Method for preparing polymer elastomer by mixing ethane and high-carbon alkane in subcritical state and polymer elastomer

Abstract

The invention provides a method for preparing a polymer elastomer by mixing ethane and high-carbon alkane in a subcritical state and the polymer elastomer. According to the method, a mixed solvent composed of an organic solvent and a light component containing ethane is adopted, so that a polymerization reaction system is in a subcritical state conveniently, the diffusion performance and the mass transfer speed of polymerization monomers (molecules such as olefin) are increased, the viscosity of the reaction system can be reduced, and the production efficiency is improved. Particularly, in the process of preparing the polymer elastomer, accurate regulation and control (monomer insertion rate) of the polymer structure can be realized by adjusting process parameters, and the polymer elastomer with high comonomer content is obtained. Meanwhile, compared with other solvent systems, the light component ethane has lower subcritical process conditions (temperature and pressure), and the recovery energy consumption and the production cost of solvent separation of the subcritical polymerization process are effectively reduced.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to a method for preparing a polymer elastomer by mixing ethane and higher alkanes in a subcritical state and a polymer elastomer. Background Art

[0002] Polymer elastomers are a class of polymer materials with high elasticity and reversible deformation ability, and are widely used in fields such as rubber products, sealing materials, shock-absorbing materials or medical materials.

[0003] Currently, the traditional preparation methods of polymer elastomers mainly include gas-phase polymerization and slurry polymerization. However, both of the above methods have limitations. For example, gas-phase polymerization has high requirements for catalysts, high catalyst costs, and high requirements for the design and control of reactors. Especially when preparing elastomers, more complex reaction conditions are required; slurry polymerization has high requirements for stirring and heat transfer equipment, etc.

[0004] Compared with gas-phase polymerization and slurry polymerization, the solution polymerization method has been widely used in the production of high-performance polymer elastomers, such as ethylene-α-olefin copolymers, ethylene-propylene rubbers, propylene-based elastomers or vinyl elastomers, etc., due to mild conditions, the ability to provide a uniform reaction environment, easy control of molecular weight, and high flexibility.

[0005] However, in the solution polymerization method, the polymer has poor solubility, and it is very easy to cause wall adhesion or pipeline blockage inside the equipment during the devolatilization separation process of the unreacted materials and the polymer. At the same time, higher energy consumption is required for solution polymerization devolatilization. Therefore, the solvent devolatilization separation and recovery of the solution polymerization process are relatively difficult, and the α-olefin insertion rate of the polymer elastomer obtained by the solution polymerization method is low and not easy to be regulated. Summary of the Invention

[0006] In view of this, the purpose of the present invention is to provide a method for preparing a polymer elastomer by mixing ethane and higher alkanes in a subcritical state and a polymer elastomer. The method can overcome the disadvantages of difficult solvent separation and poor polymer solubility in traditional solution polymerization, and can accurately regulate the content of comonomers and improve the α-olefin insertion rate.

[0007] To achieve this purpose, the present invention adopts the following technical solutions:

[0008] In the first aspect, the present invention provides a method for preparing a polymer elastomer, including the following steps:

[0009] Mix the polymerization monomers, main catalyst, cocatalyst and mixed solvent, and carry out a polymerization reaction in a subcritical state to obtain a polymer elastomer.

[0010] Preferably, the mixed solvent comprises an organic solvent and a light component, and the light component comprises any one or more of ethane, carbon dioxide or methane.

[0011] Preferably, the mass ratio of the organic solvent to the light component is (30-1):1.

[0012] Preferably, the organic solvent is selected from one or more of substituted or unsubstituted C3-C12 straight-chain alkanes, substituted or unsubstituted C3-C12 isoalkanes, substituted or unsubstituted C5-C12 cycloalkanes, and substituted or unsubstituted C6-C8 aromatic hydrocarbons.

[0013] Preferably, the organic solvent is selected from any one or more of propane, n-butane, isobutane, cyclobutane, n-pentane, isopentane, neopentane, cyclopentane, n-hexane, cyclohexane, methylcyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, undecane, dodecane, toluene or xylene.

