (ethylene for short) to propylene was 1:4, the polymerization temperature was 25° C., and the polymerization pressure was 0.5 MPa.

[0188] Comparative Example G1

[0189] The copolymer of ethylene and propylene was prepared by the same method as in Example 8, except that the ethylene gas was not treated in the purification tank 1, the purification tank 2, and the purification tank 3 in sequence. In other words, the copolymer of ethylene and propylene was prepared by directly using commercially available ethylene gas and propylene through solution polymerization.

[0190] Example 9

[0191] The copolymer of ethylene and propylene was prepared in the same manner as in Example 8, except that the mass ratio of activated ethylene gas (ethylene for short) to propylene was 1:3.

[0192] Comparative Example G2

[0193] The copolymer of ethylene and propylene was prepared by the same method as in Example 9, except that the ethylene gas was not treated in the purification tank 1, the purification tank 2, and the purification tank 3 in sequence. In other words, the copolymer of ethylene and propylene was prepared by directly using commercially available ethylene gas and propylene through solution polymerization.

[0194] Furthermore, the activities of the copolymers of ethylene and propylene prepared in Examples 8-9 and Comparative Examples G1-G2 were tested. The specific test results are shown in Table 8.

[0195] Table 8

[0196]

[0197] As shown in Table 8, it can be seen from Examples 8 and 9 that the activated ethylene gas is activated by using the purification tank provided by the present invention, and the obtained activated ethylene gas is copolymerized with propylene, and has a high polymerization reaction activity.

[0198] In summary, the present invention provides a method for treating ethylene gas, by activating ethylene to obtain activated ethylene gas. The activated ethylene is applied to the preparation of polyolefin elastomers through solution polymerization, which can significantly improve the polymerization reaction activity of the polyolefin elastomer, and then a vinyl polyolefin elastomer or a copolymer of ethylene and α-olefin with higher performance can be prepared. Compared with other methods for preparing polyolefin elastomers, the present invention activates ethylene gas through three purification tanks, which has low cost. The prepared polyolefin elastomer has excellent physical and mechanical properties, aging resistance and UV resistance, good low temperature performance and rheological properties, higher transparency and more stable size, and good affinity with polyolefins, which lays a foundation for future copolymerization with α-olefins or with polar monomers. It can be used in the fields of automotive parts, wires and cables, machine tools, shoemaking, seals, and hot melt adhesives, and better meets market demand.

[0199] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for treating ethylene gas, characterized in that: The processing method comprises: The commercially available ethylene gas is sequentially passed through a primary purification tank, a secondary purification tank, and a tertiary purification tank to obtain activated ethylene gas; Wherein, the primary purification tank is loaded with a triglyceride solution of Cu(Qc)2 or a triglyceride solution of Zn(benzimidazole)2 or pure triglyceride, wherein Qc represents quinoline-5-carboxylate; The secondary purification tank is loaded with anhydrous ether; The tertiary purification tank is loaded with an organic solvent containing trace amounts of water, wherein the organic solvent is selected from at least one of isobutane, n-pentane, isopentane, n-hexane, methylcyclopentane, n-heptane, methylcyclohexane, isooctane, and a mixture of toluene and C4-C8 isomeric saturated alkanes.

2. The processing method according to claim 1, characterized in that: In the primary purification tank, the concentration of Cu(Qc)2 or Zn(benzimidazole)2 is 1 μmol / L-100 μmol / L.

3. The processing method according to claim 2, characterized in that: The Cu(Qc)2 is obtained by ball milling copper hydroxide and quinoline-5-carboxylic acid in the presence of N,N-dimethylformamide and ethanol; The Zn(benzimidazole)2 is obtained by dissolving benzimidazole and zinc in acetic acid in proportion, and then refluxing and rotary evaporating.

4. A method for preparing a polyolefin elastomer, characterized in that: The preparation method uses the activated ethylene gas obtained by the ethylene gas treatment method according to any one of claims 1 to 3 as a reaction raw material for solution polymerization.

5. The preparation method according to claim 4, characterized in that: The preparation method comprises: Passing the main catalyst, the co-catalyst and the activated ethylene gas into a reaction kettle containing a polymerization solvent to carry out a solution polymerization reaction to obtain a polyolefin elastomer, wherein the polyolefin elastomer is a homopolymer of the activated ethylene gas; The polymerization solvent is the same as the organic solvent loaded in the three-stage purification tank, and the molar ratio of trace water in the polymerization solvent to the co-catalyst is 1:2-1:

6.

6. The preparation method according to claim 4, characterized in that: The preparation method comprises: In the presence of the main catalyst and the co-catalyst, C3-C 12 α-olefin and the activated ethylene gas, and carry out solution polymerization to obtain a polyolefin elastomer, wherein the polyolefin elastomer is C3-C 12 Copolymers of alpha-olefins and ethylene.

7. The preparation method according to claim 5 or 6, characterized in that: The co-catalyst is selected from at least one of triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, sesquiethylaluminum chloride, monoisobutylaluminum chloride, and diisobutylaluminum dichloride; The main catalyst is a nickel diimide catalyst, and the nickel diimide catalyst has a structure as shown in the following formula (1): Formula (1), wherein R is selected from at least one of isobutyl, phenyl and hydrogen.

8. The preparation method according to claim 6, characterized in that: The comonomer used in the solution polymerization reaction with ethylene gas is selected from C3-C8 α-olefins.

9. The preparation method according to claim 7, characterized in that: The polymerization temperature in the solution polymerization reaction is 25° C.-45° C., and the polymerization pressure is 0.6 MPa-2.0 MPa.

10. A polyolefin elastomer prepared by the method for preparing a polyolefin elastomer according to claim 9, characterized in that: The polyolefin elastomer is a homopolymer of activated ethylene gas, or a copolymer of activated ethylene gas and C3-C 12 Copolymers of α-olefins.

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