Propylene / alpha-olefin copolymer elastomers containing a silicon-containing five-membered ring structural unit and methods for making the same

Abstract

The application discloses a propylene / alpha-olefin copolymer elastomer containing a silicon-containing five-membered ring structure unit and a preparation method thereof, and belongs to the technical field of polymer preparation. The propylene / alpha-olefin copolymer elastomer containing the silicon-containing five-membered ring structure unit is composed of 2-20 mol% of alpha-olefin structure units, 5-10 mol% of the silicon-containing five-membered ring structure units and the balance of propylene structure units. The propylene / alpha-olefin copolymer elastomer containing the silicon-containing five-membered ring structure unit has the characteristics of low glass transition temperature, high strength, good toughness and high elasticity, and the glass transition temperature is -20-10 DEG C, the weight average molecular weight is 150-300 kDa, the molecular weight distribution index is 1.1-3.3, the tensile strength is 7-25 MPa, the elongation at break is 1000-1600%, the toughness is 10-150 MJ m ‑3 , and the elastic recovery rate is 60-98%.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polymer preparation, in particular to a propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structure unit and a preparation method thereof. BACKGROUND

[0002] Polyolefin elastomer (POE) is a kind of ethylene-octene copolymer with an octene content of 20-30 mol%. The performance of POE mainly depends on the content of octene. With the increase of the content of octene, the tensile strength and hardness decrease, the elongation at break increases, and the elastic property is enhanced. With the decrease of the content of octene, the tensile strength and hardness increase, the elongation at break decreases, and the plasticity is enhanced. POE is widely used, which can be used as rubber, thermoplastic elastomer, plastic modifier and toughening agent. It can not only toughen and modify polyolefin plastics compatible with it, but also modify engineering plastics such as nylon and polyester incompatible with it. Compared with ethylene-propylene-diene rubber (EPDM), ethylene-propylene rubber (EPM) and SBS, POE has its unique advantages: 1. Excellent processing performance and mechanical properties. Commercial POE is in a free-flowing granular state, which is easier to mix with polymers. Although the Mooney viscosity is low, the mechanical properties can be comparable to high Mooney viscosity materials, eliminating the shortcomings of low Mooney viscosity, good processing performance and poor mechanical properties of general elastomers. 2. After crosslinking, the thermal aging resistance, ultraviolet light resistance and weather resistance are better than those of EPDM. 3. POE has low embrittlement temperature, and has the best toughening effect on PP, which can maintain high yield strength and flowability while toughening. When the content of comonomer is controlled within a certain range, in addition to ethylene-octene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer and other ethylene-olefin copolymers also exhibit elastomer properties, which are called generalized polyolefin elastomers.

[0003] However, the existing POE still has the problem of poor mechanical properties, especially poor tensile strength or elastic recovery rate. Moreover, the elastic recovery rate and the tensile strength show a trade-off relationship. Copolymers with low crystallinity have good elastic recovery rate, but usually have weak strength. Therefore, in the development of new polyolefin elastomers, achieving a good balance between elastic recovery and mechanical strength is a challenge. How to obtain polyolefin elastomers with good balance between elastic recovery and mechanical strength is the focus of research by those skilled in the art at this stage. SUMMARY

[0004] The purpose of the present application is to provide a propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structure unit and a preparation method thereof, in order to solve the problems existing in the prior art.

[0005] To achieve the above-mentioned purpose, the present application provides the following solutions:

[0006] One of the technical solutions of the present application: a propylene / alpha-olefin copolymer elastomer containing a silicon-containing five-membered ring structure unit, which is composed of 2-20 mol% of alpha-olefin structure units, 5-10 mol% of silicon-containing five-membered ring structure units, and the balance of propylene structure units;

[0007] The raw material of the silicon-containing five-membered ring structure unit includes one of allyl vinyl dimethyl silane, allyl vinyl diphenyl silane, and allyl vinyl methyl phenyl silane;

[0008] The raw material of the alpha-olefin structure unit includes one or more of 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

[0009] Further, the structural formula of the silicon-containing five-membered ring structure unit is (R1 and R2 are each independently selected from -CH3 or -Ph), the structural formula of the alpha-olefin structure unit is (N is selected from 7, 9, 11, 13, 15, and 17, corresponding to the alpha-olefin species), and the structural formula of the propylene structure unit is

[0010] The present application improves the mechanical properties of the polymer by introducing a silicon-containing rigid cyclic structure unit and a long chain branch into the copolymer backbone. First, the introduction of long-chain alpha-olefins can reduce the crystallinity of the polymer, effectively improving its toughness and elastic recovery performance, and the introduction of cyclic structures can make the copolymer maintain good mechanical strength. Through the synergistic cooperation of long-chain alpha-olefins and cyclic structures, a copolymer elastomer with relatively good mechanical strength and elastic recovery rate can be obtained.

[0011] The reason why the present application chooses to introduce a silicon-containing five-membered ring structure unit instead of a four-membered ring structure unit or a six-membered ring structure unit is that the four-membered ring has too much ring tension and cannot be synthesized, and the six-membered ring is too large to be fully cyclized and may have a pendant double bond, which is prone to crosslinking and affects the mechanical properties of the material.

[0012] Further, the weight average molecular weight (M w ) of the propylene / alpha-olefin copolymer elastomer containing the silicon-containing five-membered ring structure unit is 150-300 kDa, and the molecular weight distribution index (M w / M n ) is 1.1-3.3.