[0014] Preferably, the temperature of the polymerization reaction is 130-200 °C and the pressure is 3-8 MPa.

[0015] Preferably, the mass ratio of the polymerization monomer, the main catalyst, the cocatalyst and the mixed solvent is (4-5):(2-3):1:(15-30).

[0016] Preferably, the polymerization reaction is carried out in any one of batch polymerization, semi-continuous polymerization or continuous polymerization.

[0017] Preferably, the polymerization reaction is carried out under anhydrous and anaerobic conditions.

[0018] Preferably, the reactor for the polymerization reaction is a kettle reactor or a tubular reactor.

[0019] Preferably, the main catalyst is a metallocene catalyst or a non-metallocene catalyst.

[0020] Preferably, the cocatalyst is selected from any one or more of methylaluminoxane compounds, modified methylaluminoxane compounds, tris(pentafluorophenyl)boron compounds, triphenylcarbenium tetrakis(pentafluorophenyl)borate compounds, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate compounds, triisobutylaluminum or trimethylaluminum.

[0021] Preferably, the main catalyst is selected from any one or more of bis(indenyl)zirconium dichloride, bis(indenyl)dimethylzirconium, bis(cyclopentadienyl)dimethylhafnium, bis[2-(3',5'-di-tert-butylphenyl)-indenyl]zirconium dichloride, bis(2-methyl-4,5-phenyl-indenyl)zirconium dichloride, bis(cyclopentadienyl)-bis(phenoxy)zirconium, vinylidene-bridged bis(indenyl)zirconium dichloride, dimethylsilylene-bridged bis(indenyl)zirconium dichloride, diphenylmethylene-bridged (cyclopentadienyl)(fluorenyl)zirconium dichloride, diphenylmethylene-bridged (cyclopentadienyl)(2-dimethylamino-fluorenyl)zirconium dichloride, dimethylsilylene-bridged (tetramethylcyclopentadienyl)(tert-butylamino)dimethyltitanium, dimethylsilylene-bridged (3-pyrrolylindenyl)(tert-butylamino)dimethyltitanium, pentamethylcyclopentadienyl(2-phenylphenoxy)titanium dichloride, pentamethylcyclopentadienyl(2,6-diisopropylphenoxy)titanium dichloride, bis(3-methylsalicylidene-pentafluorophenylimino)titanium dichloride, bis(salicylidene-phenylimino)titanium dichloride, [N-(3,5-di-tert-butylsalicylidene)-2-diphenylphosphinobenzylimino]titanium trichloride or (2,3,4-trihydro-8-diphenylphosphino-quinolyl)tribenzylzirconium.

[0022] Preferably, the polymerization monomer is selected from ethylene and α-olefins.

[0023] In a second aspect, the present invention provides a polymer elastomer prepared by the above preparation method, wherein the weight average molecular weight of the polymer elastomer is 3000-1500000 g / mol, and the molecular weight distribution index is 1.0-5.0.

[0024] Preferably, the polymer elastomer includes but is not limited to any one or more of ethylene-α-olefin copolymers, propylene-based polymer elastomers, vinyl elastomers, or ethylene-propylene-diene rubbers.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0026] The present invention uses a mixed solvent composed of an organic solvent and a light component ethane, which facilitates the control of the polymerization temperature above the boiling point and below the critical temperature of the reaction system, and the polymerization pressure is controlled below the critical pressure, so that the polymerization reaction system is in a subcritical state, increasing the diffusion performance and mass transfer rate of the polymerization monomers (such as ethylene and α-olefins), which can not only greatly reduce the viscosity of the reaction system, but also improve the production efficiency. In particular, in the process of preparing the polymer elastomer of the present invention, the precise regulation of the polymer structure (monomer insertion rate) can be achieved by adjusting the process parameters, and a polymer elastomer with a high copolymer monomer content insertion rate can be obtained. At the same time, the light component ethane has lower subcritical process conditions compared with other solvent systems, making the polymerization conditions milder and the requirements for equipment manufacturing lower, greatly reducing the production cost of the subcritical polymerization process. In addition, compared with the reaction systems of other organic solvents, the boiling point of the reaction system in the subcritical state is lower, thus greatly reducing the energy consumption for solvent separation and recovery. Detailed Embodiments

