Ethylene copolymer as well as preparation method and application thereof

Abstract

The invention provides an ethylene copolymer and a preparation method and application thereof, the ethylene copolymer comprises an ethylene monomer, an alpha-olefin monomer and a functionalized styrene monomer, the molar ratio of the alpha-olefin monomer to the ethylene monomer is 1: (4-24), and the molar ratio of the functionalized styrene monomer to the alpha-olefin monomer is 1: (2-10); wherein the functionalized styrene monomer has a structure as shown in a formula I: # imgabs0 #, and R is an amino substituted alkylene group, an amino substituted phenyl group, a carbazolyl group, a carboxyl substituted benzopyrone group, a benzopyranyl group and a carboxyl substituted alkylene group. The ethylene copolymer contains specific functional groups and is easy to further functionalize.

Description

Technical Field

[0001] The present invention belongs to the technical field of polyolefin elastomer materials, and particularly relates to an ethylene copolymer, a preparation method thereof, and an application thereof. Background Art

[0002] Polyolefin elastomer materials are an important variety of synthetic polymer materials, which actually refer to random copolymers of ethylene and higher α-olefins (POE). At present, the production of this product is mainly concentrated in several suppliers such as Dow and ExxonMobil. Among them, Dow Chemical transformed the Dowlex process into the Insite process in 1993, using a mixture of Isopar saturated isoparaffins and C 8 ~C 9 as a solvent, and using a CGC constrained geometry metallocene catalyst to carry out solution polymerization in a loop reactor to manufacture POE elastomers. ExxonMobil uses a bridged metallocene catalyst to produce random copolymers of ethylene, propylene, and α-olefins.

[0003] POE elastomers are products with excellent comprehensive properties. They have now become popular products in the polyolefin family and have high profits. However, at present, China has not developed a process suitable for the industrial production of POE products. There have also been research reports on the preparation of POE products in China, but there are few methods for self-preparing a POE material containing functional groups. Chinese Patent CN114316096A discloses a functionalized polyolefin elastomer and a preparation method thereof, using a specific vanadium-based Z-N type catalyst to catalyze the ternary copolymerization of ethylene, α-olefin, and vinyl norbornene, and can synthesize an ethylene / propylene / VNB ternary copolymerized polyolefin elastomer with a high content of side-chain vinyl groups. Chinese Patent CN115572341A discloses a class of functionalized polyolefin elastomers and a preparation method thereof, using a metallocene compound containing heteroatom coordination to catalyze the copolymerization of ethylene, aliphatic or aromatic monolefins, and functionalized monomers. The polymerization temperature is 140-230°C, and the polymerization pressure is 8-14 MPa. The obtained copolymer is an ethylene / α-olefin / functionalized monomer ternary copolymer or an ethylene / styrene / functionalized monomer ternary copolymer, but it can only achieve the ternary copolymerization of specific functionalized monomers by selecting specific heteroatom coordination in the catalyst.

[0004] However, the existing technical methods can only introduce specific functional groups into the copolymer, which has certain limitations. Summary of the Invention

[0005] The main object of the present invention is to provide an ethylene copolymer, a preparation method thereof, and an application thereof. The ethylene copolymer of the present invention contains specific functional groups and is easy to be further functionalized.

[0006] To achieve the above object, the present invention provides an ethylene copolymer, which comprises an ethylene monomer, an α-olefin monomer, and a functionalized styrene monomer. The molar ratio of the α-olefin monomer to the ethylene monomer is 1:4 to 24, and the molar ratio of the functionalized styrene monomer to the α-olefin monomer is 1:2 to 10;

[0007] Among them, the functionalized styrene monomer has the following structure of Formula I:

[0008]

[0009] Among them, R is an amino-substituted olefin group, an amino-substituted phenyl group, a carbazolyl group, a carboxyl-substituted benzopyranone group, a benzopyranyl group, or a carboxyl-substituted olefin group.

[0010] For the ethylene copolymer of the present invention, among them, the functionalized styrene monomer is at least one of monomers 1-6, and the monomers 1-6 have the following structures:

[0011]

[0012] For the ethylene copolymer of the present invention, among them, the α-olefin monomer is selected from one of 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene.

[0013] For the ethylene copolymer of the present invention, among them, the density of the ethylene copolymer is 0.85 to 0.90 g / cm 3 , the molar percentage content of the α-olefin monomer is 5 to 20%, and the molar percentage content of the functionalized styrene monomer is 1.0 to 5.0%.

[0014] To achieve the above object, the present invention provides a preparation method of the above ethylene copolymer, comprising the following steps:

[0015] Step 1, mixing the α-olefin monomer, the functionalized styrene monomer, a solvent, and a cocatalyst;

[0016] Step 2, introducing ethylene, adding a metallocene catalyst, and carrying out a copolymerization reaction to obtain an ethylene copolymer.

[0017] For the preparation method of the ethylene copolymer of the present invention, among them, the temperature of the copolymerization reaction is 100°C to 240°C, and the pressure is 2 MPa to 4 MPa; and / or the reaction time is 10 min to 20 min.

[0018] For the preparation method of the ethylene copolymer of the present invention, among them, the metallocene catalyst is R 1 (CpR 2 n)(FluR 3 m)MQ 2, where Cp is cyclopentadienyl, Flu is fluorenyl, R 2 and R 3 are each independently selected from H, C 1 ~C 12 alkyl, C 6 ~C 12 aryl or halogen, m and n are integers from 0 to 4, R 1 is a bridging group connecting cyclopentadienyl and fluorenyl, M is zirconium or hafnium, Q is halogen or C 1 ~C 6 alkyl.

[0019] The method for preparing the ethylene copolymer according to the present invention, wherein the metallocene catalyst is selected from isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, dibenzylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, dimethylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, diphenylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride and vinylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride.

[0020] The method for preparing the ethylene copolymer according to the present invention, wherein the cocatalyst is an aluminoxane compound; the molar ratio of the metallocene catalyst to the cocatalyst is 1:200 to 1000.

[0021] The ethylene copolymer according to the present invention can be used as a polyolefin elastomer material.

