Propylene / alpha-olefin copolymer elastomer containing silicon five-membered ring structural unit and preparation method of propylene / alpha-olefin copolymer elastomer

Abstract

The invention discloses a propylene / alpha-olefin copolymer elastomer containing a silicon five-membered ring structural unit and a preparation method of the propylene / alpha-olefin copolymer elastomer, and belongs to the technical field of polymer preparation. The propylene / alpha-olefin copolymer elastomer containing the silicon-containing five-membered ring structural unit consists of 2 to 20 mol percent of alpha-olefin structural unit, 5 to 10 mol percent of silicon-containing five-membered ring structural unit and the balance of propylene structural unit. The glass transition temperature of the propylene / alpha-olefin copolymer elastomer containing the silicon five-membered ring structural unit is-20 DEG C to 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 >, the elastic recovery rate is 60-98%, and the propylene / alpha-olefin copolymer elastomer containing the silicon five-membered ring structural unit has the advantages of being low in glass transition temperature, high in strength, good in toughness, high in elasticity and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer preparation, and particularly relates to a propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit and a preparation method thereof. Background Art

[0002] Polyolefin elastomer (POE) is an ethylene-octene copolymer, and the octene content thereof is between 20 and 30 mol%. The properties of POE mainly depend on the octene content. When the octene content increases, the tensile strength and hardness decrease, the elongation at break increases, and the elastic properties are enhanced; when the octene content decreases, the tensile strength and hardness increase, the elongation at break decreases, and the plasticity is enhanced. POE has a wide range of uses. It can be used as a rubber, a thermoplastic elastomer, a plastic modifier and a toughening agent. It can not only toughen and modify polyolefin plastics compatible with it, but also modify engineering plastics such as nylon and polyester that are incompatible with it. Compared with ethylene propylene diene monomer rubber (EPDM), ethylene propylene rubber (EPM), and styrene-butadiene-styrene (SBS), POE has its unique advantages: First, it has excellent processing performance and mechanical properties. Commercial POE is in a free-flowing particle state, which is easier to mix with polymers; although the Mooney viscosity is low, the mechanical properties can be comparable to those of high Mooney viscosity materials, eliminating the disadvantages of general elastomers with low Mooney viscosity, good processing performance but poor mechanical properties. Second, after crosslinking, the thermal aging, ultraviolet resistance, weather resistance, etc. are all better than EPDM. Third, POE has a low embrittlement temperature and the best toughening effect on PP. While toughening, it can still maintain a relatively high yield strength and fluidity. When the content of the comonomer is controlled within a certain range, in addition to ethylene-octene copolymers, ethylene-olefin copolymers such as ethylene-butene copolymers and ethylene-hexene copolymers also exhibit elastomeric properties and are called generalized polyolefin elastomers.

[0003] However, the existing POE still has problems of poor mechanical properties, especially poor tensile strength or elastic recovery rate. Moreover, since the elastic recovery rate and the tensile strength show a trade-off relationship. Copolymers with low crystallinity have good elastic recovery rates but usually weak strengths. Therefore, in the process of developing new polyolefin elastomers, achieving a good balance between elastic recovery and mechanical strength is a challenge. And how to obtain a polyolefin elastomer with a good balance between elastic recovery and mechanical strength is the focus of current research by those skilled in the art. Summary of the Invention

[0004] The object of the present invention is to provide a propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit and a preparation method thereof to solve the problems existing in the above-mentioned prior art.

[0005] To achieve the above object, the present invention provides the following solutions:

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

[0007] The raw material of the silicon-containing five-membered ring structural unit includes one of allyl vinyl dimethylsilane, allyl vinyl diphenylsilane, and allyl vinyl methylphenylsilane;

[0008] 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.

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

[0010] In the present invention, by introducing a silicon-containing rigid cyclic structural unit and long branches into the copolymer backbone, the mechanical properties of the polymer are improved. First, the introduction of long-chain α-olefins can reduce the crystallinity of the polymer, effectively improving its toughness and elastic recovery properties, and the introduction of the cyclic structure can enable the copolymer to maintain good mechanical strength. Through the synergistic cooperation of long-chain α-olefins and the cyclic structure, a copolymer elastomer with relatively good mechanical strength and elastic recovery rate can be obtained.

[0011] The reason why the present invention chooses to introduce a silicon-containing five-membered ring structural unit rather than a four-membered ring structural unit or a six-membered ring structural unit is that the ring tension of the four-membered ring is too large to be synthesized, while the ring formed by the six-membered ring is too large and cannot be completely cyclized, and may carry pendant double bonds, which is likely to cause crosslinking and affect the mechanical properties of the material.

[0012] Further, the weight average molecular weight (M w ) of the ethylene / 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.