[0027] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0028] Aiming at the problems in the prior art that the separation and recovery of solvents in the preparation method of polymer elastomers are difficult, and the insertion rate of α-olefins in the polymer elastomers is low and difficult to regulate, the present invention provides a method for preparing a polymer elastomer by mixing ethane and a high-carbon alkane in a subcritical state, including the following steps:

[0029] After mixing the polymerization monomer, the main catalyst, the co-catalyst and the mixed solvent, a polymerization reaction occurs in a subcritical state to obtain a polymer elastomer.

[0030] In the present invention, the polymerization monomer is selected from ethylene and α-olefins. Specifically, the α-olefin can be propylene, butene, hexene, octene or heptene, etc. The present invention has no particular limitation on the source of the polymerization monomer, and general commercially available products can be used. In the present invention, all the polymerization monomers need to remove water, oxygen, sulfur, chlorine, etc. In some embodiments of the present invention, when preparing the polymer elastomer, the α-olefin insertion rate content of the polymerization monomer can be regulated within 20-50 wt%, such as 20 wt%, 30 wt%, 40 wt% or 50 wt%, etc.

[0031] In the present invention, the main catalyst is a metallocene catalyst or a non-metallocene catalyst. In some embodiments of the present invention, the main catalyst is selected from any one or more of bis(indenyl)zirconium dichloride, bis(indenyl)dimethylzirconium, bis(cyclopentadienyl)dimethylhafnium, bis[2-(3',5'-di-tert-butylphenyl)-indenyl]zirconium dichloride, bis(2-methyl-4,5-phenyl-indenyl)zirconium dichloride, bis(cyclopentadienyl)-bis(phenoxy)zirconium, vinylidene-bridged bis(indenyl)zirconium dichloride, dimethylsilylene-bridged bis(indenyl)zirconium dichloride, diphenylmethylene-bridged cyclopentadienyl-fluorenyl zirconium dichloride, diphenylmethylene-bridged cyclopentadienyl-(2-dimethylamino-fluorenyl) zirconium dichloride, dimethylsilylene-bridged tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium, dimethylsilylene-3-pyrrolylindenyl-tert-butylamino-dimethyltitanium, pentamethylcyclopentadienyl-(2-phenylphenoxy)-titanium dichloride, pentamethylcyclopentadienyl-(2,6-diisopropylphenoxy)-titanium dichloride, bis(3-methylsalicylidene-pentafluorophenylimino)titanium dichloride, bis(salicylidene-phenylimino)titanium dichloride, [N-(3,5-di-tert-butylsalicylidene)-2-diphenylphosphinobenzylimino]titanium trichloride or (2,3,4-trihydro-8-diphenylphosphino-quinolyl)tribenzylzirconium.

[0032] In the present invention, the cocatalyst is selected from any one or more of methylaluminoxane compounds, modified methylaluminoxane compounds, tris(pentafluorophenyl)boron compounds, triphenylcarbenium tetrakis(pentafluorophenyl)borate compounds, N,N-dimethylaniline tetrakis(pentafluorophenyl)borate compounds, triisobutylaluminum or trimethylaluminum.

[0033] In the present invention, the mixed solvent includes an organic solvent and a light component. The light component includes any one or more of ethane, carbon dioxide or methane, preferably ethane. The reason for introducing the light component including ethane in the present invention is as follows: ① Ethane enables the reaction system to reach the subcritical state under milder conditions; ② Under the subcritical state, alkanes and alkenes have extremely strong diffusion rates and mass transfer capabilities, which can improve the insertion rate of polymers and product performance; ③ The subcritical state under the ethane reaction system will not introduce new impurities, which is beneficial to the recovery of unreacted materials; ④ The subcritical state under the ethane reaction system is more easily separated from the polymer.