[0022] Advantages of the present invention:

[0023] In the present invention, ethylene, an α-olefin and a functionalized styrene monomer are copolymerized to obtain a functionalized copolymer. Among them, the content of the functionalized monomer can be regulated within a certain range to adapt to different application fields; more importantly, the present invention introduces a reactive functional group with fluorescence characteristics into the macromolecular chain, and the obtained copolymer has a bright white effect, which can offset the yellowing phenomenon caused by the extension of the material use time, and can effectively improve the service life of the polyolefin elastomer material; compared with the blending method of traditional polymer materials and functionalized small molecules with fluorescence whitening effect, the material use performance is more stable.. In addition, while not destroying the excellent performance of the copolymer, the present invention directly introduces a functionalized group into the macromolecular chain, which can effectively improve the copolymer blend phase separation, improve the adhesion performance of the copolymer, and make the copolymer easy to dye and improve the compatibility of the copolymer with fillers during the mixing process; furthermore, the synthesized functionalized copolymer can be further post-functionalized to introduce other functional groups, endowing the material with more use functions, and used as a new type of functional polymer material, having unique potential application value. Specific embodiments

[0024] The technical solution of the present invention will be described in detail below. The following embodiments are implemented on the premise of the technical solution of the present invention, and the detailed implementation process is given. However, the protection scope of the present invention is not limited to the following embodiments. For the structures or experimental methods without specific conditions in the following embodiments, they are usually in accordance with conventional conditions.

[0025] The present invention provides an ethylene copolymer, which includes ethylene monomers, α-olefin monomers and functionalized styrene monomers. The molar ratio of the α-olefin monomers to the ethylene monomers is 1:4 to 24, and the molar ratio of the functionalized styrene monomers to the α-olefin monomers is 1:2 to 10.

[0026] Among them, the functionalized styrene monomer has the following structural formula Ⅰ:

[0027]

[0028] Among them, R is an amino-substituted olefin group, an amino-substituted phenyl group, a carbazolyl group, a carboxyl-substituted benzopyranone group, a benzopyranyl group, or a carboxyl-substituted olefin group.

[0029] There is no particular limitation on the α-olefin in the present invention. In one embodiment, the α-olefin is selected from any one of 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene.

[0030] In the present invention, the functionalized styrene monomer is a compound obtained by substituting the hydrogen on the benzene ring of styrene with the functional group R. The present invention does not particularly limit the substitution position of the functional group R. In one embodiment, the functional group R substitutes the hydrogen at the ortho or para position to the vinyl group on the benzene ring, and preferably substitutes the hydrogen at the para position to the vinyl group on the benzene ring.

[0031] In one embodiment, the olefin group in the amino-substituted olefin group is an allyl group, and the amino substitutes the hydrogen on the terminal double bond carbon of the allyl group. In one embodiment, the amino in the amino-substituted phenyl group is ortho-substituted, meta-substituted or para-substituted, and preferably para-substituted. In one embodiment, the carbazolyl group is specifically a 9-carbazolyl group, that is, the nitrogen in the carbazolyl group is connected to the benzene ring of styrene. In one embodiment, the benzene ring carbon of the benzopyranone group is connected to styrene. Specifically, it can be the carbon numbered 5 in the benzopyranone nomenclature that is connected to the benzene ring; in another embodiment, the carboxyl group is located on the pyran ring, for example, adjacent to the keto group. In one embodiment, the carbon on the benzene ring of the benzopyranyl group is connected to styrene. Specifically, it can be the carbon numbered 5 in the benzopyran nomenclature that is connected to the benzene ring; in one embodiment, the olefin group in the carboxyl-substituted olefin group is an allyl group, and the carboxyl group substitutes the hydrogen on the terminal double bond carbon of the allyl group.

[0032] In one embodiment, the functionalized styrene monomer of the present invention is at least one of monomers 1-6, and the monomers 1-6 have the following structures:

[0033]

[0034] In one embodiment, the density of the ethylene copolymer of the present invention is 0.85 to 0.90 g / cm 3 , the molar percentage content of the α-olefin monomer is 5 to 20%, and the molar percentage content of the functionalized styrene monomer is 1.0 to 5.0%.

[0035] In one embodiment, the present invention also provides a method for preparing the above-mentioned ethylene copolymer, comprising the following steps:

[0036] Step 1, mixing an α-olefin monomer, a functionalized styrene monomer, a solvent and a cocatalyst;

[0037] Step 2, introducing ethylene, adding a metallocene catalyst, and carrying out a copolymerization reaction to obtain an ethylene copolymer.

[0038] In one embodiment, the metallocene catalyst of the present invention is R 1 (CpR 2 n)(FluR 3 m)MQ 2 , wherein Cp is a cyclopentadienyl group, Flu is a fluorenyl group, R 2 and R 3 are each independently selected from H, an alkyl group of C 1 to C 12 , an aryl group of C 6 to C 12 or a halogen, m and n are integers from 0 to 4, R 1 is a bridging group connecting the cyclopentadienyl group and the fluorenyl group, M is zirconium or hafnium, and Q is a halogen or an alkyl group of C 1 to C 6 . In another embodiment, R 1 of the present invention is isopropylidene, diphenylmethylene, dimethylsilyl, diphenylsilyl, or vinylidene. In yet another embodiment, the metallocene catalyst of the present invention is selected from isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, dimethylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, diphenylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, and vinyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride.

[0039] In one embodiment, the cocatalyst of the present invention is an aluminoxane compound; in another embodiment, the cocatalyst is any one of methylaluminoxane and ethylaluminoxane. In yet another embodiment, the molar ratio of the metallocene catalyst to the cocatalyst is 1:200 to 1000.

[0040] The present invention does not particularly limit the solvent. In one embodiment, the solvent is selected from at least one of cyclohexane, n-hexane, n-octane, nonane, or decane.

[0041] The present invention does not particularly limit the synthesis method of the functionalized styrene monomer. For example, it can be synthesized according to the reference Org. Lett. 2022, 24, 8694 - 8697.

[0042] The ethylene copolymerization process of the present invention is carried out in an inert gas atmosphere. The present invention does not particularly limit the inert gas, such as nitrogen, argon, etc. In one embodiment, the reactor is first heated, and then the air in the reactor is replaced with an inert gas, and then the reaction raw materials, solvent, etc. are added.

[0043] In one embodiment, the temperature of the copolymerization reaction of the present invention is 100 °C to 240 °C, the reaction pressure is 2 MPa to 4 MPa, and the time is 10 min to 20 min. During the reaction process, ethylene is continuously introduced to maintain the reaction pressure in the reactor. When the reaction reaches the preset reaction time, the reaction is terminated to obtain an ethylene / α-olefin / functionalized styrene copolymer.

[0044] In a specific embodiment, the preparation method of the ethylene copolymer of the present invention is as follows:

[0045] Perform the preliminary reaction; before the copolymerization reaction, first turn on the heating unit of the reactor to heat the reactor, and at the same time use an inert gas such as nitrogen or argon to purge the reactor to replace the air in the reactor; or introduce ethylene gas to replace the air in the reactor to make the copolymerization reaction proceed under anaerobic conditions.