[0013] Another technical solution of the present invention: A preparation method of the ethylene / α-olefin copolymer elastomer containing the silicon-containing five-membered ring structural unit, comprising the following steps:

[0014] Using propylene, α-olefin and silicon-containing α,ω-diene as reaction monomers, a random copolymerization reaction is carried out 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 structural unit;

[0015] The silicon-containing α,ω-diene includes one of allylvinyl dimethylsilane, allylvinyl diphenylsilane, diallyl dimethylsilane, diallyl methylphenylsilane and diallyl diphenylsilane;

[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 allylvinyl dimethylsilane.

[0019] Furthermore, the catalyst includes a pyridineamine hafnium metal catalyst.

[0020] Furthermore, the cocatalyst includes an organic borate.

[0021] Furthermore, the chain transfer agent includes triisobutylaluminum.

[0022] Furthermore, the random copolymerization reaction is carried out in a hydrocarbon compound solvent.

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

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

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

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

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

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

[0029] Furthermore, the preparation method of the propylene / α-olefin copolymer elastomer containing a silicon five-membered ring structural unit by subjecting propylene, an α-olefin, and a silicon-containing α,ω-diene as reaction monomers to a random copolymerization reaction under the action of a catalyst, a cocatalyst, and a chain transfer agent includes:

[0030] First, mix the silicon-containing α,ω-diene, α-olefin, chain transfer agent, and hydrocarbon compound solvent, then introduce propylene gas, and add the catalyst and cocatalyst to carry out a random copolymerization reaction (propylene gas is continuously introduced until the random copolymerization reaction ends).

[0031] Furthermore, the time of the random copolymerization reaction is 2 to 30 min.

[0032] Furthermore, after the random copolymerization reaction for 2 to 30 min, it further includes the steps of adding ethanol to terminate the random copolymerization reaction to obtain a reaction solution, mixing the reaction solution with a precipitant, carrying out sedimentation, and then filtering, washing, and vacuum drying.

[0033] Furthermore, the precipitant includes a mixed solution of ethanol and hydrochloric acid.

[0034] Optionally, the precipitant is composed of ethanol and hydrochloric acid with a concentration of 37 wt% in a volume ratio of 100:1.

[0035] The third technical solution of the present invention: An application of the above-mentioned propylene / α-olefin copolymer elastomer containing a silicon five-membered ring structural unit in the preparation of elastic shoe soles, elastic ball toys, automotive sealing strips, or elastic swimsuits.

[0036] The present invention uses a silicon-containing α,ω-diene and an α-olefin to copolymerize with propylene to obtain a polyolefin elastomer with a polymer backbone containing a silicon ring rigid cyclic unit and a long side chain, realizing the preparation of a novel polyolefin elastomer with a silicon five-membered ring structural unit in the main chain. Among them, the mechanical properties and thermal properties of the copolymer can be adjusted by controlling the types and contents of the comonomers. High-temperature nuclear magnetic resonance carbon spectrum and hydrogen spectrum are used to characterize the microscopic 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 invention uses a pyridineamine hafnium metal catalyst and a boron-containing compound cocatalyst to form a catalytic system, combined with an alkyl aluminum chain transfer agent, and synthesizes a series of propylene / α-olefin random copolymer elastomers with a silicon five-membered ring structural unit in the main chain and controllable thermodynamic and mechanical properties by adjusting the types and contents of the comonomers. First, based on the fact that the catalyst has a certain copolymerization ability for the silicon-containing α,ω-diene, α-olefin, and propylene, the effects of monomer concentration, monomer type on the polymer composition and properties, and the content of the comonomer on the microstructure are systematically studied to achieve efficient regulation of the mechanical properties of the elastomer.13 The 13C NMR and 1 1H NMR results show that the introduction of the silicon-containing α,ω-diene in the copolymer only forms a cyclic structural unit without branched or crosslinked structures on the ring (i.e., the silicon-containing α,ω-diene is only inserted in a cyclic manner without branched structures). Through uniaxial tensile and stepped cyclic tensile tests, it is found that the introduction of the silicon-containing cyclic structural unit improves the mechanical properties of the material. In addition, the mechanical properties of all elastomers can be optimized by changing the content of the comonomer and the length of the side chain respectively, and elastomers with both high strength and high elastic recovery can be obtained. Therefore, the monomer type and insertion rate play a crucial role in determining the mechanical properties of excellent elastomers.

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

[0039] Currently, there is little research on the controlled copolymerization of silicon-containing dienes with other olefins. In the prior art, silicon-containing polyolefins are mostly synthesized by anionic ring-opening polymerization, condensation polymerization, and coupling reactions. However, the polymers obtained by these methods have relatively low molecular weights and the polymer structures are not clear. Therefore, starting from the controlled polymerization of silicon-containing dienes with other olefins, the present invention prepares an elastomer with a well-defined main chain containing a silicon-containing ring structure and a long side chain structure by optimizing the polymerization conditions, thus promoting the development of high-performance polyolefin elastomers.