[0034] In the present invention, the organic solvent is selected from one or more of substituted or unsubstituted C3-C12 linear alkanes, substituted or unsubstituted C3-C12 isoparaffins, substituted or unsubstituted C5-C12 cycloalkanes, and substituted or unsubstituted C6-C8 aromatic hydrocarbons. In some embodiments of the present invention, the organic solvent is selected from any one or more of propane, n-butane, isobutane, cyclobutane, n-pentane, isopentane, neopentane, cyclopentane, n-hexane, cyclohexane, methylcyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, undecane, dodecane, toluene or xylene, preferably n-hexane and / or octane. In the present invention, the organic solvent needs to be dehydrated, oxygen, CO, CO2, etc.

[0035] In some embodiments of the present invention, the mass ratio of the organic solvent to the light components is (30-1):1, such as 1:1, 5:1, 10:1, 15:1, 20:1, 25:1 or 30:1, etc.

[0036] In the present invention, preferably under anhydrous and anaerobic conditions, the polymerization monomer, the main catalyst, the cocatalyst and the mixed solvent are mixed according to the mass ratio of (4-5):(2-3):1:(15-30), such as 4:2:1:15, 4:3:1:20, 4.5:2:1:25 or 5:3:1:30, etc. The mixing is preferably carried out in a reaction kettle under stirring conditions.

[0037] After the mixing is completed, according to the present invention, after adjusting the reaction system to the subcritical state, a polymerization reaction occurs to obtain the elastic polymer. Among them, the polymerization reaction mode can adopt any one of batch polymerization, semi-continuous polymerization or continuous polymerization; the polymerization reaction is carried out under anhydrous and anaerobic conditions; the reactor for the polymerization reaction is a kettle reactor or a tubular reactor. Among them, when using the batch or semi-continuous polymerization process, the mixed solvent, the polymerization monomer, the cocatalyst solution and the main catalyst solution can be quantitatively added into the reactor in sequence, or can be added into the reactor at the same time. When using the continuous polymerization process, the mixed solvent, the polymerization monomer, the cocatalyst solution and the main catalyst solution need to be continuously added into the reaction kettle.

[0038] In the present invention, the subcritical state means that the temperature of the polymerization reaction is within the subcritical range, that is, higher than the boiling point temperature of the reaction system and lower than the critical temperature; at the same time, the pressure of the polymerization reaction needs to be lower than the critical pressure.

[0039] Specifically, through experimental exploration in the present invention, the temperature of the polymerization reaction is limited to 130-200°C, preferably 150-190°C; at the same time, the pressure of the polymerization reaction is limited to 3-8 MPa, preferably 4-8 MPa, so that the polymerization reaction system is in the subcritical state.

[0040] It should be noted that in the present invention, the subcritical state is crucial for the overall polymerization reaction because: ① Under the subcritical state, the reactant alkanes and alkenes have extremely strong diffusion and mass transfer capabilities, which can improve the insertion rate of the polymer; ② Under the subcritical state, the molecules such as alkanes and alkenes have stronger permeability to the weakly polar or non-polar substance of the polymer, which is conducive to improving the product performance; ③ When separating the unreacted materials from the polymer, the required energy consumption is lower, saving energy; ④ Compared with the traditional solution polymerization, in the post-treatment devolatilization process, it will not cause problems such as wall hanging, adhesion, and pipeline blockage inside the equipment.

[0041] If the temperature and pressure of the polymerization reaction are not within the above ranges, the insertion rate of α-olefins in the product is low and difficult to control. At the same time, when recovering and separating the post-treatment materials, the energy consumption is high, and it is easy to cause problems such as wall hanging, adhesion, and pipeline blockage of the equipment.

[0042] In some embodiments of the present invention, preferably under anhydrous and anaerobic conditions, a mixed solvent, a polymerization monomer, a cocatalyst solution, and a main catalyst solution are quantitatively added into a batch reactor or a tubular reactor simultaneously or sequentially. Among them, the mixed solvent is composed of an organic solvent and a light component including ethane mixed in a mass ratio of (30 - 1):1. By controlling the addition amount of ethane, the reaction system is in a subcritical state, and a polymerization reaction occurs to obtain a polymer elastomer.