[0013] The second technical solution of the present application: a preparation method of the above-mentioned propylene / alpha-olefin copolymer elastomer containing a silicon-containing five-membered ring structure unit, which comprises the following steps:

[0014] The propylene / α-olefin copolymer elastomer containing the silicon-containing five-membered ring structure unit is obtained by random copolymerization of propylene, an α-olefin and a silicon-containing α,ω-diene under the action of a catalyst, a cocatalyst and a chain transfer agent;

[0015] The silicon-containing α,ω-diene includes one of allyl vinyl dimethyl silane, allyl vinyl diphenyl silane, diallyl dimethyl silane, diallyl methyl phenyl silane and diallyl diphenyl silane.

[0016] The α-olefin includes one or more of 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

[0017] Preferably, the α-olefin is 1-hexadecene and / or 1-octadecene.

[0018] Preferably, the silicon-containing α,ω-diene is allyl vinyl dimethyl silane.

[0019] Further, the catalyst includes a pyridyl amine hafnium metal catalyst.

[0020] Further, the cocatalyst includes an organic boron salt.

[0021] Further, the chain transfer agent includes triisobutyl aluminum.

[0022] Further, the random copolymerization is performed in a hydrocarbon compound solvent.

[0023] Optionally, the hydrocarbon compound solvent includes one or more of benzene and its homologues, naphthalene and its homologues, alkane and its homologues and cycloalkane and its homologues.

[0024] Preferably, the hydrocarbon compound solvent is toluene.

[0025] Further, the molar ratio of the catalyst to the chain transfer agent is 1:5-500.

[0026] Further, the molar ratio of the catalyst to the silicon-containing α,ω-diene is 1:500-2000.

[0027] Further, the molar ratio of the α-olefin to the silicon-containing α,ω-diene is 1:0.1-10.

[0028] Further, the molar ratio of the catalyst to the cocatalyst is 1:1-3000.

[0029] Further, the random copolymerization reaction of propylene, alpha-olefin and silicon-containing alpha, omega-diene as reaction monomers in the presence of a catalyst, a cocatalyst and a chain transfer agent to obtain the propylene / alpha-olefin copolymer elastomer containing the silicon-containing five-membered ring structure unit comprises:

[0030] First, the silicon-containing alpha, omega-diene, alpha-olefin, chain transfer agent and hydrocarbon compound solvent are mixed, then propylene gas is introduced, and the catalyst and cocatalyst are added to perform the random copolymerization reaction (propylene gas is continuously introduced until the random copolymerization reaction is completed).

[0031] Further, the random copolymerization reaction is performed for 2-30 min.

[0032] Further, after the random copolymerization reaction is performed for 2-30 min, the steps of adding ethanol to terminate the random copolymerization reaction to obtain a reaction liquid, mixing the reaction liquid with a precipitant, performing sedimentation, and then filtering, washing and vacuum drying are further included.

[0033] Further, the precipitant comprises a mixed solution of ethanol and hydrochloric acid.

[0034] Alternatively, the precipitant is prepared by mixing ethanol and hydrochloric acid with a concentration of 37 wt% at a volume ratio of 100:1.

[0035] The third technical solution of the present application is the use of the propylene / alpha-olefin copolymer elastomer containing the silicon-containing five-membered ring structure unit in the preparation of an elastic shoe sole, a bouncy ball toy, a car sealing strip or an elastic swimsuit.

[0036] The present application utilizes the copolymerization of the silicon-containing alpha, omega-diene and alpha-olefin with propylene to obtain a polyolefin elastomer with a polymer backbone containing a silicon ring rigid cyclic unit and a long side chain, and realizes the preparation of a novel polyolefin elastomer containing a silicon-containing five-membered ring structure unit in the main chain. By controlling the types and contents of the comonomers, the mechanical properties and thermal properties of the copolymer can be adjusted. High-temperature nuclear magnetic resonance carbon spectrum and hydrogen spectrum are used to characterize the micro-chemical structure of the copolymer, high-temperature GPC is used to determine the molecular weight and its distribution of the copolymer, DSC is used to study the thermal behavior of the copolymer, and a universal testing machine is used to test the mechanical properties of the copolymer.

[0037] The present application uses a pyridine amine hafnium metal catalyst and a boron-containing compound cocatalyst to form a catalyst system, and combines an alkyl aluminum chain transfer agent to synthesize a series of propylene / alpha-olefin random copolymer elastomers containing a silicon-containing five-membered ring structure unit in the main chain with controllable thermodynamic properties and mechanical properties by adjusting the types and contents of the comonomers. First, according to the certain degree of copolymerization ability of the catalyst for the silicon-containing alpha, omega-diene and alpha-olefin and propylene, the effects of monomer concentration and monomer type on the composition and properties of the polymer, and the effects of comonomer content on the microstructure are systematically studied to realize efficient regulation and control of the mechanical properties of the elastomer.13 C NMR and 1 The H NMR results show that the introduction of the silicon-containing alpha, omega-diene in the copolymer only forms a cyclic structure unit without branched structure or cross-linked structure on the ring (i.e. the silicon-containing alpha, omega-diene is only inserted in a cyclic manner without branched structure). Through uniaxial stretching and stepwise cyclic stretching tests, it is found that the introduction of the silicon-containing cyclic structure unit improves the mechanical properties of the material. In addition, the mechanical properties of all the elastomers can be optimized by changing the content of the comonomer and the length of the side chain, respectively, and the elastomers with high strength and high elastic recovery can be obtained. Therefore, the monomer type and the insertion rate play a crucial role in determining the mechanical properties of the excellent elastomers.

[0038] The application provides a propylene / alpha-olefin copolymer elastomer containing a silicon-containing five-membered ring structure unit, the weight average molecular weight of the copolymer elastomer is 150-300 kDa, the PDI is 1.1-3.3, the copolymerization activity is 1-10 kg polymer mmol -1 h -1 , the breaking strength is 7-25 MPa, the breaking elongation is 1000-1600%, the toughness is 10-150 MJ m -3 , and the elastic recovery rate is 60-98%.