[0046] Before the copolymerization reaction, turn on the stirring unit of the reactor, and add the solvent, α-olefin monomer, functionalized styrene monomer, and cocatalyst to the reactor under stirring conditions to make them fully dissolve to form a solution environment for the copolymerization reaction.

[0047] Introduce ethylene gas into the reactor. After the temperature and pressure in the reactor reach the preset conditions of the copolymerization reaction and are stable, add a precisely metered metallocene catalyst to the reactor to carry out the ternary copolymerization of ethylene, α-olefin, and functionalized styrene monomer.

[0048] During the copolymerization reaction process, ethylene gas needs to be continuously introduced into the reactor to keep the pressure and temperature in the reactor stable; during this process, part of the ethylene dissolves in the solvent and undergoes a ternary copolymerization reaction with the α-olefin monomer and the functionalized styrene monomer in the solution; in one embodiment, the molar ratio of the α-olefin to the metallocene catalyst is 50 to 100. When the total residence time of the material in the reactor is 15 min to 20 min, the reaction is terminated; the total residence time of the material in the reactor refers to the process time from the addition of the metallocene catalyst to the termination of the reaction; the termination of the reaction can be achieved by introducing air into the reactor to terminate the reaction, or introducing carbon dioxide gas into it to terminate the reaction, or adding a hydrochloric acid-ethanol solution to the solution to terminate the reaction.

[0049] In the above technical solution, the temperature of the copolymerization reaction is relatively high, and the polymer dissolves in the solvent. The polymer can be separated from the unreacted monomers and the solvent by means such as flash evaporation. The recovered solvent can be recycled for use in the copolymerization reaction.

[0050] The ethylene / α-olefin / functionalized styrene copolymer of the present invention can be used as a polyolefin elastomer.

[0051] Hereinafter, the technical solution of the present invention will be further described in detail with specific examples.

[0052] Unless otherwise specified, the materials, reagents, etc. involved hereinafter are all commercially available products well-known to those skilled in the art; unless otherwise specified, the methods are all well-known methods in the art. Unless otherwise defined, the technical terms or scientific terms used shall have the ordinary meaning understood by those of ordinary skill in the art to which the present invention pertains.

[0053] Example 1

[0054] The copolymerization reaction of this example was carried out in a 2 L reaction kettle. The specific steps are as follows:

[0055] Heat the reactor, set the heating temperature to 100 °C; open argon, and flush the reactor three times to displace the air therein; keep the temperature constant; start stirring, set the stirring speed to 400 rpm; sequentially add cyclohexane, 1-octene, monomer 1 and methylaluminoxane to the reactor; among them, the addition amount of cyclohexane in the reaction kettle is 1 L, the addition amount of 1-octene is 56 g, the addition amount of monomer 1 is 33 g, and the addition amount of methylaluminoxane is 116 mg; introduce ethylene into the reactor to make the pressure in the reactor stable at 2.0 MPa; after the temperature and pressure are stable to the preset conditions, add 4.3 mg of isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride to the reactor; start timing; 10 wt% hydrochloric acid acidified ethanol solution was added to terminate the polymerization when the total residence time of the material in the reactor was 15 min from the addition of the metallocene compound.

[0056] The product was washed with alcohol, filtered by suction, dried, and weighed to obtain 177.2 g of the copolymer. The density of the copolymer was measured by a densitometer to be 0.873 g / cm 3 ; The structure of the copolymer was analyzed by NMR. The molar content of 1-octene in the copolymer was 12.6%, and the molar content of the monomer 1 structural unit in the copolymer was 4.8%.

[0057] Example 2

[0058] The copolymerization reaction of this example was carried out in a 2 L reaction kettle. The specific steps are as follows:

[0059] The reactor was heated, and the heating temperature was set to 100 °C; nitrogen was turned on, and the reactor was rinsed three times to displace the air therein; the temperature was kept constant; stirring was started, and the stirring speed was set to 400 rpm; n-hexane, 1-octene, monomer 6, and methylaluminoxane were successively added to the reactor; among them, the addition amount of n-hexane in the reaction kettle was 1 L, the addition amount of 1-octene was 56 g, the addition amount of monomer 6 was 16 g, and the addition amount of methylaluminoxane was 232 mg; ethylene was introduced into the reactor to make the pressure in the reactor stable at 2.5 MPa; after the temperature and pressure were stable to the preset conditions, 4.3 mg of isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride was added to the reactor; timing was started; 10% hydrochloric acid acidified ethanol solution was added to terminate the polymerization when the total residence time of the material in the reactor was 20 min starting from the addition of the metallocene compound.

[0060] The product was washed with alcohol, filtered by suction, dried, and weighed to obtain 177.2 g of the copolymer. The density of the copolymer was measured by a densitometer to be 0.872 g / cm 3 ; The structure of the copolymer was analyzed by NMR. The molar content of 1-octene in the copolymer was 11.6%, and the molar content of the monomer 6 structural unit in the copolymer was 2.8%.

[0061] Example 3

[0062] The copolymerization reaction of this example was carried out in a 2 L reaction kettle. The specific steps are as follows:

[0063] Heat the reactor and set the heating temperature to 120 °C; turn on the argon gas and flush the reactor three times to displace the air inside; maintain a constant temperature; start stirring and set the stirring speed to 400 rpm; sequentially add n-octane, 1-octene, monomer 2, and methylaluminoxane to the reactor; among them, the addition amount of n-octane in the reaction kettle is 1 L, the addition amount of 1-octene is 28 g, the addition amount of monomer 2 is 3 g, and the addition amount of methylaluminoxane is 350 mg; introduce ethylene into the reactor to stabilize the pressure inside the reactor at 2.5 MPa; after the temperature and pressure are stabilized to the preset conditions, add 6.5 mg of isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride to the reactor; start timing; when the total residence time of the materials in the reactor is 15 min starting from the addition of the metallocene compound, introduce air to terminate the polymerization.

[0064] The product is washed with alcohol, filtered by suction, dried, weighed, and 163.9 g of copolymer is obtained. The density of the copolymer is measured by a densitometer to be 0.895 g / cm 3 ; The structure of the copolymer is analyzed by NMR. The molar content of 1-octene in the copolymer is 8.6%, and the molar content of the structural unit of monomer 2 in the copolymer is 1.2%.