[0040] The present invention discloses the following technical effects:

[0041] By introducing a silicon-containing rigid cyclic structural unit and long branched chains into the copolymer backbone, the present invention improves the mechanical properties of the polymer. The glass transition temperature of the propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit of the present invention is -20 - 10 °C, the tensile strength is 7 - 25 MPa, the elongation at break is 1000 - 1600%, the toughness is 10 - 150 MJm -3 , and the elastic recovery rate is 60 - 98%. It has the characteristics of low glass transition temperature, high strength, good toughness, and high elasticity, achieving a balance between strength and elasticity.

[0042] The present invention uses a silicon-containing α,ω-diene, an α-olefin, and propylene as reaction monomers, a hafnium metal catalyst of pyridineamine and a boron compound cocatalyst to form a catalytic system, combined with an alkylaluminum chain transfer agent. By optimizing the polymerization conditions, a polyolefin elastomer with a silicon-containing rigid cyclic unit and a long side chain is copolymerized, thereby realizing the controllable synthesis of a silicon-containing cyclic elastomer in the main chain. The silicon-containing α,ω-diene insertion rate of the propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structure unit prepared by the present invention can be adjusted between 5 and 10 mol%, the α-olefin insertion rate can be adjusted between 2 and 20 mol%, and the molecular weight can be adjusted between 150 and 300 kDa. By adjusting the monomer type and insertion rate, the mechanical properties of the copolymer elastomer can be optimized. Brief Description of the Drawings

[0043] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

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

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

[0046] Figure 3 GPC curves of the copolymer elastomers prepared in Examples 1-3

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

[0048] Figure 5 Stress-strain diagram of the copolymer elastomer prepared in Example 2

[0049] Figure 6 Stress-strain cycle diagram of the copolymer elastomer prepared in Example 2

[0050] Figure 7 Stress-strain cycle diagram of the copolymer elastomer prepared in Example 3

[0051] Figure 8 Stress-strain diagram of the copolymer elastomer prepared in Comparative Example 2

[0052] Figure 9 Stress-strain cycle diagram of the copolymer elastomer prepared in Comparative Example 2​​ Detailed Embodiments

[0053] The various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be construed as a limitation on the present invention, but rather as a more detailed description of certain aspects, features, and implementation manners of the present invention.

[0054] It should be understood that the terms used in the present invention are only for describing specific embodiments and are not intended to limit the present invention. Additionally, for the numerical ranges in the present invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any intermediate value within any stated value or stated range, as well as each smaller range between any other stated value or intermediate value within the stated range, is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded from the range.

[0055] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although the present invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

[0056] Without departing from the scope or spirit of the present invention, various improvements and changes can be made to the specific embodiments of the present invention specification, which are obvious to those skilled in the art. Other embodiments obtained from the specification of the present invention are obvious to those skilled in the art. The specification and examples of the present invention are merely exemplary.

[0057] Regarding the terms "comprising", "including", "having", "containing", etc. used herein, they are all open-ended terms, meaning including but not limited to.

[0058] It should be noted that the aspects not detailedly described in the present invention are all conventional operation means in the art and are not the focus of the present invention.

[0059] As a first aspect of the present invention, the present invention provides a propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit, which is composed of 2 - 20 mol% of α-olefin structural units, 5 - 10 mol% of silicon-containing five-membered ring structural units, and the balance of propylene structural units;

[0060] The raw materials of the silicon-containing five-membered ring structural unit include one of allyl vinyl dimethylsilane, allyl vinyl diphenylsilane, and allyl vinyl methylphenylsilane;

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

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

[0063] Among them, 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 a 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 a 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 regarded as the original polymer matrix, the present invention is equivalent to introducing a silicon-containing rigid cyclic structural unit and long branches into the polypropylene backbone. Through the synergistic cooperation of the long-chain α-olefin and the cyclic structure (the cooperation of their types and insertion rates), a copolymer elastomer with relatively good mechanical strength and elasticity is obtained, achieving a good balance between mechanical strength (i.e., fracture strength) and elastic recovery rate. Isotactic polypropylene generally has a relatively high crystallinity, and crystallization can provide strength as physical cross-linking points. Therefore, isotactic polypropylene has high strength but no elasticity. The insertion of comonomers will disrupt the crystallization of polypropylene, thereby reducing the mechanical strength of the material and increasing the elastic recovery of the material. POEs such as ethylene-octene copolymers are equivalent to inserting comonomers into high-crystalline polymer matrices such as polyethylene and polypropylene, reducing the strength of the original polymer and increasing its elastic recovery. However, the level of improvement in elastic recovery that can be achieved in the prior art is limited, and the limited improvement in elastic recovery is often accompanied by a significant decrease in mechanical strength, and a good balance between mechanical strength and elastic recovery cannot be achieved. Through the technical solution of the present invention, while achieving a significant increase in elastic recovery, it is ensured that the mechanical strength will not be significantly reduced, achieving a good balance between mechanical strength and elastic recovery, and having obvious advantages over the prior art.