[0039] At present, there is little research on the controllable copolymerization of the silicon-containing diene and other olefins. In the prior art, the silicon-containing polyolefin is synthesized through anionic ring-opening polymerization, condensation polymerization and coupling reaction, but the molecular weight of the polymer obtained through the above methods is relatively low, and the structure of the polymer is not clear. Therefore, the application takes the controllable polymerization of the silicon-containing diene and other olefins as the starting point, prepares the elastomer with a main chain containing a silicon-containing ring structure and a long side chain structure by optimizing the polymerization conditions, and thus the development of the high-performance polyolefin elastomer is promoted.

[0040] The application discloses the following technical effects:

[0041] The application improves the mechanical properties of the polymer by introducing the silicon-containing rigid cyclic structure unit and the long branch on the copolymer skeleton. The glass transition temperature of the propylene / alpha-olefin copolymer elastomer containing the silicon-containing five-membered ring structure unit is -20-10 DEG C, the tensile strength is 7-25 MPa, the breaking elongation is 1000-1600%, the toughness is 10-150 MJ m -3 , and the elastic recovery rate is 60-98%, so that the balance between the strength and the elasticity is realized.

[0042] The application uses a silicon-containing alpha, omega-diene, an alpha-olefin and propylene as reaction monomers, a pyridylamine hafnium metal catalyst and a boron-containing compound cocatalyst to form a catalytic system, and combines an alkyl aluminum chain transfer agent to copolymerize a polyolefin elastomer with a silicon-containing rigid cyclic unit and a long side chain by optimizing polymerization conditions, so as to realize the controllable synthesis of a main chain silicon-containing ring elastomer. BRIEF DESCRIPTION OF DRAWINGS

[0043] In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the drawings needed in the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative effort on the basis of these drawings.

[0044] Figure 1 The GPC curve of the copolymer elastomer prepared in Example 1. 13 C NMR spectrum.

[0045] Figure 2 The GPC curve of the copolymer elastomer prepared in Example 1. 1 H NMR spectrum.

[0046] Figure 3 The GPC curve of the copolymer elastomer prepared in Examples 1-3.

[0047] Figure 4 The DSC curve of the copolymer elastomer prepared in Example 1.

[0048] Figure 5 The stress-strain curve of the copolymer elastomer prepared in Example 2.

[0049] Figure 6 The stress-strain cycle curve of the copolymer elastomer prepared in Example 2.

[0050] Figure 7 The stress-strain cycle curve of the copolymer elastomer prepared in Example 3.

[0051] Figure 8 The stress-strain curve of the copolymer elastomer prepared in Comparative Example 2.

[0052] Figure 9 The stress-strain cycle curve of the copolymer elastomer prepared in Comparative Example 2. DETAILED DESCRIPTION

[0053] The present application will now be described in detail by way of various exemplary embodiments thereof, which should not be construed as restricting the present application but being rather illustrative of certain aspects, features and embodiments thereof.

[0054] It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. Additionally, for a range of values of a parameter, unless otherwise stated, each intervening value of the parameter, as well as any other stated or intervening value of the parameter, is encompassed. The intervening values of the parameter are obtained by simply "slicing" or interpolating the range of values of the parameter disclosed. In each instance, the upper and lower limits of these intervening values are also contemplated, as are intensifying values of or intervening ranges between any stated value or intervening value of the parameter. The upper and lower limits and any intervening value of the parameter can independently comprise the maximum and minimum limits of the range, or independently exclude the maximum and minimum limits of the range.

[0055] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice of the present application. All documents mentioned herein are incorporated by reference to disclose and describe the methods and / or materials in connection with which the documents are cited. In case of conflict between the present specification and any document incorporated by reference, the present specification will control.

[0056] Various modifications and changes can be made to the specific embodiments of the present application described herein without departing from the scope or spirit of the application. Other embodiments of the application will be apparent to those of ordinary skill in the art from the description and examples presented herein. The description and examples are illustrative of the application and are not intended to limit the scope of the application.

[0057] As used herein, the terms "comprises", "comprising", "includes", "including", "has", "having" or variants thereof are open-ended, and specifically do not exclude additional, unrecited elements or method steps.

[0058] It should be noted that any parts of the present application not specifically described are conventional in the art and are not a focus of the present application.

[0059] As a first aspect of the present application, the present application provides a propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structure unit, which consists of 2 to 20 mol% of an α-olefin structure unit, 5 to 10 mol% of a silicon-containing five-membered ring structure unit, and a balance of a propylene structure unit;

[0060] The raw material of the silicon-containing five-membered ring structure unit includes one of allyl vinyl dimethyl silane, allyl vinyl diphenyl silane, and allyl vinyl methyl phenyl silane;

[0061] The raw material of the α-olefin structural unit includes one or more of 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

[0062] As an embodiment of the present application, the propylene / α-olefin copolymer elastomer containing the silicon-containing five-membered ring structural unit is a random copolymer, and the structural formula can be represented as

[0063] wherein x is 0.05-0.10 (i.e. the content of the silicon-containing five-membered ring structural unit in the propylene / α-olefin copolymer elastomer containing the silicon-containing five-membered ring structural unit is 5-10 mol%), y is 0.02-0.20 (i.e. the content of the α-olefin structural unit in the propylene / α-olefin copolymer elastomer containing the silicon-containing five-membered ring structural unit is 2-20 mol%), N is selected from 5, 7, 9, 11, 13, 15 and 17 (corresponding to the type of α-olefin), and R1 and R2 are each independently selected from -CH3 or -Ph (phenyl).