[0043] Exemplarily, in some embodiments of the present invention, preferably under the protection of an inert gas, the main catalyst and the cocatalyst are respectively formulated into solutions and stored in a feeding tank, and the polymerization monomer and the organic solvent are stored in their respective feeding tanks. The inert gas can be a gas well-known to those skilled in the art, such as nitrogen.

[0044] Then, first preheat the reaction kettle and the pipeline to 130 - 180 °C, preferably 150 °C; start stirring, and set the rotation speed to 300 - 800 r / min, preferably 500 r / min; open the bottom feed valve and the top discharge valve of the kettle, and open the 4 high-pressure metering pumps in sequence. Each metering pump continuously inputs its respective liquid material into the reaction kettle at a set flow rate. After the reaction kettle is filled with materials, it overflows from the top discharge valve of the kettle, and the pressure in the kettle is controlled by a proportional valve; when the pressure in the kettle reaches the set value of 3 - 8 MPa, open the organic solvent feed valve and the ethane feed valve, and the polymerization monomer is quantitatively and continuously input into the reaction kettle through a mass flow controller; all materials continuously overflow from the top discharge valve of the reaction kettle, are depressurized through a proportional valve, and continuously discharge from the product discharge port. After the system reaches a steady state, the temperature in the kettle is controlled at 130 - 200 °C, and the residence time of the materials in the reaction kettle is 10 - 30 min, preferably 16 - 25 min. The continuously flowing materials are washed several times with a large amount of acidified ethanol, filtered and drained, and vacuum dried at 120 - 150 °C for more than 3 - 5 h.

[0045] In the above technical solution, all the materials used are preferably treated to remove water, oxygen, and other harmful substances.

[0046] The present invention also provides a polymer elastomer prepared by the above preparation method. The weight-average molecular weight of the polymer elastomer is 3000 - 1500000 g / mol, and the molecular weight distribution index is 1.0 - 5.0.

[0047] Among them, the polymer elastomer includes, but is not limited to, any one or more of ethylene-α-olefin copolymer, propylene-based polymer elastomer, vinyl elastomer, or ethylene-propylene-diene monomer rubber.

[0048] In summary, the present invention discloses a preparation method of a polymer elastomer. In the polymerization process, a mixed solvent of ethane and an organic solvent is used to form a subcritical state in the polymerization reaction system, which not only reduces the viscosity of the polymerization system, but also improves the internal mass transfer and heat transfer production efficiency of the polymerization reactor. At the same time, it also improves the insertion rate and product performance of the product. In particular, when preparing the polymer elastomer, precise control of the polymer structure is achieved through adjustment of process parameters, and a polymer elastomer with a high polymer monomer content is obtained. In addition, compared with other solvent systems, the mixed solvent of ethane and an organic solvent (such as alkane) has lower supercritical and subcritical process conditions, making the polymerization conditions milder, with lower requirements for the process and equipment, and greatly reducing the production cost of the subcritical process. Since the reaction system is in a subcritical state and has a lower boiling point than the reaction solvent in the system without ethane, this process can also effectively reduce the energy consumption of solvent flash evaporation separation and recovery.

[0049] To further illustrate the present invention, the following examples are used for detailed description. The experimental raw materials used in the following examples of the present invention are all commercially available products.

[0050] Examples 1 - 7 are the results of continuous polymerization of the polymer elastomer in a subcritical state.

[0051] The feed molar concentration used in the present invention refers to the initial concentration of the monomer / copolymer in the solution in the reaction kettle when it enters the reaction kettle, and the feed molar concentration ratio refers to the initial molar concentration ratio of the comonomer to the monomer in the solution in the reaction kettle before the reaction.

[0052] Example 1

[0053] In this example, the main catalyst is a commercially available CGC catalyst, the co-catalyst is a modified methylaluminoxane, the mixed solvent is composed of an organic solvent and light component ethane mixed in proportion, the comonomers are ethylene and 1-butene, and the organic solvent can be n-hexane. Before the experiment, under nitrogen protection, the main catalyst and the co-catalyst are respectively formulated into solutions with the organic solvent, and the concentrations are both controlled at about 1.5%, stored in the feeding tank. The comonomers and the organic solvent are stored in their respective feeding tanks, and ethane needs to be stored in a steel cylinder at room temperature.