[0065] Example 4

[0066] The copolymerization reaction of this example is carried out in a 2 L reaction kettle. The specific steps are as follows:

[0067] Heat the reactor and set the heating temperature to 120 °C; turn on the argon gas and flush the reactor three times to displace the air inside; maintain a constant temperature; start stirring and set the stirring speed to 400 rpm; sequentially add n-nonane, 1-hexene, monomer 1, and methylaluminoxane to the reactor; among them, the addition amount of n-nonane in the reaction kettle is 1 L, the addition amount of 1-hexene is 84 g, the addition amount of monomer 1 is 16 g, and the addition amount of methylaluminoxane is 464 mg; introduce ethylene into the reactor to stabilize the pressure inside the reactor at 3.0 MPa; after the temperature and pressure are stabilized to the preset conditions, add 6.5 mg of isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride to the reactor; start timing; when the total residence time of the materials in the reactor is 15 min starting from the addition of the metallocene compound, introduce air to terminate the polymerization.

[0068] The product is washed with alcohol, filtered by suction, dried, weighed, and 200.9 g of copolymer is obtained. The density of the copolymer is measured by a densitometer to be 0.854 g / cm 3 ; The structure of the copolymer is analyzed by NMR. The molar content of 1-hexene in the copolymer is 19.6%, and the molar content of the structural unit of monomer 1 in the copolymer is 3.2%.

[0069] Example 5

[0070] The copolymerization reaction of this example was carried out in a 2L reactor. The specific steps are as follows:

[0071] Heat the reactor and set the heating temperature to 120 °C; open argon and flush the reactor three times to displace the air therein; maintain a constant temperature; start stirring and set the stirring speed to 400 rpm; sequentially add n-decane, 1-nonene, monomer 3, and methylaluminoxane to the reactor; among them, the addition amount of n-decane in the reactor is 1L, the addition amount of 1-nonene is 126g, the addition amount of monomer 3 is 13g, and the addition amount of methylaluminoxane is 580mg; introduce ethylene into the reactor to make the pressure in the reactor stable at 4.0 MPa; after the temperature and pressure are stable to the preset conditions, add 4.3 mg of isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride to the reactor; start timing; when the total residence time of the material in the reactor is 15 min starting from the addition of the metallocene compound, add a 10% hydrochloric acid-acidified ethanol solution to terminate the polymerization.

[0072] The product was washed with alcohol, filtered by suction, dried, weighed, and 277.8 g of copolymer was obtained. The density of the copolymer was measured by a densitometer to be 0.852 g / cm 3 ; The structure of the copolymer was analyzed by NMR. The molar content of 1-nonene in the copolymer was 19.8%, and the molar content of the structural unit of monomer 3 in the copolymer was 1.8%.

[0073] Example 6

[0074] The copolymerization reaction of this example was carried out in a 2L reactor. The specific steps are as follows:

[0075] Heat the reactor and set the heating temperature to 160 °C; open argon and flush the reactor three times to displace the air therein; maintain a constant temperature; start stirring and set the stirring speed to 400 rpm; sequentially add cyclohexane, 1-decene, monomer 5, and methylaluminoxane to the reactor; among them, the addition amount of cyclohexane in the reactor is 1L, the addition amount of 1-decene is 140g, the addition amount of monomer 5 is 19g, and the addition amount of methylaluminoxane is 232mg; introduce ethylene into the reactor to make the pressure in the reactor stable at 2.5 MPa; after the temperature and pressure are stable to the preset conditions, add 4.3 mg of isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride to the reactor; start timing; when the total residence time of the material in the reactor is 15 min starting from the addition of the metallocene compound, add a 10% hydrochloric acid-acidified ethanol solution to terminate the polymerization.

[0076] The product was washed with alcohol, filtered by suction, dried, weighed, and 316.5 g of copolymer was obtained. The density of the copolymer was measured by a densitometer to be 0.853 g / cm 3;The structure of the copolymer was analyzed by NMR. The molar content of 1-decene in the copolymer was 18.6%, and the molar content of monomer 5 structural units in the copolymer was 2.2%.

[0077] Example 7

[0078] The copolymerization reaction of this example was carried out in a 2 L reactor. The specific steps are as follows:

[0079] The reactor was heated, and the heating temperature was set at 200 °C; nitrogen was turned on, and the reactor was flushed three times to displace the air therein; the temperature was kept constant; stirring was started, and the stirring speed was set at 400 rpm; n-hexane, 1-octene, monomer 5, and methylaluminoxane were added to the reactor in sequence; among them, the addition amount of n-hexane in the reactor was 1 L, the addition amount of 1-octene was 28 g, the addition amount of monomer 5 was 4 g, and the addition amount of methylaluminoxane was 232 mg; ethylene was introduced into the reactor to make the pressure in the reactor stable at 2.5 MPa; after the temperature and pressure were stabilized to the preset conditions, 4.3 mg of isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride was added to the reactor; timing was started; 20 minutes after the addition of the metallocene compound, carbon dioxide was introduced to terminate the polymerization when the total residence time of the materials in the reactor was 20 min.

[0080] The product was washed with alcohol, filtered by suction, dried, weighed, and 163.9 g of copolymer was obtained. The density of the copolymer was measured by a densitometer to be 0.892 g / cm 3 ;The structure of the copolymer was analyzed by NMR. The molar content of 1-octene in the copolymer was 7.6%, and the molar content of monomer 5 structural units in the copolymer was 1.1%.

[0081] Example 8

[0082] The copolymerization reaction of this example was carried out in a 2 L reactor. The specific steps are as follows:

[0083] The reactor was heated, and the heating temperature was set at 240 °C; argon was turned on, and the reactor was flushed three times to displace the air therein; the temperature was kept constant; stirring was started, and the stirring speed was set at 400 rpm; n-octane, 1-octene, monomer 3, and methylaluminoxane were added to the reactor in sequence; among them, the addition amount of n-octane in the reactor was 1 L, the addition amount of 1-octene was 56 g, the addition amount of monomer 3 was 12 g, and the addition amount of methylaluminoxane was 232 mg; ethylene was introduced into the reactor to make the pressure in the reactor stable at 2.5 MPa; after the temperature and pressure were stabilized to the preset conditions, 4.3 mg of isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride was added to the reactor; timing was started; 15 minutes after the addition of the metallocene compound, a 10% hydrochloric acid acidified ethanol solution was added to terminate the polymerization.

[0084] The product was washed with alcohol, filtered by suction, dried, and weighed to obtain 137.9 g of the copolymer. The density of the copolymer was measured by a densitometer to be 0.884 g / cm 3 ; The structure of the copolymer was analyzed by NMR. The molar content of 1-hexene in the copolymer was 9.6%, and the molar content of the monomer 3 structural unit in the copolymer was 1.8%.