[0064] If polypropylene is taken as the original polymer matrix, the present application is equivalent to introducing a silicon-containing rigid ring structure unit and a long chain branch into the polypropylene skeleton, and through the synergistic cooperation of the long-chain α-olefin and the ring structure (the cooperation of the types and insertion rates of the two), a copolymer elastomer with relatively good mechanical strength and elasticity is obtained, and a good balance between the mechanical strength (i.e. the breaking strength) and the elastic recovery rate is achieved. Isotactic polypropylene generally has a high crystallinity, and the crystallization can provide strength as a physical crosslinking point, so isotactic polypropylene has high strength but no elasticity. The insertion of the comonomer will destroy the crystallization of polypropylene, thereby reducing the mechanical strength of the material and improving the elastic recovery of the material. The POE such as ethylene-octene copolymer is equivalent to inserting a comonomer into the high-crystallinity polymer matrix such as polyethylene or polypropylene to reduce the strength of the original polymer and improve the elastic recovery. However, the existing technology can only achieve a limited improvement in the elastic recovery, and the limited improvement in the elastic recovery is often accompanied by a significant decrease in the mechanical strength, and a good balance between the mechanical strength and the elastic recovery cannot be achieved. Through the technical solution of the present application, the mechanical strength is ensured not to decrease significantly while the elastic recovery is greatly improved, and a good balance between the mechanical strength and the elastic recovery is achieved, which has obvious advantages over the existing technology.

[0065] As a preferred embodiment of the present application, the weight average molecular weight (M w ) of the propylene / α-olefin copolymer elastomer containing the silicon-containing five-membered ring structural unit is 150-300 kDa, and the molecular weight distribution index (M w / M n ) is 1.1-3.3.

[0066] As a second aspect of the present application, the present application provides a method for preparing the propylene / α-olefin copolymer elastomer containing the silicon-containing five-membered ring structure unit as described above, comprising the following steps:

[0067] carrying out random copolymerization reaction under the action of a catalyst, a cocatalyst and a chain transfer agent, to obtain the propylene / α-olefin copolymer elastomer containing the silicon-containing five-membered ring structure unit;

[0068] The silicon-containing α,ω-diene includes one of allyl vinyl dimethyl silane, allyl vinyl diphenyl silane and allyl methyl phenyl silane.

[0069] The α-olefin includes one or more of 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

[0070] As a preferred embodiment of the present application, the method for preparing further comprises the following more specific steps:

[0071] The silicon-containing α,ω-diene, the α-olefin, the chain transfer agent and the hydrocarbon compound solvent are mixed first, then propylene gas is introduced (the pressure of the propylene gas in the reaction container is 0.1 MPa, and the propylene gas is continuously introduced until the end of the polymerization reaction), and the catalyst and the cocatalyst are added, to carry out random copolymerization reaction, and after 2-30 min, ethanol is added to terminate the polymerization reaction, to obtain a reaction liquid;

[0072] The reaction liquid is mixed with a precipitator, and then is subjected to settlement, filtration, washing and vacuum drying, to obtain the propylene / α-olefin copolymer elastomer containing the silicon-containing five-membered ring structure unit.

[0073] As a preferred embodiment of the present application, the catalyst and the cocatalyst are added in the form of a mixed solution of catalyst / cocatalyst / hydrocarbon compound solvent.

[0074] As a preferred embodiment of the present application, the α-olefin is 1-hexadecene and / or 1-octadecene.

[0075] As a preferred embodiment of the present application, the silicon-containing α,ω-diene is allyl vinyl dimethyl silane.

[0076] As a preferred embodiment of the present application, the catalyst includes a pyridyl amine hafnium metal catalyst.

[0077] As a preferred embodiment of the present application, the cocatalyst includes an organic boron salt.

[0078] As a preferred embodiment of the present application, the chain transfer agent includes triisobutyl aluminum.

[0079] As a preferred embodiment of the present application, the random copolymerization reaction is carried out in a hydrocarbon compound solvent.

[0080] As a preferred embodiment of the present application, the hydrocarbon compound solvent includes one or more of benzene and its homologues, naphthalene and its homologues, alkane and its homologues, and cycloalkane and its homologues.

[0081] As a preferred embodiment of the present application, the hydrocarbon compound solvent is toluene.

[0082] As a preferred embodiment of the present application, the molar ratio of the catalyst to the chain transfer agent is 1:5-500.

[0083] As a preferred embodiment of the present application, the molar ratio of the catalyst to the silicon-containing α,ω-diene is 1:500-2000.

[0084] As a preferred embodiment of the present application, the molar ratio of the α-olefin to the silicon-containing α,ω-diene is 1:0.1-10.

[0085] As a preferred embodiment of the present application, the molar ratio of the catalyst to the cocatalyst is 1:1-3000.

[0086] As a preferred embodiment of the present application, the precipitant includes a mixed solution of ethanol and hydrochloric acid.

[0087] As a preferred embodiment of the present application, the precipitant is formed by mixing ethanol and hydrochloric acid with a concentration of 37wt% at a volume ratio of 100:1.

[0088] As a preferred embodiment of the present application, the activity of the random copolymerization reaction is 1-10 kg polymer mmol - 1 h -1 .

[0089] As a preferred embodiment of the present application, the propylene / α-olefin copolymer elastomer containing the silicon-containing five-membered ring structural unit has the following properties: T g = -20-10℃, tensile strength of 7-25 MPa, elongation at break of 1000-1600%, toughness of 10-150 MJm -3 , and elastic recovery rate of 60-98%.

[0090] As a third aspect of the present application, the present application provides a use of the propylene / α-olefin copolymer elastomer containing the silicon-containing five-membered ring structural unit in the preparation of an elastic shoe sole, a bouncy ball toy, a car sealing strip, or an elastic swimsuit.

[0091] The structure information of the main raw materials involved in the specific embodiments of the present application is shown in Table 1.

[0092] Table 1

[0093]

[0094] The technical solutions of the present application are further described below in combination with specific embodiments.