[0065] As a preferred embodiment of the present invention, the weight-average molecular weight (M w ) of the propylene / α-olefin copolymer elastomer containing a 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 invention, the present invention provides a method for preparing an elastomer of propylene / α-olefin copolymer containing the above-mentioned silicon-containing five-membered ring structural unit, comprising the following steps:

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

[0068] The silicon-containing α,ω-diene includes one of allyl vinyl dimethylsilane, allyl vinyl diphenylsilane and allyl methylphenylsilane;

[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 invention, the more specific steps of the preparation method include:

[0071] First, mix the silicon-containing α,ω-diene, α-olefin, chain transfer agent and hydrocarbon compound solvent, then introduce propylene gas (the pressure of propylene gas in the reaction vessel is 0.1 MPa, and propylene gas is continuously introduced until the polymerization reaction ends), and add the catalyst and cocatalyst to carry out random copolymerization reaction. After reacting for 2 - 30 min, add ethanol to terminate the polymerization reaction to obtain a reaction solution;

[0072] Mix the reaction solution with a precipitant, carry out sedimentation, then filter, wash and vacuum dry to obtain the elastomer of propylene / α-olefin copolymer containing the silicon-containing five-membered ring structural unit.

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

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

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

[0076] As a preferred embodiment of the present invention, the catalyst includes a pyridineamine hafnium metal catalyst.

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

[0078] As a preferred embodiment of the present invention, the chain transfer agent includes triisobutylaluminum.

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

[0080] As a preferred embodiment of the present invention, the hydrocarbon compound solvent includes one or more of benzene and its homologues, naphthalene and its homologues, alkanes and their homologues, and cycloalkanes and their homologues.

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

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

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

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

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

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

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

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

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

[0090] As a third aspect of the present invention, the present invention provides an application of the above-mentioned propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit in the preparation of elastic shoe soles, elastic ball toys, automotive sealing strips, or elastic swimsuits.

[0091] The structural information of the main raw materials involved in the specific implementation manner of the present invention is shown in Table 1.

[0092] Table 1

[0093]

[0094] The technical solution of the present invention will be further described below in conjunction with specific embodiments.

[0095] Except as otherwise specified, all raw materials used in the following examples and comparative examples are ordinary commercially available products. Among them, the organic borate is [Ph3C][B(C6F5)4].

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

[0097] In the process of synthesizing the catalyst, unless otherwise specified, the operations involved are carried out by professionals familiar with the technical field in an MBraun glove box or under the protection of inert gases such as nitrogen or argon using standard Schlenk techniques. At the same time, the solvents involved in the present invention are anhydrous and oxygen-free solvents after post-treatment. In addition, in the process of preparing the silicon-containing five-membered ring structural unit propylene / α-olefin copolymer elastomer, all polymerization reactions need to be carried out under anhydrous and oxygen-free conditions. The glassware such as ampoules, syringes, and polymerization bottles involved in the preparation steps for weighing and transferring catalysts, cocatalysts, chain transfer agents, solvents, etc. have been treated with anhydrous and oxygen-free conditions. All operations sensitive to moisture and oxygen are carried out by professionals familiar with the technical field in an MBraun glove box or under the protection of nitrogen using standard Schlenk techniques. Steps without specific operation temperature or reaction temperature are carried out at room temperature (20 - 30 °C).

[0098] Example 1

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

[0100] Using a Schlenk experimental apparatus and maintaining a vacuum of -0.1 MPa, successively add 60 mL of toluene, 0.7 mL of allyl vinyl dimethylsilane, 2 mL of 1-hexadecene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) into the polymerization flask. Then, introduce propylene gas (the pressure of propylene gas in the polymerization flask is 0.1 MPa, and propylene gas is continuously introduced until the reaction ends, the same below), stir at 600 rpm for 10 min, and then add 16.8 mL of a pyridylamine hafnium metal catalyst / organic borate / toluene mixed solution (i.e., a mixed solution of pyridylamine hafnium metal catalyst, organic borate, and toluene, containing 10 μmol of pyridylamine hafnium metal catalyst and 20 μmol of organic borate), and stir and react at 600 rpm for 10 min; after the polymerization ends, inject 0.1 mL of ethanol to terminate the polymerization to obtain a reaction solution. Finally, slowly pour the reaction solution dropwise into a beaker containing 500 mL of an ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) mixed solution for precipitation, and then obtain the copolymer elastomer through filtration, washing, and vacuum drying.