[0085] Example 9

[0086] The copolymerization reaction of this example was carried out in a 2 L reaction kettle. The specific steps are as follows:

[0087] The reactor was heated, and the heating temperature was set to 120 °C; argon was turned on, and the reactor was rinsed three times to displace the air therein; the temperature was kept constant; stirring was started, and the stirring speed was set to 400 rpm; n-nonane, 1-hexene, monomer 1, and ethylaluminoxane were sequentially added to the reactor; among them, the addition amount of n-nonane in the reaction kettle was 1 L, the addition amount of 1-hexene was 42 g, the addition amount of monomer 1 was 16 g, and the addition amount of ethylaluminoxane was 432 mg; ethylene was introduced into the reactor to make the pressure in the reactor stable at 2.5 MPa; after the temperature and pressure were stable to the preset conditions, 4.3 mg of isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride was added to the reactor; timing was started; 15 minutes after the addition of the metallocene compound, air was introduced to terminate the polymerization when the total residence time of the materials in the reactor was 15 min.

[0088] The product was washed with alcohol, filtered by suction, dried, and weighed to obtain 117.0 g of the copolymer. The density of the copolymer was measured by a densitometer to be 0.885 g / cm 3 ; The structure of the copolymer was analyzed by NMR. The molar content of 1-hexene in the copolymer was 10.6%, and the molar content of the monomer 1 structural unit in the copolymer was 2.8%.

[0089] Example 10

[0090] The copolymerization reaction of this example was carried out in a 2 L reaction kettle. The specific steps are as follows:

[0091] Heat the reactor and set the heating temperature to 120 °C; turn on the argon gas and flush the reactor three times to displace the air therein; maintain a constant temperature; start stirring and set the stirring speed to 400 rpm; sequentially add n-decane, 1-heptene, monomer 1, and ethylaluminoxane to the reactor; wherein, the addition amount of n-decane in the reaction kettle is 1 L, the addition amount of 1-heptene is 49 g, the addition amount of monomer 1 is 16 g, and the addition amount of ethylaluminoxane is 432 mg; introduce ethylene into the reactor to make the pressure in the reactor stable at 2.5 MPa; after the temperature and pressure are stable to the preset conditions, add 6.5 mg of isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride to the reactor; start timing; when the total residence time of the materials in the reactor is 15 min starting from the addition of the metallocene compound, add 10% hydrochloric acid-ethanol solution to terminate the polymerization.

[0092] The product was washed with alcohol, filtered by suction, dried, weighed, and 131.9 g of copolymer was obtained. The density of the copolymer was measured by a densitometer to be 0.886 g / cm 3 ; The structure of the copolymer was analyzed by NMR. The molar content of 1-heptene in the copolymer was 9.8%, and the molar content of the structural unit of monomer 1 in the copolymer was 2.8%.

[0093] Example 11

[0094] The copolymerization reaction of this example was carried out in a 2 L reaction kettle. The specific steps are as follows:

[0095] Heat the reactor and set the heating temperature to 120 °C; turn on the argon gas and flush the reactor three times to displace the air therein; maintain a constant temperature; start stirring and set the stirring speed to 400 rpm; sequentially add n-hexane, 1-nonene, monomer 2, and ethylaluminoxane to the reactor; wherein, the addition amount of n-hexane in the reaction kettle is 1 L, the addition amount of 1-nonene is 63 g, the addition amount of monomer 2 is 16 g, and the addition amount of ethylaluminoxane is 864 mg; introduce ethylene into the reactor to make the pressure in the reactor stable at 2.5 MPa; after the temperature and pressure are stable to the preset conditions, add 8.6 mg of isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride to the reactor; start timing; when the total residence time of the materials in the reactor is 15 min starting from the addition of the metallocene compound, add 10% hydrochloric acid-ethanol solution to terminate the polymerization.

[0096] The product was washed with alcohol, filtered by suction, dried, weighed, and 158.9 g of copolymer was obtained. The density of the copolymer was measured by a densitometer to be 0.888 g / cm 3 ; The structure of the copolymer was analyzed by NMR. The molar content of 1-nonene in the copolymer was 9.0%, and the molar content of the structural unit of monomer 2 in the copolymer was 2.8%.

[0097] Example 12

[0098] The copolymerization reaction of this example was carried out in a 2L reactor. The specific steps are as follows:

[0099] Heat the reactor and set the heating temperature to 120 °C; open argon and flush the reactor three times to displace the air therein; maintain a constant temperature; start stirring and set the stirring speed to 400 rpm; sequentially add n-hexane, 1-decene, monomer 1 and methylaluminoxane into the reactor; among them, the addition amount of n-hexane in the reactor is 1L, the addition amount of 1-decene is 35g, the addition amount of monomer 1 is 16g, and the addition amount of methylaluminoxane is 116mg; introduce ethylene into the reactor to make the pressure in the reactor stable at 2.5 MPa; after the temperature and pressure are stable to the preset conditions, add 4.3 mg of isopropylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride into the reactor; start timing; when the total residence time of the materials in the reactor is 15 min after adding the metallocene compound, introduce carbon dioxide to terminate the polymerization.

[0100] The product was washed with alcohol, filtered by suction, dried, weighed, and 102.9 g of copolymer was obtained. The density of the copolymer was measured by a densitometer to be 0.893 g / cm 3 ; The structure of the copolymer was analyzed by NMR. The molar content of 1-decene in the copolymer was 8.1%, and the molar content of the structural unit of monomer 1 in the copolymer was 3.8%.

[0101] Example 13

[0102] The copolymerization reaction of this example was carried out in a 2L reactor. The specific steps are as follows:

[0103] Heat the reactor and set the heating temperature to 100 °C; open argon and flush the reactor three times to displace the air therein; maintain a constant temperature; start stirring and set the stirring speed to 400 rpm; sequentially add cyclohexane, 1-octene, monomer 4 and methylaluminoxane into the reactor; among them, the addition amount of cyclohexane in the reactor is 1L, the addition amount of 1-octene is 11g, the addition amount of monomer 4 is 1g, and the addition amount of methylaluminoxane is 232mg; introduce ethylene into the reactor to make the pressure in the reactor stable at 3.0 MPa; after the temperature and pressure are stable to the preset conditions, add 5.6 mg of dibenzylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride into the reactor; start timing; when the total residence time of the materials in the reactor is 20 min after adding the metallocene compound, introduce air to terminate the polymerization.