[0054] The specific steps are as follows: Preheat the reaction kettle and pipelines to 140 °C, start stirring, and set the rotation speed to 500 r / min; Open the bottom feed valve and the top discharge valve of the kettle, open the 4 high-pressure chemical metering pumps in sequence, and each metering pump continuously inputs the comonomers, the main catalyst solution, the co-catalyst solution, and the organic solvent into the reaction kettle at the set flow rate at the same time. After the materials fill the reaction kettle, they overflow from the top discharge valve of the kettle, and the pressure in the kettle is controlled by a proportional valve; When the pressure in the kettle reaches the set value of 4 MPa, open the ethylene feed valve and the ethane feed valve, and ethylene and ethane are quantitatively and continuously input into the reaction kettle through an ethylene mass flow controller. All the materials continuously overflow from the discharge valve at the top of the reaction kettle, and the pressure is relieved through the proportional valve, and the materials are continuously discharged from the product discharge port. After the system reaches a steady state, the flow rate of the organic solvent is about 4.047 kg / h, 1-butene is 1.375 kg / h, ethylene is 1.375 kg / h, ethane is 0.153 kg / h, the feeding amount of the main catalyst is 2.636 g / min, the feeding amount of the co-catalyst is 5 g / min, the molar concentration ratio of the co-catalyst to the main catalyst is 700, the feeding mass flow ratio of 1-butene to ethylene is 1, the temperature in the kettle is controlled at 150 °C and the pressure in the kettle is controlled at 4 MPa at steady state, and the residence time of the materials in the reaction kettle is 16 min. The continuously flowing materials are washed several times with a large amount of acidified ethanol, filtered and dried, and vacuum dried at 120 °C for more than 5 h to obtain a polymer elastomer. The experimental results are shown in Table 2.

[0055] In this example, the mass ratio of the organic solvent to ethane in the kettle is 26.45. All the materials used in this experiment have been treated to remove water, oxygen and other harmful substances.

[0056] The feeding composition and reaction state of this example are shown in Table 1.

[0057] The mass insertion rate and molar insertion rate of butene in the above polymer elastomer are determined by infrared method:

[0058] Mass insertion rate = mass of butene in the polymer elastomer molecular chain / (mass of butene + mass of ethylene);

[0059] Molar insertion rate = number of moles of butene in the polymer elastomer molecular chain / (number of moles of butene + number of moles of ethylene).

[0060] Melting point (Tm ) Measured by TA Instruments Q200, the method is as follows:

[0061] Take 5.0 - 7.0 mg of the polymer sample and heat it to 160 °C at a rate of 30 °C / min, hold for 5 min to eliminate the thermal history, then cool it to -90 °C at a rate of 10 °C / min, hold for another 3 min and then heat it to 160 °C at a rate of 10 °C / min. The melting point of the polymer elastomer is obtained from the second heating curve.

[0062] The molecular weight and molecular weight distribution index are measured by Gel Permeation Chromatography.

[0063] In this example, the test results of the butene insertion rate, molecular weight, and degree of polymerization of the polymer elastomer are shown in Table 2.

[0064] Example 2

[0065] Compared with Example 1, the difference is that the flow rate of the organic solvent is about 3.957 kg / h and the flow rate of ethane is about 0.243 kg / h, and other parameters and steps are the same as those in Example 1.

[0066] The feed composition and reaction status of this example are shown in Table 1.

[0067] In this example, the test methods for the butene insertion rate, molecular weight, and degree of polymerization of the polymer elastomer refer to Example 1, and the test results are shown in Table 2.

[0068] Example 3

[0069] Compared with Example 1, the difference is that the flow rate of the organic solvent is about 3.856 kg / h and the flow rate of ethane is about 0.344 kg / h, and other parameters and steps are the same as those in Example 1.

[0070] The feed composition and reaction status of this example are shown in Table 1.

[0071] In this example, the test methods for the butene insertion rate, molecular weight, and degree of polymerization of the polymer elastomer refer to Example 1, and the test results are shown in Table 2.