[0101] Example 2

[0102] A propylene / α-olefin copolymer elastomer containing a silicon five-membered ring structural unit is prepared as follows:

[0103] Using a Schlenk experimental apparatus and maintaining a vacuum of -0.1 MPa, successively add 60 mL of toluene, 0.7 mL of allyl vinyl dimethylsilane, 3 mL of 1-hexadecene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) into the polymerization flask. Then, introduce propylene gas (0.1 MPa), stir at 600 rpm for 10 min, and then add 15.8 mL of a pyridylamine hafnium metal catalyst / organic borate / toluene mixed solution (containing 10 μmol of pyridylamine hafnium metal catalyst and 20 μmol of organic borate), and stir and react at 600 rpm for 10 min; after the polymerization ends, inject 0.1 mL of ethanol to terminate the polymerization to obtain a reaction solution. Finally, slowly pour the reaction solution dropwise into a beaker containing 500 mL of an ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) mixed solution for precipitation, and then obtain the copolymer elastomer through filtration, washing, and vacuum drying.

[0104] Example 3

[0105] A propylene / α-olefin copolymer elastomer containing a silicon five-membered ring structural unit is prepared as follows:

[0106] Using a Schlenk experimental setup and maintaining a vacuum of -0.1 MPa, successively add 60 mL of toluene, 0.7 mL of allyl vinyl dimethylsilane, 4 mL of 1-hexadecene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) into the polymerization flask. Then, introduce propylene gas (0.1 MPa) and stir at 600 rpm for 10 min. Next, add 14.8 mL of a mixed solution of hafnium pyridylamine metal catalyst / organic borate / toluene (containing 10 μmol of hafnium pyridylamine metal catalyst and 20 μmol of organic borate), and stir and react at 600 rpm for 10 min. After the polymerization ends, inject 0.1 mL of ethanol to terminate the polymerization, obtaining a reaction solution. Finally, slowly pour the reaction solution dropwise into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtain the copolymer elastomer through filtration, washing, and vacuum drying.

[0107] Example 4

[0108] A propylene / α-olefin copolymer elastomer containing a silicon five-membered ring structural unit is prepared as follows:

[0109] Using a Schlenk experimental setup and maintaining a vacuum of -0.1 MPa, successively add 60 mL of toluene, 0.7 mL of allyl vinyl methyl phenylsilane, 2 mL of 1-tetradecene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) into the polymerization flask. Then, introduce propylene gas (0.1 MPa) and stir at 600 rpm for 10 min. Next, add 16.8 mL of a mixed solution of hafnium pyridylamine metal catalyst / organic borate / toluene (containing 10 μmol of hafnium pyridylamine metal catalyst and 20 μmol of organic borate), and stir and react at 600 rpm for 10 min. After the polymerization ends, inject 0.1 mL of ethanol to terminate the polymerization, obtaining a reaction solution. Finally, slowly pour the reaction solution dropwise into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtain the copolymer elastomer through filtration, washing, and vacuum drying.

[0110] Example 5

[0111] A propylene / α-olefin copolymer elastomer containing a silicon five-membered ring structural unit is prepared as follows:

[0112] Using a Schlenk experimental setup and maintaining a vacuum of -0.1 MPa, successively add 60 mL of toluene, 0.7 mL of allyl vinyl diphenylsilane, 2 mL of 1-tetradecene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) into the polymerization flask. Then, introduce propylene gas (0.1 MPa) and stir at 600 rpm for 10 min. Next, add 16.8 mL of a mixed solution of hafnium pyridylamine metal catalyst / organic borate / toluene (containing 10 μmol of hafnium pyridylamine metal catalyst and 20 μmol of organic borate), and stir and react at 600 rpm for 10 min. After the polymerization ends, inject 0.1 mL of ethanol to terminate the polymerization to obtain a reaction solution. Finally, gradually pour the reaction solution dropwise into a beaker containing a 500 mL ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) mixed solution for sedimentation, and then obtain the copolymer elastomer through filtration, washing, and vacuum drying.

[0113] Example 6

[0114] A propylene / α-olefin copolymer elastomer containing a silicon five-membered ring structural unit is prepared as follows:

[0115] Using a Schlenk experimental setup and maintaining a vacuum of -0.1 MPa, successively add 60 mL of toluene, 0.7 mL of allyl vinyl methylphenylsilane, 2 mL of 1-decene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) into the polymerization flask. Then, introduce propylene gas (0.1 MPa) and stir at 600 rpm for 10 min. Next, add 16.8 mL of a mixed solution of hafnium pyridylamine metal catalyst / organic borate / toluene (containing 10 μmol of hafnium pyridylamine metal catalyst and 20 μmol of organic borate), and stir and react at 600 rpm for 10 min. After the polymerization ends, inject 0.1 mL of ethanol to terminate the polymerization to obtain a reaction solution. Finally, gradually pour the reaction solution dropwise into a beaker containing a 500 mL ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) mixed solution for sedimentation, and then obtain the copolymer elastomer through filtration, washing, and vacuum drying.