[0104] The product was washed with alcohol, filtered by suction, dried, weighed, and 24.9 g of copolymer was obtained. The density of the copolymer was measured by a densitometer to be 0.900 g / cm 3; The structure of the copolymer was analyzed by NMR. The molar content of 1-octene in the copolymer was 5.1%, and the molar content of monomer 4 structural units in the copolymer was 1.0%.

[0105] Example 14

[0106] The copolymerization reaction of this example was carried out in a 2L reactor. The specific steps are as follows:

[0107] The reactor was heated, and the heating temperature was set at 120 °C; nitrogen was turned on, and the reactor was flushed three times to displace the air therein; the constant temperature was maintained; stirring was started, and the stirring speed was set at 400 rpm; n-hexane, 1-hexene, monomer 6, and methylaluminoxane were added to the reactor in sequence; among them, the addition amount of n-hexane in the reactor was 1L, the addition amount of 1-hexene was 84g, the addition amount of monomer 6 was 14g, and the addition amount of methylaluminoxane was 232mg; ethylene was introduced into the reactor to make the pressure in the reactor stable at 2.5 MPa; after the temperature and pressure were stable to the preset conditions, 8.4 mg of dibenzylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride was added to the reactor; timing was started; 10% hydrochloric acid-ethanol solution was added to terminate the polymerization when the total residence time of the materials in the reactor was 15 min starting from the addition of the metallocene compound.

[0108] The product was washed with alcohol, filtered by suction, dried, and weighed to obtain 197.0 g of copolymer. The density of the copolymer was measured by a densitometer to be 0.852 g / cm 3 ; The structure of the copolymer was analyzed by NMR. The molar content of 1-hexene in the copolymer was 20.2%, and the molar content of monomer 6 structural units in the copolymer was 1.9%.

[0109] Example 15

[0110] The copolymerization reaction of this example was carried out in a 2L reactor. The specific steps are as follows:

[0111] The reactor was heated, and the heating temperature was set at 160 °C; argon was turned on, and the reactor was flushed three times to displace the air therein; the constant temperature was maintained; stirring was started, and the stirring speed was set at 400 rpm; n-octane, 1-heptene, monomer 2, and ethylaluminoxane were added to the reactor in sequence; among them, the addition amount of n-hexane in the reactor was 1L, the addition amount of 1-heptene was 98g, the addition amount of monomer 2 was 93g, and the addition amount of ethylaluminoxane was 576mg; ethylene was introduced into the reactor to make the pressure in the reactor stable at 2.0 MPa; after the temperature and pressure were stable to the preset conditions, 5.6 mg of dibenzylidene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride was added to the reactor; timing was started; air was introduced to terminate the polymerization when the total residence time of the materials in the reactor was 20 min starting from the addition of the metallocene compound.

[0112] The product was washed with alcohol, filtered by suction, dried, and weighed to obtain 382.0 g of the copolymer. The density of the copolymer was measured by a densitometer to be 0.850 g / cm 3 ; The structure of the copolymer was analyzed by NMR. The molar content of 1-heptene in the copolymer was 20.2%, and the molar content of the structural unit of monomer 2 in the copolymer was 4.9%.

[0113] Example 16

[0114] The copolymerization reaction in this example was carried out in a 2 L reactor. The specific steps are as follows:

[0115] The reactor was heated, and the heating temperature was set to 120 °C; argon was opened, and the reactor was rinsed three times to displace the air therein; the temperature was kept constant; stirring was started, and the stirring speed was set to 400 rpm; n-nonane, 1-nonene, monomer 6, and methylaluminoxane were successively added to the reactor; among them, the addition amount of n-nonane in the reactor was 1 L, the addition amount of 1-nonene was 126 g, the addition amount of monomer 6 was 36 g, and the addition amount of methylaluminoxane was 116 mg; ethylene was introduced into the reactor to make the pressure in the reactor stable at 2.0 MPa; after the temperature and pressure were stabilized to the preset conditions, 4.5 mg of dimethylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride was added to the reactor; timing was started; 20 min after the addition of the metallocene compound, carbon dioxide was introduced to terminate the polymerization when the total residence time of the materials in the reactor was 20 min.

[0116] The product was washed with alcohol, filtered by suction, dried, and weighed to obtain 324.0 g of the copolymer. The density of the copolymer was measured by a densitometer to be 0.862 g / cm 3 ; The structure of the copolymer was analyzed by NMR. The molar content of 1-nonene in the copolymer was 16.3%, and the molar content of the structural unit of monomer 6 in the copolymer was 3.8%.

[0117] Example 17

[0118] The copolymerization reaction in this example was carried out in a 2 L reactor. The specific steps are as follows:

[0119] Heat the reactor and set the heating temperature to 160 °C; turn on nitrogen and flush the reactor three times to displace the air inside; maintain a constant temperature; start stirring and set the stirring speed to 400 rpm; sequentially add n-decane, 1-octene, monomer 5, and methylaluminoxane to the reactor; among them, the addition amount of n-decane in the reaction kettle is 1 L, the addition amount of 1-octene is 56 g, the addition amount of monomer 5 is 16 g, and the addition amount of methylaluminoxane is 580 mg; introduce ethylene into the reactor to make the pressure inside the reactor stable at 2.5 MPa; after the temperature and pressure are stable to the preset conditions, add 4.5 mg of dimethylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride to the reactor; start timing; 15 minutes after the total residence time of the materials in the reactor since the addition of the metallocene compound, introduce air to terminate the polymerization.

[0120] The product is washed with alcohol, filtered by suction, dried, weighed, and 143.5 g of copolymer is obtained. The density of the copolymer is measured by a densitometer to be 0.886 g / cm 3 ; The structure of the copolymer is analyzed by NMR. The molar content of 1-octene in the copolymer is 7.8%, and the molar content of the structural unit of monomer 5 in the copolymer is 0.8%.

[0121] Example 18

[0122] The copolymerization reaction of this example is carried out in a 2 L reaction kettle. The specific steps are as follows:

[0123] Heat the reactor and set the heating temperature to 200 °C; turn on argon and flush the reactor three times to displace the air inside; maintain a constant temperature; start stirring and set the stirring speed to 400 rpm; sequentially add n-hexane, 1-octene, monomer 3, and ethylaluminoxane to the reactor; among them, the addition amount of n-nonane in the reaction kettle is 1 L, the addition amount of 1-octene is 112 g, the addition amount of monomer 3 is 18 g, and the addition amount of ethylaluminoxane is 432 mg; introduce ethylene into the reactor to make the pressure inside the reactor stable at 3.0 MPa; after the temperature and pressure are stable to the preset conditions, add 6.8 mg of dimethylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride to the reactor; start timing; 20 minutes after the total residence time of the materials in the reactor since the addition of the metallocene compound, add 10% hydrochloric acid-ethanol solution to terminate the polymerization.