[0072] Example 4

[0073] Compared with Example 1, the difference is that the flow rate of the organic solvent is about 3.742 kg / h and the flow rate of ethane is about 0.458 kg / h, and other parameters and steps are the same as those in Example 1.

[0074] The feed composition and reaction status of this example are shown in Table 1.

[0075] In this embodiment, the test methods for the butene insertion rate, molecular weight, and degree of polymerization of the polymer elastomer refer to Example 1, and the test results are shown in Table 2.

[0076] Example 5

[0077] Compared with Example 1, the difference is that the flow rate of the organic solvent is about 4.000 kg / h and the flow rate of ethane is about 0.740 kg / h, and other parameters and steps are the same as those in Example 1.

[0078] The feed composition and reaction status of this embodiment are shown in Table 1.

[0079] In this embodiment, the test methods for the butene insertion rate, molecular weight, and degree of polymerization of the polymer elastomer refer to Example 1, and the test results are shown in Table 2.

[0080] Example 6

[0081] Compared with Example 1, the difference is that the flow rate of the organic solvent is about 4.000 kg / h and the flow rate of ethane is about 1.125 kg / h, and other parameters and steps are the same as those in Example 1.

[0082] The feed composition and reaction status of this embodiment are shown in Table 1.

[0083] In this embodiment, the test methods for the butene insertion rate, molecular weight, and degree of polymerization of the polymer elastomer refer to Example 1, and the test results are shown in Table 2.

[0084] Example 7

[0085] Compared with Example 1, the difference is that the flow rate of the organic solvent is about 4.000 kg / h and the flow rate of ethane is about 1.681 kg / h, and other parameters and steps are the same as those in Example 1.

[0086] The feed composition and reaction status of this embodiment are shown in Table 1.

[0087] In this embodiment, the test methods for the butene insertion rate, molecular weight, and degree of polymerization of the polymer elastomer refer to Example 1, and the test results are shown in Table 2.

[0088] Example 8

[0089] Compared with Example 1, the difference is that the organic solvent is changed to cyclopentane, the flow rate is about 4.000 kg / h, and the flow rate of ethane is about 1.681 kg / h, and other parameters and steps are the same as those in Example 1.

[0090] The feed composition and reaction status of this embodiment are shown in Table 1.

[0091] In this embodiment, the test methods for the butene insertion rate, molecular weight, and degree of polymerization of the polymer elastomer refer to Example 1, and the test results are shown in Table 2.

[0092] Example 9

[0093] Compared with Example 1, the difference is that the organic solvent is changed to toluene, the flow rate is about 4.000 kg / h, the ethane flow rate is about 1.681 kg / h, and the other parameters and steps are consistent with Example 1.

[0094] The feed composition and reaction state of this embodiment are shown in Table 1.

[0095] In this embodiment, the testing method of the butene insertion rate, molecular weight and degree of polymerization of the polymer elastomer is referred to Example 1, and the test results are shown in Table 2.

[0096] Table 1

[0097]

[0098]

[0099] Table 2

[0100]

[0101]

[0102] From the comparison of Examples 1 to 7 of the data in Table 2, it can be seen that as the proportion of ethane increases, the molar and mass insertion rates of the reactants increase year-on-year, achieving the purpose of controlling the insertion rate of the reactants by adjusting the ethane content, thereby indirectly adjusting the performance of the product and providing more options for product development and application.

[0103] From the comparison of Examples 8 to 9 with Examples 1 to 7 in the data of Table 2, it can be seen that after the organic solvent is replaced, the molar insertion rate and mass insertion rate of the reactants are low, which is not conducive to the normal progress of the polymerization reaction.

[0104] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a polymer elastomer by mixing ethane and higher alkanes in a subcritical state, characterized in that, It includes the following steps: After mixing the polymerization monomer, the main catalyst, the cocatalyst and the mixed solvent, a polymerization reaction occurs under subcritical conditions to obtain a polymer elastomer; The mixed solvent includes an organic solvent and a light component, and the light component includes any one or more of ethane, carbon dioxide or methane; The mass ratio of the organic solvent to the light component is (30 - 1):

1.