[0116] Example 7

[0117] A propylene / α-olefin copolymer elastomer containing a silicon five-membered ring structural unit is prepared as follows:

[0118] Using a Schlenk experimental apparatus and maintaining a vacuum of -0.1 MPa, successively add 60 mL of toluene, 0.7 mL of allyl vinyl methyl phenyl silane, 2 mL of 1-octadecene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) into the polymerization flask. Then, introduce propylene gas (0.1 MPa) and stir at 600 rpm for 10 min. After that, add 16.8 mL of a mixed solution of hafnium pyridylamine metal catalyst / organic borate / toluene (containing 10 μmol of hafnium pyridylamine metal catalyst and 20 μmol of organic borate), and stir and react at 600 rpm for 10 min. After the polymerization is completed, inject 0.1 mL of ethanol to terminate the polymerization to obtain a reaction solution. Finally, slowly pour the reaction solution dropwise into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtain the copolymer elastomer through filtration, washing, and vacuum drying.

[0119] Example 8

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

[0121] Using a Schlenk experimental apparatus and maintaining a vacuum of -0.1 MPa, successively add 60 mL of toluene, 0.5 mL of allyl vinyl diphenyl silane, 0.5 mL of 1-hexadecene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) into the polymerization flask. Then, introduce propylene gas (0.1 MPa) and stir at 600 rpm for 10 min. After that, add 18.5 mL of a mixed solution of hafnium pyridylamine metal catalyst / organic borate / toluene (containing 10 μmol of hafnium pyridylamine metal catalyst and 20 μmol of organic borate), and stir and react at 600 rpm for 10 min. After the polymerization is completed, inject 0.1 mL of ethanol to terminate the polymerization to obtain a reaction solution. Finally, slowly pour the reaction solution dropwise into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtain the copolymer elastomer through filtration, washing, and vacuum drying.

[0122] Example 9

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

[0124] Using a Schlenk experimental apparatus and maintaining a vacuum of -0.1 MPa, successively add 60 mL of toluene, 0.5 mL of allyl vinyldiphenylsilane, 0.5 mL of 1-octadecene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) into the polymerization flask. Then, introduce propylene gas (0.1 MPa) and stir at 600 rpm for 10 min. Subsequently, add 18.5 mL of a mixed solution of hafnium pyridylamine metal catalyst / organic borate / toluene (containing 10 μmol of hafnium pyridylamine metal catalyst and 20 μmol of organic borate), and stir and react at 600 rpm for 10 min. After the polymerization ends, inject 0.1 mL of ethanol to terminate the polymerization, obtaining a reaction solution. Finally, slowly pour the reaction solution dropwise into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtain the copolymer elastomer through filtration, washing, and vacuum drying.

[0125] Example 10

[0126] A propylene / α-olefin copolymer elastomer containing a silicon five-membered ring structural unit is prepared as follows:

[0127] Using a Schlenk experimental apparatus and maintaining a vacuum of -0.1 MPa, successively add 60 mL of toluene, 1.5 mL of allyl vinyldiphenylsilane, 0.5 mL of 1-octadecene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) into the polymerization flask. Then, introduce propylene gas (0.1 MPa) and stir at 600 rpm for 10 min. Subsequently, add 17.5 mL of a mixed solution of hafnium pyridylamine metal catalyst / organic borate / toluene (containing 10 μmol of hafnium pyridylamine metal catalyst and 20 μmol of organic borate), and stir and react at 600 rpm for 10 min. After the polymerization ends, inject 0.1 mL of ethanol to terminate the polymerization, obtaining a reaction solution. Finally, slowly pour the reaction solution dropwise into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtain the copolymer elastomer through filtration, washing, and vacuum drying.

[0128] Example 11

[0129] A propylene / α-olefin copolymer elastomer containing a silicon five-membered ring structural unit is prepared as follows:

[0130] Using a Schlenk experimental apparatus and maintaining a vacuum of -0.1 MPa, successively add 60 mL of toluene, 1.5 mL of allyl vinyl diphenylsilane, 0.5 mL of 1-octadecene, 0.5 mL of 1-eicosene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) into the polymerization flask. Then, introduce propylene gas (0.1 MPa) and stir at 600 rpm for 10 min. Subsequently, add 17.0 mL of a mixed solution of hafnium pyridylamine metal catalyst / organic borate / toluene (containing 10 μmol of hafnium pyridylamine metal catalyst and 20 μmol of organic borate), and stir and react at 600 rpm for 10 min. After the polymerization is completed, inject 0.1 mL of ethanol to terminate the polymerization to obtain a reaction solution. Finally, slowly pour the reaction solution dropwise into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtain the copolymer elastomer through filtration, washing, and vacuum drying.