[0095] Each raw material used in the following examples and comparative examples is a common commercially available product, except for the special description, wherein the organoboron salt is [Ph3C][B(C6F5)4].

[0096] The pyridyl amido hafnium metal catalyst used in the following examples and comparative examples is synthesized according to the prior art (Angewandte Chemie 2006, 45(20), 3278-3283), and the structural formula is The silicon-containing α,ω-diene is synthesized according to the prior art (Macromolecules 2014, 47, 6627-6634).

[0097] In the process of synthesizing the catalyst, the operations involved, except for the special description, are performed by the professionals familiar with the technical field in the MBraun glove box or using the standard Schlenk technique under the protection of inert gas such as nitrogen or argon, and the solvents involved in the present application are all anhydrous and oxygen-free solvents after post-treatment. In addition, in the process of preparing the propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit, all the polymerization reactions need to be carried out under anhydrous and oxygen-free conditions, the glassware involved in the preparation steps, such as ampoules, syringes, polymerization bottles, etc., for weighing and transferring catalysts, co-catalysts, chain transfer agents, solvents, etc., are all treated with anhydrous and oxygen-free, and all the operations sensitive to moisture and oxygen are performed by the professionals familiar with the technical field in the MBraun glove box or using the standard Schlenk technique under the protection of nitrogen. The steps without specific description of the operation temperature or the reaction temperature are all carried out at room temperature (20-30℃).

[0098] Example 1

[0099] A propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit, the preparation steps are as follows:

[0100] A Schlenk experimental device was used, and 60 mL of toluene, 0.7 mL of allylvinyl dimethyl silane, 2 mL of 1-hexadecene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) were sequentially added to a polymerization bottle under a vacuum of -0.1 MPa. Then, propylene gas was introduced (the pressure of the propylene gas in the polymerization bottle was 0.1 MPa, and the introduction of the propylene gas was continued until the end of the reaction, and the same was true below) at 600 rpm for 10 min. Then, 16.8 mL of a mixed solution of the hafnium metal catalyst of pyridylamine, the organoboron salt, and toluene (i.e., a mixed solution of the hafnium metal catalyst of pyridylamine, the organoboron salt, and toluene, which contained 10 μmol of the hafnium metal catalyst of pyridylamine and 20 μmol of the organoboron salt) was added, and the reaction was stirred at 600 rpm for 10 min. After the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization, and a reaction solution was obtained. Finally, the reaction solution was dropped into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio of 100:1) to be precipitated, and then the copolymer elastomer was obtained by filtration, washing, and vacuum drying.

[0101] Example 2

[0102] A propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit was prepared by the following steps:

[0103] A Schlenk experimental device was used, and 60 mL of toluene, 0.7 mL of allylvinyl dimethyl silane, 2 mL of 1-hexadecene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) were sequentially added to a polymerization bottle under a vacuum of -0.1 MPa. Then, propylene gas was introduced (the pressure of the propylene gas in the polymerization bottle was 0.1 MPa, and the introduction of the propylene gas was continued until the end of the reaction, and the same was true below) at 600 rpm for 10 min. Then, 16.8 mL of a mixed solution of the hafnium metal catalyst of pyridylamine, the organoboron salt, and toluene (i.e., a mixed solution of the hafnium metal catalyst of pyridylamine, the organoboron salt, and toluene, which contained 10 μmol of the hafnium metal catalyst of pyridylamine and 20 μmol of the organoboron salt) was added, and the reaction was stirred at 600 rpm for 10 min. After the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization, and a reaction solution was obtained. Finally, the reaction solution was dropped into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio of 100:1) to be precipitated, and then the copolymer elastomer was obtained by filtration, washing, and vacuum drying.

[0104] Example 3

[0105] A propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit was prepared by the following steps:

[0106] A Schlenk experimental device was used, and 60 mL of toluene, 0.7 mL of allylvinyl dimethyl silane, 4 mL of 1-hexadecene, 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL), and then propylene gas (0.1 MPa) were sequentially added to a polymerization bottle under a vacuum of -0.1 MPa, stirred at 600 rpm for 10 min, and then 14.8 mL of a mixed solution of a pyridylamine hafnium metal catalyst / organoboron salt / toluene (containing 10 μmol of the pyridylamine hafnium metal catalyst and 20 μmol of the organoboron salt) was added, and the reaction was stirred at 600 rpm for 10 min. After the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization, and a reaction solution was obtained. Finally, the reaction solution was dropped into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) to precipitate, and then a copolymer elastomer was obtained by filtration, washing, and vacuum drying.

[0107] Example 4

[0108] A propylene / α-olefin copolymer elastomer containing a silicon five-membered ring structural unit was prepared by the following steps:

[0109] A Schlenk experimental device was used, and 60 mL of toluene, 0.7 mL of allylvinyl dimethyl silane, 4 mL of 1-hexadecene, 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL), and then propylene gas (0.1 MPa) were sequentially added to a polymerization bottle under a vacuum of -0.1 MPa, stirred at 600 rpm for 10 min, and then 14.8 mL of a mixed solution of a pyridylamine hafnium metal catalyst / organoboron salt / toluene (containing 10 μmol of the pyridylamine hafnium metal catalyst and 20 μmol of the organoboron salt) was added, and the reaction was stirred at 600 rpm for 10 min. After the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization, and a reaction solution was obtained. Finally, the reaction solution was dropped into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) to precipitate, and then a copolymer elastomer was obtained by filtration, washing, and vacuum drying.