[0124] The product is washed with alcohol, filtered by suction, dried, weighed, and 260.2 g of copolymer is obtained. The density of the copolymer is measured by a densitometer to be 0.861 g / cm 3 ; The structure of the copolymer is analyzed by NMR. The molar content of 1-octene in the copolymer is 16.2%, and the molar content of the structural unit of monomer 3 in the copolymer is 2.8%.

[0125] Example 19

[0126] The copolymerization reaction of this example was carried out in a 2L reactor. The specific steps are as follows:

[0127] Heat the reactor, set the heating temperature to 120 °C; open argon, flush the reactor three times to displace the air therein; keep the temperature constant; start stirring, set the stirring speed to 400 rpm; sequentially add cyclohexane, 1-hexene, monomer 4 and ethylaluminoxane to the reactor; among them, the addition amount of cyclohexane in the reactor is 1L, the addition amount of 1-hexene is 84g, the addition amount of monomer 4 is 47g, and the addition amount of ethylaluminoxane is 576mg; introduce ethylene into the reactor to make the pressure in the reactor stable at 3.0 MPa; after the temperature and pressure are stable to the preset conditions, add 5.8 mg of diphenylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride to the reactor; start timing; when the total residence time of the material in the reactor is 15 min starting from the addition of the metallocene compound, add 10% hydrochloric acid-ethanol solution to terminate the polymerization.

[0128] The product was washed with alcohol, filtered by suction, dried, weighed, and 260.9 g of copolymer was obtained. The density of the copolymer was measured by a densitometer to be 0.856 g / cm 3 ; The structure of the copolymer was analyzed by NMR. The molar content of 1-hexene in the copolymer was 17.1%, and the molar content of the structural unit of monomer 4 in the copolymer was 3.9%.

[0129] Example 20

[0130] The copolymerization reaction of this example was carried out in a 2L reactor. The specific steps are as follows:

[0131] Heat the reactor, set the heating temperature to 200 °C; open argon, flush the reactor three times to displace the air therein; keep the temperature constant; start stirring, set the stirring speed to 400 rpm; sequentially add n-hexane, 1-octene, monomer 5 and methylaluminoxane to the reactor; among them, the addition amount of n-hexane in the reactor is 1L, the addition amount of 1-octene is 56g, the addition amount of monomer 5 is 9g, and the addition amount of methylaluminoxane is 116mg; introduce ethylene into the reactor to make the pressure in the reactor stable at 2.5 MPa; after the temperature and pressure are stable to the preset conditions, add 5.8 mg of diphenylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride to the reactor; start timing; when the total residence time of the material in the reactor is 20 min starting from the addition of the metallocene compound, introduce carbon dioxide to terminate the polymerization.

[0132] The product was washed with alcohol, filtered by suction, dried, weighed, and 131.2 g of copolymer was obtained. The density of the copolymer was measured by a densitometer to be 0.882 g / cm 3;The structure of the copolymer was analyzed by NMR. The molar content of 1-octene in the copolymer was 9.1%, and the molar content of the structural unit of monomer 5 in the copolymer was 0.9%.

[0133] Example 21

[0134] The copolymerization reaction of this example was carried out in a 2L reactor. The specific steps are as follows:

[0135] The reactor was heated, and the heating temperature was set at 100 °C; argon was opened, and the reactor was flushed three times to displace the air therein; the temperature was kept constant; stirring was started, and the stirring speed was set at 400 rpm; n-octane, 1-decene, monomer 3 and methylaluminoxane were successively added to the reactor; among them, the addition amount of n-octane in the reactor was 1L, the addition amount of 1-decene was 70g, the addition amount of monomer 3 was 36g, and the addition amount of methylaluminoxane was 522mg; ethylene was introduced into the reactor to make the pressure in the reactor stable at 4.0 MPa; after the temperature and pressure were stable to the preset conditions, 8.7 mg of diphenylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride was added to the reactor; timing was started; 10% hydrochloric acid ethanol solution was added to terminate the polymerization when the total residence time of the materials in the reactor was 15 min since the addition of the metallocene compound.

[0136] The product was washed with alcohol, filtered by suction, dried, weighed, and 211.6 g of copolymer was obtained. The density of the copolymer was measured by a densitometer to be 0.881 g / cm 3 ;The structure of the copolymer was analyzed by NMR. The molar content of 1-decene in the copolymer was 9.8%, and the molar content of the structural unit of monomer 3 in the copolymer was 3.9%.

[0137] Example 22

[0138] The copolymerization reaction of this example was carried out in a 2L reactor. The specific steps are as follows:

[0139] The reactor was heated, and the heating temperature was set at 120 °C; nitrogen was opened, and the reactor was flushed three times to displace the air therein; the temperature was kept constant; stirring was started, and the stirring speed was set at 400 rpm; n-nonane, 1-octene, monomer 3 and methylaluminoxane were successively added to the reactor; among them, the addition amount of n-nonane in the reactor was 1L, the addition amount of 1-octene was 112g, the addition amount of monomer 3 was 74g, and the addition amount of methylaluminoxane was 580mg; ethylene was introduced into the reactor to make the pressure in the reactor stable at 4.0 MPa; after the temperature and pressure were stable to the preset conditions, 4.2 mg of vinyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride was added to the reactor; timing was started; air was introduced to terminate the polymerization when the total residence time of the materials in the reactor was 20 min since the addition of the metallocene compound.

[0140] The product was washed with alcohol, filtered by suction, dried, weighed, and 371.6 g of copolymer was obtained. The density of the copolymer was measured by a densitometer to be 0.850 g / cm 3 ; The structure of the copolymer was analyzed by NMR. The molar content of 1-octene in the copolymer was 19.8%, and the molar content of monomer 3 structural units in the copolymer was 4.9%.

[0141] Example 23

[0142] The copolymerization reaction in this example was carried out in a 2 L reaction kettle. The specific steps are as follows:

[0143] The reactor was heated, and the heating temperature was set to 160 °C; argon was turned on, and the reactor was rinsed three times to displace the air therein; the temperature was kept constant; stirring was started, and the stirring speed was set to 400 rpm; n-decane, 1-hexene, monomer 5, and methylaluminoxane were successively added to the reactor; among them, the addition amount of n-decane in the reaction kettle was 1 L, the addition amount of 1-hexene was 84 g, the addition amount of monomer 5 was 47 g, and the addition amount of methylaluminoxane was 522 mg; ethylene was introduced into the reactor to make the pressure in the reactor stable at 2.5 MPa; after the temperature and pressure were stable to the preset conditions, 6.3 mg of vinyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride was added to the reactor; timing was started; 15 minutes after the addition of the metallocene compound, when the total residence time of the materials in the reactor was 15 min, carbon dioxide was introduced to terminate the polymerization.