2. The preparation method according to claim 1, characterized in that, The organic solvent is selected from one or more of substituted or unsubstituted straight-chain alkanes with C3 - C12, substituted or unsubstituted isoalkanes with C3 - C12, substituted or unsubstituted cycloalkanes with C5 - C12, and substituted or unsubstituted aromatic hydrocarbons with C6 - C8.

3. The preparation method according to claim 2, characterized in that, The organic solvent is selected from any one or more of propane, n-butane, isobutane, cyclobutane, n-pentane, isopentane, neopentane, cyclopentane, n-hexane, cyclohexane, methylcyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, undecane, dodecane, toluene or xylene.

4. The preparation method according to any one of claims 1 to 3, characterized in that, The temperature of the polymerization reaction is 130 - 200 °C, and the pressure is 3 - 8 MPa; The mass ratio of the polymerization monomer, the main catalyst, the cocatalyst and the mixed solvent is (4 - 5):(2 - 3):1:(15 - 30).

5. The preparation method according to any one of claims 1 to 4, characterized in that, The polymerization reaction mode adopts any one of batch polymerization, semi-continuous polymerization or continuous polymerization; The polymerization reaction is carried out under anhydrous and anaerobic conditions; The reactor for the polymerization reaction is a tank reactor or a tubular reactor.

6. The preparation method according to any one of claims 1 to 5, characterized in that The main catalyst is a metallocene catalyst or a non-metallocene catalyst; The cocatalyst is selected from any one or more of methylaluminoxane compounds, modified methylaluminoxane compounds, tris(pentafluorophenyl)boron compounds, triphenylcarbenium tetrakis(pentafluorophenyl)borate compounds, N,N-dimethylaniline tetrakis(pentafluorophenyl)borate compounds, triisobutylaluminum or trimethylaluminum.

7. The preparation method according to any one of claims 1 to 6, characterized in that, The main catalyst is selected from any one or more of bis(indenyl)zirconium dichloride, bis(indenyl)dimethylzirconium, bis(cyclopentadienyl)dimethylhafnium, bis[2-(3',5'-di-tert-butylphenyl)-indenyl]zirconium dichloride, bis(2-methyl-4,5-phenyl-indenyl)zirconium dichloride, bis(cyclopentadienyl)-bis(phenoxy)zirconium, vinylidene-bridged bis(indenyl)zirconium dichloride, dimethylsilyl-bridged bis(indenyl)zirconium dichloride, diphenylcarbene-bridged-cyclopentadienyl-fluorenyl zirconium dichloride, diphenylcarbene-bridged-cyclopentadienyl-(2-dimethylamino-fluorenyl)zirconium dichloride, dimethylsilyl-bridged-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium, dimethylsilyl-bridged-3-pyrrolylindenyl-tert-butylamino-dimethyltitanium, pentamethylcyclopentadienyl-(2-phenylphenoxy)-titanium dichloride, pentamethylcyclopentadienyl-(2,6-diisopropylphenoxy)-titanium dichloride, bis(3-methylsalicylidene-pentafluorobenzylimino)titanium dichloride, bis(salicylidene-benzylimino)titanium dichloride, [N-(3,5-di-tert-butylsalicylidene)-2-diphenylphosphinophenylimino]titanium trichloride or (2,3,4-trihydro-8-diphenylphosphino-quinolyl)tribenzylzirconium.

8. The preparation method according to any one of claims 1 to 7, characterized in that, The polymerization monomer is selected from ethylene and α-olefins.

9. A polymer elastomer prepared by the preparation method according to any one of claims 1 to 7, characterized in that, The weight-average molecular weight of the polymer elastomer is 3,000 to 1,500,000 g / mol, and the molecular weight distribution index is 1.0 to 5.

0.

10. The polymer elastomer according to claim 9, wherein, The polymer elastomer includes, but is not limited to, any one or more of ethylene-α-olefin copolymers, propylene-based polymer elastomers, vinyl elastomers, or ethylene-propylene-diene rubbers.

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