[0110] Example 5

[0111] A propylene / α-olefin copolymer elastomer containing a silicon five-membered ring structural unit was prepared by the following steps:

[0112] A Schlenk experimental device was used, and 60 mL of toluene, 0.7 mL of allylvinylphenylsilane, 2 mL of 1-decene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) were sequentially added to a polymerization bottle under a vacuum of -0.1 MPa. Then, propylene gas (0.1 MPa) was introduced, and the mixture was stirred at 600 rpm for 10 min. Then, 16.8 mL of a mixed solution of a pyridylamine hafnium metal catalyst / organoboron salt / toluene (containing 10 μmol of the pyridylamine hafnium metal catalyst and 20 μmol of the organoboron salt) was added, and the mixture was stirred at 600 rpm for 10 min. After the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization, and a reaction solution was obtained. Finally, the reaction solution was dropped into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio of 100:1) to precipitate, and then the copolymer elastomer was obtained by filtration, washing, and vacuum drying.

[0113] Example 6

[0114] A propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit was prepared by the following steps:

[0115] A Schlenk experimental device was used, and 60 mL of toluene, 0.7 mL of allylvinylphenylsilane, 2 mL of 1-decene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) were sequentially added to a polymerization bottle under a vacuum of -0.1 MPa. Then, propylene gas (0.1 MPa) was introduced, and the mixture was stirred at 600 rpm for 10 min. Then, 16.8 mL of a mixed solution of a pyridylamine hafnium metal catalyst / organoboron salt / toluene (containing 10 μmol of the pyridylamine hafnium metal catalyst and 20 μmol of the organoboron salt) was added, and the mixture was stirred at 600 rpm for 10 min. After the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization, and a reaction solution was obtained. Finally, the reaction solution was dropped into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio of 100:1) to precipitate, and then the copolymer elastomer was obtained by filtration, washing, and vacuum drying.

[0116] Example 7

[0117] A propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit was prepared by the following steps:

[0118] A Schlenk experimental device was used, and 60 mL of toluene, 0.7 mL of allylvinylmethylphenylsilane, 2 mL of 1-octadecene, 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL), and then propylene gas (0.1 MPa) were sequentially added to a polymerization bottle under a vacuum of -0.1 MPa, stirred at 600 rpm for 10 min, and then 16.8 mL of a mixed solution of a pyridylamine hafnium metal catalyst / organoboron salt / toluene (containing 10 μmol of the pyridylamine hafnium metal catalyst and 20 μmol of the organoboron salt) was added, and the reaction was stirred at 600 rpm for 10 min. After the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization, and a reaction solution was obtained. Finally, the reaction solution was dropped into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) to precipitate, and then a copolymer elastomer was obtained by filtration, washing, and vacuum drying.

[0119] Example 8

[0120] A propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit was prepared by the following steps:

[0121] A Schlenk experimental device was used, and 60 mL of toluene, 0.7 mL of allylvinylmethylphenylsilane, 2 mL of 1-octadecene, 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL), and then propylene gas (0.1 MPa) were sequentially added to a polymerization bottle under a vacuum of -0.1 MPa, stirred at 600 rpm for 10 min, and then 16.8 mL of a mixed solution of a pyridylamine hafnium metal catalyst / organoboron salt / toluene (containing 10 μmol of the pyridylamine hafnium metal catalyst and 20 μmol of the organoboron salt) was added, and the reaction was stirred at 600 rpm for 10 min. After the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization, and a reaction solution was obtained. Finally, the reaction solution was dropped into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) to precipitate, and then a copolymer elastomer was obtained by filtration, washing, and vacuum drying.

[0122] Example 9

[0123] A propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit was prepared by the following steps:

[0124] A Schlenk experimental device was used, and 60 mL of toluene, 0.5 mL of allylvinyl diphenyl silane, 0.5 mL of 1-octadecene, 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL), and then propylene gas (0.1 MPa) were sequentially added to a polymerization bottle under a vacuum of -0.1 MPa, stirred at 600 rpm for 10 min, and then 18.5 mL of a mixed solution of a pyridylamine hafnium metal catalyst / organoboron salt / toluene (containing 10 μmol of the pyridylamine hafnium metal catalyst and 20 μmol of the organoboron salt) was added, and the reaction was stirred at 600 rpm for 10 min. After the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization, and a reaction solution was obtained. Finally, the reaction solution was dropped into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) to precipitate, and then a copolymer elastomer was obtained by filtration, washing, and vacuum drying.

[0125] Example 10

[0126] A propylene / α-olefin copolymer elastomer containing a silicon five-membered ring structural unit was prepared by the following steps:

[0127] A Schlenk experimental device was used, and 60 mL of toluene, 1.5 mL of allylvinyl diphenyl silane, 0.5 mL of 1-octadecene, 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL), and then propylene gas (0.1 MPa) were sequentially added to a polymerization bottle under a vacuum of -0.1 MPa, stirred at 600 rpm for 10 min, and then 17.5 mL of a mixed solution of a pyridylamine hafnium metal catalyst / organoboron salt / toluene (containing 10 μmol of the pyridylamine hafnium metal catalyst and 20 μmol of the organoboron salt) was added, and the reaction was stirred at 600 rpm for 10 min. After the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization, and a reaction solution was obtained. Finally, the reaction solution was dropped into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) to precipitate, and then a copolymer elastomer was obtained by filtration, washing, and vacuum drying.

[0128] Example 11

[0129] A propylene / α-olefin copolymer elastomer containing a silicon five-membered ring structural unit was prepared by the following steps:

[0130] A Schlenk experimental device was used, and 60 mL of toluene, 1.5 mL of allylvinyl dimethyl silane, 0.5 mL of 1-decene, 0.5 mL of 1-hexadecene, 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL), and then propylene gas (0.1 MPa) were sequentially added to a polymerization bottle under a vacuum of -0.1 MPa, stirred at 600 rpm for 10 min, and then 17.0 mL of a mixed solution of a pyridylamine hafnium metal catalyst / organoboron salt / toluene (containing 10 μmol of the pyridylamine hafnium metal catalyst and 20 μmol of the organoboron salt) was added, and the reaction was stirred at 600 rpm for 10 min. After the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization, and a reaction solution was obtained. Finally, the reaction solution was dropped into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) to be precipitated, and then a copolymer elastomer was obtained through filtration, washing, and vacuum drying.