[0144] The product was washed with alcohol, filtered by suction, dried, weighed, and 260.8 g of copolymer was obtained. The density of the copolymer was measured by a densitometer to be 0.852 g / cm 3 ; The structure of the copolymer was analyzed by NMR. The molar content of 1-hexene in the copolymer was 18.7%, and the molar content of monomer 5 structural units in the copolymer was 3.6%.

[0145] Example 24

[0146] The copolymerization reaction in this example was carried out in a 2 L reaction kettle. The specific steps are as follows:

[0147] Heat the reactor and set the heating temperature to 100 °C; turn on nitrogen and flush the reactor three times to displace the air therein; maintain a constant temperature; start stirring and set the stirring speed to 400 rpm; sequentially add cyclohexane, 1-nonene, monomer 5, and ethylaluminoxane to the reactor; wherein, the addition amount of cyclohexane in the reaction kettle is 1 L, the addition amount of 1-nonene is 63 g, the addition amount of monomer 5 is 16 g, and the addition amount of ethylaluminoxane is 464 mg; introduce ethylene into the reactor to stabilize the pressure in the reactor at 3.0 MPa; after the temperature and pressure are stabilized to the preset conditions, add 8.4 mg of vinyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride to the reactor; start timing; 10% hydrochloric acid ethanol solution is added to terminate the polymerization when the total residence time of the material in the reactor is 15 min starting from the addition of the metallocene compound.

[0148] The product was washed with alcohol, filtered by suction, dried, weighed, and 157.2 g of copolymer was obtained. The density of the copolymer was measured by a densitometer to be 0.873 g / cm 3 ; The structure of the copolymer was analyzed by NMR. The molar content of 1-nonene in the copolymer was 10.9%, and the molar content of the structural unit of monomer 5 in the copolymer was 2.1%.

[0149] Example 25

[0150] The copolymerization reaction of this example was carried out in a 2 L reaction kettle. The specific steps are as follows:

[0151] Heat the reactor and set the heating temperature to 240 °C; turn on argon and flush the reactor three times to displace the air therein; maintain a constant temperature; start stirring and set the stirring speed to 400 rpm; sequentially add cyclohexane, 1-decene, monomer 3, and ethylaluminoxane to the reactor; wherein, the addition amount of cyclohexane in the reaction kettle is 1 L, the addition amount of 1-decene is 70 g, the addition amount of monomer 3 is 9 g, and the addition amount of ethylaluminoxane is 116 mg; introduce ethylene into the reactor to stabilize the pressure in the reactor at 2.0 MPa; after the temperature and pressure are stabilized to the preset conditions, add 4.2 mg of vinyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride to the reactor; start timing; carbon dioxide is introduced to terminate the polymerization when the total residence time of the material in the reactor is 15 min starting from the addition of the metallocene compound.

[0152] The product was washed with alcohol, filtered by suction, dried, weighed, and 158.2 g of copolymer was obtained. The density of the copolymer was measured by a densitometer to be 0.870 g / cm 3 ; The structure of the copolymer was analyzed by NMR. The molar content of 1-decene in the copolymer was 12.0%, and the molar content of the structural unit of monomer 3 in the copolymer was 1.1%.

[0153] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention. However, these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. An ethylene copolymer, characterized in that The ethylene copolymer comprises ethylene monomer, α-olefin monomer and functionalized styrene monomer, the molar ratio of the α-olefin monomer to the ethylene monomer is 1:4-24, and the molar ratio of the functionalized styrene monomer to the α-olefin monomer is 1:2-10; Wherein, the functionalized styrene monomer has the following structure: Here, R is one of an amino-substituted olefin group, an amino-substituted phenyl group, a carbazole group, a carboxyl-substituted benzopyrone group, a benzopyranyl group, and a carboxyl-substituted olefin group.

2. The ethylene copolymer according to claim 1, characterized in that The functionalized styrene monomer is at least one of monomers 1-6, and the monomers 1-6 have the following structure:

3. The ethylene copolymer according to claim 1, characterized in that The α-olefin monomer is selected from one of 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene.

4. The ethylene copolymer according to claim 1, characterized in that The density of the ethylene copolymer is 0.85 to 0.90 g / cm 3 The molar percentage of the α-olefin monomer is 5 to 20%, and the molar percentage of the functionalized styrene monomer is 1.0 to 5.0%.

5. The method for preparing an ethylene copolymer according to any one of claims 1 to 4, characterized in that: The steps include: Step 1, mixing α-olefin monomer, functionalized styrene monomer, solvent and co-catalyst; Step 2, introducing ethylene and adding a metallocene catalyst to carry out copolymerization reaction to obtain an ethylene copolymer.

6. The method for preparing an ethylene copolymer according to claim 5, characterized in that: The copolymerization reaction temperature is 100° C. to 240° C., the pressure is 2 MPa to 4 MPa; and / or the copolymerization reaction time is 10 min to 20 min.

7. The method for preparing an ethylene copolymer according to claim 5, characterized in that: The metallocene catalyst is R1(CpR2n)(FluR3m)MQ2, wherein Cp is a cyclopentadienyl group, Flu is a fluorenyl group, R2 and R3 are independently selected from H, C1 to C 12 Alkyl, C6~C 12 An aryl group or a halogen group, m and n are integers of 0 to 4, R1 is a bridging group connecting the cyclopentadienyl group and the fluorenyl group, M is zirconium or hafnium, and Q is a halogen group or a C1 to C6 alkyl group.

8. The method for preparing an ethylene copolymer according to claim 7, characterized in that: The metallocene catalyst is selected from isopropylidene(cyclopentadiene)(9-fluorenyl)zirconium dichloride, diphenylidene(cyclopentadiene)(9-fluorenyl)zirconium dichloride, dimethylsilyl(cyclopentadiene)(9-fluorenyl)zirconium dichloride, diphenylsilyl(cyclopentadiene)(9-fluorenyl)zirconium dichloride and vinylidene(cyclopentadiene)(9-fluorenyl)zirconium dichloride.

9. The method for preparing an ethylene copolymer according to claim 5, characterized in that: The co-catalyst is an aluminoxane compound; the molar ratio of the metallocene catalyst to the co-catalyst is 1:200-1000.

10. Use of the ethylene copolymer according to any one of claims 1 to 4 in polyolefin elastomers.

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