[0131] Example 12

[0132] A propylene / α-olefin copolymer elastomer containing a silicon five-membered ring structural unit is prepared as follows:

[0133] Using a Schlenk experimental apparatus and maintaining a vacuum of -0.1 MPa, successively add 60 mL of toluene, 1.5 mL of allyl vinyl dimethylsilane, 0.5 mL of 1-decene, 0.5 mL of 1-hexadecene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) into the polymerization flask. Then, introduce propylene gas (0.1 MPa) and stir at 600 rpm for 10 min. Subsequently, add 17.0 mL of a mixed solution of hafnium pyridylamine metal catalyst / organic borate / toluene (containing 10 μmol of hafnium pyridylamine metal catalyst and 20 μmol of organic borate), and stir and react at 600 rpm for 10 min. After the polymerization is completed, inject 0.1 mL of ethanol to terminate the polymerization to obtain a reaction solution. Finally, slowly pour the reaction solution dropwise into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtain the copolymer elastomer through filtration, washing, and vacuum drying.

[0134] Comparative Example 1

[0135] A propylene / α-olefin copolymer elastomer containing a silicon five-membered ring structural unit is prepared as follows:

[0136] Using a Schlenk experimental setup and maintaining a vacuum of -0.1 MPa, successively add 60 mL of toluene, 2.0 mL of diallyldimethylsilane, 2 mL of 1-hexadecene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) into the polymerization flask. Then, introduce propylene gas (0.1 MPa) and stir at 600 rpm for 10 min. Next, add 15.5 mL of a mixed solution of hafnium pyridylamine metal catalyst / organic borate / toluene (containing 10 μmol of hafnium pyridylamine metal catalyst and 20 μmol of organic borate), and stir and react at 600 rpm for 10 min. After the polymerization is completed, inject 0.1 mL of ethanol to terminate the polymerization to obtain a reaction solution. Finally, slowly pour the reaction solution dropwise into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtain the copolymer elastomer through filtration, washing, and vacuum drying.

[0137] Comparative Example 2

[0138] A propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit is prepared as follows:

[0139] Using a Schlenk experimental setup and maintaining a vacuum of -0.1 MPa, successively add 60 mL of toluene, 4 mL of 1-eicosene, and 0.5 mL of a toluene solution of triisobutylaluminum (1 mmol / mL) into the polymerization flask. Then, introduce propylene gas (0.1 MPa) and stir at 600 rpm for 10 min. Next, add 15.5 mL of a mixed solution of hafnium pyridylamine metal catalyst / organic borate / toluene (containing 10 μmol of hafnium pyridylamine metal catalyst and 20 μmol of organic borate), and stir and react at 600 rpm for 10 min. After the polymerization is completed, inject 0.1 mL of ethanol to terminate the polymerization to obtain a reaction solution. Finally, slowly pour the reaction solution dropwise into a beaker containing 500 mL of a mixed solution of ethanol / 37 wt% hydrochloric acid (volume ratio 100:1) for sedimentation, and then obtain the copolymer elastomer through 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 are tested for relevant properties. The chemical structure of the copolymer elastomers is characterized by nuclear magnetic resonance spectroscopy (NMR). The molar contents of the α-olefin structural unit and the silicon-containing five-membered ring structural unit (i.e., the insertion rates of α-olefin and silicon-containing α,ω-diene) are obtained through carbon-13 NMR. The thermal properties of the copolymer elastomers are characterized using a differential scanning calorimeter (DSC), and the molecular weight (weight-average molecular weight M w ) and molecular weight distribution (PDI) of the copolymer elastomers are characterized using high-temperature gel permeation chromatography (GPC). Among them, the1 H and 13 C NMR was measured on a Bruker-400 nuclear magnetic resonance spectrometer at 110 °C. TMS was used as the internal standard, and the solvent was deuterated o-dichlorobenzene or deuterated 1,1,2,2-tetrachloroethane. The glass transition temperature (T g ) of the copolymer elastomer was measured by a differential scanning calorimeter (Q2000 DSC). The test conditions were as follows: under a nitrogen atmosphere, the heating / cooling rate was 20 °C / min. The melting temperature (T m ) of the copolymer elastomer was measured by a differential scanning calorimeter (Q2000 DSC). The test conditions were as follows: under a nitrogen atmosphere, the heating / cooling rate was 10 °C / min. Gel permeation chromatography was measured using a PL GPC-220 gel permeation chromatograph. The tester was RI-Laser. PLEasiCal PS-1 was used as the standard sample. The packed column was Plgel 10μm MIXED-BLS, and 1,2,4-trichlorobenzene (TCB) was used as the solvent (0.05 wt% of 2,6-di-tert-butyl-4-methylphenol (BHT) was added as an antioxidant). The test temperature was 150 °C, and the flow rate was 1.0 mL / min. Uniaxial tensile tests and stepped cyclic tensile tests (elongation rates were 100%, 200%, 300%, 400%, 500%, 600%, 700%, 800%, 900%, 1000% respectively) were carried out on the copolymer elastomer. The mechanical properties of the copolymer were measured at room temperature using a universal material testing machine (SANS, CMT4203Ins). A polymer film was prepared by hot pressing with a tetrafluoroethylene template (temperature 180 °C, pressure 8 MPa, time 3 min), and then it was cut into dumbbell-shaped tensile specimens with effective dimensions of 10×2×0.5 mm 3 , and 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 13C NMR spectrum of the copolymer elastomer prepared in Example 1 13 13C NMR spectrum of the copolymer elastomer prepared in Example 1