[0131] Example 12

[0132] A propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit was prepared according to the following steps:

[0133] A Schlenk experimental device was used, and 60 mL of toluene, 1.5 mL of allylvinyl dimethyl silane, 0.5 mL of 1-decene, 0.5 mL of 1-hexadecene, 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL), and then propylene gas (0.1 MPa) were sequentially added to a polymerization bottle under a vacuum of -0.1 MPa, stirred at 600 rpm for 10 min, and then 17.0 mL of a mixed solution of a pyridylamine hafnium metal catalyst / organoboron salt / toluene (containing 10 μmol of the pyridylamine hafnium metal catalyst and 20 μmol of the organoboron salt) was added, and the reaction was stirred at 600 rpm for 10 min. After the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization, and a reaction solution was obtained. Finally, the reaction solution was dropped into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) to be precipitated, and then a copolymer elastomer was obtained through filtration, washing, and vacuum drying.

[0134] Comparative Example 1

[0135] A propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit was prepared according to the following steps:

[0136] A Schlenk experimental device was used, and 60 mL of toluene, 2.0 mL of diallyldimethylsilane, 2 mL of 1-hexadecene, 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL), and then propylene gas (0.1 MPa) were sequentially added to a polymerization bottle under a vacuum of -0.1 MPa. The mixture was stirred at 600 rpm for 10 min, and then 15.5 mL of a mixed solution of a hafnium amido complex catalyst / organoboron salt / toluene (containing 10 μmol of the hafnium amido complex catalyst and 20 μmol of the organoboron salt) was added. The mixture was stirred at 600 rpm for 10 min. After the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization, and a reaction solution was obtained. Finally, the reaction solution was dropped into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio of 100:1) to precipitate, and then the copolymer elastomer was obtained by filtration, washing, and vacuum drying.

[0137] Comparative Example 2

[0138] An α-olefin / propylene copolymer elastomer containing a silicon-containing five-membered ring structural unit was prepared according to the following steps:

[0139] A Schlenk experimental device was used, and 60 mL of toluene, 2.0 mL of diallyldimethylsilane, 2 mL of 1-hexadecene, 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL), and then propylene gas (0.1 MPa) were sequentially added to a polymerization bottle under a vacuum of -0.1 MPa. The mixture was stirred at 600 rpm for 10 min, and then 15.5 mL of a mixed solution of a hafnium amido complex catalyst / organoboron salt / toluene (containing 10 μmol of the hafnium amido complex catalyst and 20 μmol of the organoboron salt) was added. The mixture was stirred at 600 rpm for 10 min. After the polymerization was completed, 0.1 mL of ethanol was injected to terminate the polymerization, and a reaction solution was obtained. Finally, the reaction solution was dropped into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio of 100:1) to precipitate, and then the copolymer elastomer was obtained by filtration, washing, and vacuum drying.

[0140] Test Example

[0141] The copolymer elastomers obtained in Examples 1-12 and the copolymer elastomers obtained in Comparative Examples 1-2 were tested for relevant properties. Nuclear magnetic resonance spectroscopy (NMR) was used to characterize the chemical structure of the copolymer elastomers. The molar content of the α-olefin structural unit and the silicon-containing five-membered ring structural unit (i.e., the insertion rate of the α-olefin and the silicon-containing α,ω-diene) was obtained by nuclear magnetic carbon spectroscopy. Differential scanning calorimetry (DSC) was used to characterize the thermal properties of the copolymer elastomers. Gel permeation chromatography (GPC) was used to characterize the molecular weight (weight average molecular weight M w ) and the molecular weight distribution (PDI) of the copolymer elastomers. The results are shown in Table 1.1 H and 13 C10 NMR was measured by a Bruker-400 NMR spectrometer at 110 °C, with TMS as an internal standard and deuterated o-dichlorobenzene or deuterated 1,1,2,2-tetrachloroethane as the solvent. The glass transition temperature (Tg) of the copolymer elastomer was determined. g The temperature was measured using a differential scanning calorimeter (Q2000DSC) under nitrogen atmosphere conditions, with a heating / cooling rate of 20℃ / min. The copolymer melt temperature (Tm) of the copolymer elastomer was determined. m The results were measured using a differential scanning calorimeter (Q2000 DSC) under nitrogen atmosphere at a heating / cooling rate of 10 °C / min. Gel permeation chromatography was performed using a PL GPC-220 gel permeation chromatograph. The instrument was an RI-Laser, with PLEasiCal PS-1 as the standard, a Plgel 10 μm MIXED-BLS column, and 1,2,4-trichlorobenzene (TCB) as the solvent (with 0.05 wt% 2,6-di-tert-butyl-4-methylphenol (BHT) added as an antioxidant). The test temperature was 150 °C, and the flow rate was 1.0 mL / min. The copolymer elastomer was subjected to uniaxial tensile testing and stepped cyclic tensile testing (elongation at 100%, 200%, 300%, 400%, 500%, 600%, 700%, 800%, 900%, and 1000%). The mechanical properties of the copolymer were determined at room temperature using a universal testing machine (SANS, CMT4203Ins). Polymer films were prepared by hot pressing with a tetrafluoroethylene template (temperature 180℃, pressure 8MPa, time 3min), and then cut into dumbbell-shaped tensile strips with effective dimensions of 10×2×0.5mm. 3 The tensile rate during the uniaxial tensile test was 20 mm / min, and the tensile rate during the stepped cyclic tensile test was 50 mm / min.