[0143] Figure 2 13C NMR spectrum of the copolymer elastomer prepared in Example 1 13 13C NMR spectrum of the copolymer elastomer prepared in Example 1

[0144] Figure 3 GPC curves of the copolymer elastomers prepared in Examples 1-3

[0145] Figure 4 DSC curve of the copolymer elastomer prepared in Example 1

[0146] Figure 5 Stress-strain diagram of the copolymer elastomer prepared in Example 2

[0147] Figure 6 The stress-strain cyclic diagram of the copolymer elastomer prepared in Example 2.

[0148] Figure 7 The stress-strain cyclic diagram of the copolymer elastomer prepared in Example 3.

[0149] Figure 8 The stress-strain diagram of the copolymer elastomer prepared in Comparative Example 2.

[0150] Figure 9 The stress-strain cyclic diagram of the copolymer elastomer prepared in Comparative Example 2.

[0151] The polymerization data and thermodynamic data of the copolymer elastomers prepared in 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] Among them, the silicon-containing α,ω-diene insertion rate is the molar content of the silicon-containing five-membered ring structural unit in the copolymer elastomer, and the α-olefin insertion rate is the molar content of the α-olefin structural 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] Among them, the breaking strength, elongation at break and toughness are obtained by uniaxial tensile testing, and the elastic recovery rate is obtained by stepped cyclic tensile testing.

[0158] As can be seen from Table 3, the copolymer elastomer prepared in the examples of the present invention has an excellent elastic recovery rate while the breaking strength is not too low, that is, a good balance between strength and elastic recovery rate is achieved. When the breaking strength of Comparative Example 2 is reduced to the same level as that of Example 3, the achieved elastic recovery rate is only 76%, far lower than 98% of Example 3.

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

[0160] The embodiments described above are only descriptions of the preferred embodiments of the present invention, and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, various deformations and improvements made by those of ordinary skill in the art to the technical solutions of the present invention shall fall within the protection scope determined by the claims of the present invention.

Claims

1. A propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit, characterized in that, The propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit is composed of 2 to 20 mol% of α-olefin structural units, 5 to 10 mol% of silicon-containing five-membered ring structural units, and the balance of propylene structural units; The raw material of the silicon-containing five-membered ring structural unit includes one of allyl vinyl dimethylsilane, allyl vinyl diphenylsilane, and allyl vinyl methylphenylsilane; 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.

2. A method for preparing a propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit as described in claim 1, characterized in that, It includes the following steps: Using propylene, α-olefin, and silicon-containing α,ω-diene as reaction monomers, carrying out a 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 a 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 methylphenylsilane; The α-olefin includes one or more of 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

3. The preparation method according to claim 2, characterized in that, The catalyst includes a pyridineamine hafnium metal catalyst.

4. The preparation method according to claim 2, characterized in that, The cocatalyst includes an organic borate.

5. The preparation method according to claim 2, wherein, The chain transfer agent includes triisobutylaluminum.

6. The preparation method according to claim 2, wherein, The random copolymerization reaction is carried out in a hydrocarbon compound solvent.

7. The preparation method according to claim 2, characterized in that, The molar ratio of the catalyst to the chain transfer agent is 1:5 to 500; and / or, the molar ratio of the catalyst to the silicon-containing α,ω-diene is 1:500 to 2000; and / or, the molar ratio of the α-olefin to the silicon-containing α,ω-diene is 1:0.1 to 10; and / or, the molar ratio of the catalyst to the cocatalyst is 1:1 to 3000.

8. The preparation method according to claim 6, characterized in that, The step of using propylene, α-olefin, and silicon-containing α,ω-diene as reaction monomers and carrying out a 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 a silicon-containing five-membered ring structural unit includes: First, mix the silicon-containing α,ω-diene, α-olefin, chain transfer agent, and hydrocarbon compound solvent, then introduce propylene gas, and add the catalyst and cocatalyst to carry out a random copolymerization reaction.

9. The preparation method according to claim 8, characterized in that, The time of the random copolymerization reaction is 2 to 30 minutes; after the random copolymerization reaction for 2 to 30 minutes, it further includes the steps of adding ethanol to terminate the random copolymerization reaction to obtain a reaction solution, mixing the reaction solution with a precipitant, carrying out sedimentation, and then filtering, washing, and vacuum drying.

10. Application of the propylene / α-olefin copolymer elastomer containing a silicon-containing five-membered ring structural unit as described in claim 1 in the preparation of elastic shoe soles, elastic ball toys, automobile sealing strips, or elastic swimsuits.

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