[0142] Figure 1 The copolymer elastomer prepared in Example 1 13 C10 NMR spectrum.

[0143] Figure 2 The copolymer elastomer prepared in Example 1 13 C10 NMR spectrum.

[0144] Figure 3 The GPC curves are for the copolymer elastomers prepared in Examples 1-3.

[0145] Figure 4 The DSC curve of the copolymer elastomer prepared in Example 1 is shown.

[0146] Figure 5 The stress-strain diagram is for the copolymer elastomer prepared in Example 2.

[0147] Figure 6 Stress-strain cycle diagram of the copolymer elastomer prepared for Example 2.

[0148] Figure 7 Stress-strain cycle diagram of the copolymer elastomer prepared for Example 3.

[0149] Figure 8 Stress-strain diagram of the copolymer elastomer prepared for Comparative Example 2.

[0150] Figure 9 Stress-strain cycle diagram of the copolymer elastomer prepared for Comparative Example 2.

[0151] The polymerization data and thermodynamic data of the copolymer elastomers prepared for Examples 1-12 and Comparative Examples 1-2 are shown in Table 2, and the mechanical property data are shown in Table 3.

[0152] Table 2

[0153]

[0154] wherein, the insertion rate of the silicon-containing α,ω-diene is the molar content of the silicon-containing five-membered ring structure unit in the copolymer elastomer, and the insertion rate of the α-olefin is the molar content of the α-olefin structure unit in the copolymer elastomer. There is no melting point data for Example 3 because the copolymer elastomer obtained in Example 3 is an amorphous polymer.

[0155] Table 3

[0156]

[0157] wherein, the breaking strength, breaking elongation and toughness are obtained by uniaxial tensile test, and the elastic recovery rate is obtained by step cycle tensile test.

[0158] From Table 3, it can be seen that the copolymer elastomers prepared in the examples of the present application have excellent elastic recovery rate while the breaking strength is not too low, i.e. a good balance between strength and elastic recovery rate is achieved. While the breaking strength of Comparative Example 2 is reduced to the level of Example 3, the elastic recovery rate achieved is only 76%, far less than 98% of Example 3.

[0159] In addition, after replacing the silicon-containing five-membered ring structure unit with a silicon-containing six-membered ring structure unit, the strength and elasticity of Comparative Example 1 are significantly reduced compared with Example 1.

[0160] The above described embodiments are only to illustrate the preferred modes of the present application, and are not intended to limit the scope of the present application. Any modification and improvement made by those skilled in the art to the technical solutions of the present application without departing from the design spirit of the present application shall fall within the protection scope of the present application.

Claims

1. A propylene / α-olefin copolymer elastomer containing silicon five-membered ring structural units, characterized in that, The propylene / α-olefin copolymer elastomer containing silicon five-membered ring structural units is composed of 2~20 mol% α-olefin structural units, 5~10 mol% silicon five-membered ring structural units and the balance propylene structural units. The structural formula of the propylene / α-olefin copolymer elastomer containing silicon-containing five-membered ring structural units is as follows: ; Where x is 0.05~0.10, y is 0.02~0.20, N is selected from 7, 9, 11, 13, 15 and 17, and R1 and R2 are independently selected from -CH3 or -Ph respectively; The preparation steps of the propylene / α-olefin copolymer elastomer containing silicon five-membered ring structural units include: Using propylene, α-olefin and silicon-containing α,ω-diene as monomers, random copolymerization reaction is carried out in the presence of catalyst, co-catalyst and chain transfer agent to obtain the propylene / α-olefin copolymer elastomer with silicon-containing five-membered ring structural unit. The silicon-containing α,ω-diene includes one of allyl vinyl dimethylsilane, allyl vinyl diphenylsilane, and allyl vinyl methyl phenylsilane; The α-olefins include one or more of 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; The catalyst includes a pyridineamine hafnium metal catalyst; The co-catalyst includes an organoboron salt; The chain transfer agent includes triisobutylaluminum; The molar ratio of the catalyst to the chain transfer agent is 1:5~500; The molar ratio of the catalyst to the silicon-containing α,ω-diene is 1:500~2000; The molar ratio of the α-olefin and the silicon-containing α,ω-diene is 1:0.1~10; The molar ratio of the catalyst to the co-catalyst is 1:1 to 3000.

2. The propylene / α-olefin copolymer elastomer containing silicon-containing five-membered ring structural units as described in claim 1, characterized in that, The random copolymerization reaction is carried out in a hydrocarbon solvent.

3. The propylene / α-olefin copolymer elastomer containing silicon-containing five-membered ring structural units as described in claim 2, characterized in that, The random copolymerization reaction using propylene, α-olefin, and silicon-containing α,ω-diene as monomers, under the action of a catalyst, co-catalyst, and chain transfer agent, to obtain the propylene / α-olefin copolymer elastomer containing silicon five-membered ring structural units comprises: First, a mixture of silicon-containing α,ω-diene, α-olefin, chain transfer agent, and hydrocarbon solvent is introduced, followed by the introduction of propylene gas and the addition of catalyst and co-catalyst to carry out a random copolymerization reaction.

4. The propylene / α-olefin copolymer elastomer containing silicon-containing five-membered ring structural units as described in claim 3, characterized in that, The random copolymerization reaction takes 2-30 min; after the random copolymerization reaction takes 2-30 min, the reaction is terminated by adding ethanol to obtain a reaction solution, which is then mixed with a precipitant for sedimentation, followed by filtration, washing, and vacuum drying.

5. The use of a propylene / α-olefin copolymer elastomer containing silicon five-membered ring structural units as described in claim 1 in the preparation of elastic shoe soles, bouncy ball toys, automotive sealing strips, or elastic swimwear.

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