A dielectric elastomer with high dielectric constant and its preparation method and application

By chemically modifying butadiene-pentadiene rubber and introducing high dipole moment polar groups, the problem of low dielectric constant was solved, and a dielectric elastomer with a high dielectric constant was prepared, achieving excellent rebound performance and mechanical properties at a lower driving voltage, thereby expanding the scope of application.

CN119978173BActive Publication Date: 2025-09-12SHANDONG HAOHUA TIRE CO LTD +1
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Patent Information

Application Number
CN202510473032.1
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2025-04-16
Publication Date
2025-09-12
Estimated Expiration
2045-04-16

AI Technical Summary

Technical Problem

The dielectric constant of existing rubber materials is low, resulting in a low electrodeformation of the prepared dielectric elastomer, which requires a higher driving voltage, limiting the application range of the device and shortening its service life. At the same time, the resilience of polar rubber is limited by the high polar group content on the main chain.

Method used

By chemically modifying butadiene-pentadiene rubber with a high double bond side group content and introducing polar groups with high dipole moment, a dielectric elastomer with a high dielectric constant is prepared. The number of polar groups and the vulcanization process are adjusted to control its electrical and mechanical properties.

Benefits of technology

A dielectric elastomer material with excellent rebound performance, mechanical properties and high dielectric constant has been obtained. It can achieve better rebound performance at a smaller driving voltage, expand the scope of application, and is suitable for fields such as flexible actuators and soft robots.

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Abstract

The present application relates to a dielectric elastomer with a high dielectric constant, a preparation method and an application thereof, and belongs to the technical field of dielectric elastomers. In the present application, a non-polar rubber such as butadiene-vinyl rubber with a high double bond side group content is modified, specifically by introducing a high dipole moment polar group into the butadiene-vinyl rubber molecular chain by chemical modification, thereby obtaining a dielectric elastomer rubber material with a high dielectric constant. The dielectric constant can also be adjusted by adjusting the number of introduced polar groups, and the mechanical properties can be adjusted by adjusting the vulcanization process, thereby enabling the control of the electrical and mechanical properties of the butadiene-vinyl rubber dielectric elastomer, thereby expanding the applicable field of the butadiene-vinyl rubber dielectric elastomer. In addition, the material also has high elasticity, which is of great significance for its application in flexible actuators, soft robots and other fields.
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Description

Technical Field

[0001] The present application relates to a dielectric elastomer with a high dielectric constant and a preparation method and application thereof, belonging to the technical field of dielectric elastomer materials. Background Art

[0002] Dielectric elastomer (DE) actuators are essentially deformable capacitors. Their basic structure is a sandwich structure formed by coating a layer of flexible electrodes on the upper and lower surfaces of a dielectric elastomer film. When a certain voltage is applied to the flexible electrodes on the upper and lower surfaces of the DE film, electrostatic attraction is generated between the opposite charges on the upper and lower surfaces, while like charges on the same side repel each other, causing the DE film to shrink in thickness and expand in plane. After power is removed, it can return to its original shape, thereby realizing the mutual conversion between electrical energy and mechanical energy.

[0003] Rubber materials have become ideal materials for large-scale preparation of DE due to their excellent resilience and low cost. However, commonly used rubber materials such as butadiene-pentadiene rubber, natural rubber, styrene-butadiene rubber, butyl rubber, etc. have low dielectric constants, resulting in low electrodeformability of the prepared DE. Therefore, a higher driving voltage needs to be applied, which not only limits the application range of the device but also shortens the service life of the device.

[0004] At present, researchers generally use polar rubbers such as chloroprene rubber and nitrile rubber to prepare DE. However, there is a problem that the high polar group content on the main chain of the rubber molecule restricts the movement of the molecular chain, which greatly weakens the resilience of the polar rubber. In addition, its dielectric constant still needs to be improved.

[0005] Therefore, providing a DE material with a high dielectric constant, a flexible rubber main chain and good resilience is a technical problem that needs to be solved urgently and is of great significance. Summary of the Invention

[0006] In order to solve the above problems, a dielectric elastomer with a high dielectric constant, a preparation method thereof and an application thereof are provided. By modifying non-polar rubber such as butadiene-vinyl rubber with a high double bond side group content, specifically by introducing high dipole moment polar groups into the butadiene-vinyl rubber molecular chain through chemical modification, a dielectric elastomer rubber material with a high dielectric constant is obtained. In addition, the dielectric constant of the butadiene-vinyl rubber dielectric elastomer can be adjusted by adjusting the number of introduced polar groups, and the mechanical properties of the butadiene-vinyl rubber dielectric elastomer can be adjusted by adjusting the vulcanization process, thereby achieving control over the electrical and mechanical properties of the butadiene-vinyl rubber dielectric elastomer, expanding the applicable field of the prepared butadiene-vinyl rubber dielectric elastomer, which is of great significance for its application in flexible actuators, soft robots and other fields.

[0007] The present application provides a method for preparing a dielectric elastomer with a high dielectric constant, the preparation method comprising the following steps:

[0008] 1) dissolving butadiene-pentadiene rubber in an organic solvent to obtain butadiene-pentadiene rubber solution;

[0009] 2) Adding a halogenating agent to the butylene-pentadiene rubber solution to carry out a chemical modification reaction;

[0010] 3) Separating and obtaining polar butadiene-vinyl rubber from the butadiene-vinyl rubber solution after the reaction;

[0011] 4) vulcanizing the polar butadiene-pentadiene rubber to obtain the dielectric elastomer with a high dielectric constant.

[0012] In response to the problems existing in dielectric elastomer rubber materials such as chloroprene rubber and nitrile rubber currently used in the existing technology, a new dielectric elastomer material of butadiene-butadiene rubber with a high dielectric constant is provided. It not only has good rebound performance, but also has a high dielectric constant due to the high dipole moment polar groups introduced on its side groups through chemical modification. Compared with polar nitrile rubber, its dielectric constant is increased by about 41%.

[0013] Based on the chemical modification of butadiene-butadiene rubber, a new dielectric elastomer material with excellent rebound performance, mechanical properties and electrical properties was obtained. Its excellent rebound performance, mechanical properties and high dielectric constant enable it to achieve better rebound performance at a smaller driving voltage as a dielectric elastomer, making it a more ideal dielectric elastomer material than existing chloroprene rubber and nitrile rubber.

[0014] Optionally, the butadiene-vinyl rubber includes four structural units: 1,2-butadiene, 1,4-butadiene, 3,4-isoprene and 1,4-isoprene; the sum of the amounts of the 1,2-butadiene and 3,4-isoprene substances accounts for more than 40% of the total amount of the four structural unit substances.

[0015] Optionally, the sum of the amounts of the 1,2-butadiene and 3,4-isoprene substances accounts for 40-80% of the total amount of the four structural unit substances.

[0016] The NBR used is a raw NBR with a high content of pendant double bonds, such as vinyl and propylene. Because pendant double bonds are more reactive than those in the main chain, chemical modification allows more polar groups in the NBR to be grafted onto the pendant double bonds, thus preventing damage to the rubber backbone's flexibility. For example, sulfonyl chloride, a halogenating agent, reacts with pendant double bonds to form polar chlorine atoms or sulfur-containing ester groups.

[0017] The introduction of polar functional groups has the following effects: 1) The more polar functional groups introduced, the higher the dielectric constant of the elastomer; 2) However, the introduction of polar functional groups reduces the flexibility of the original molecular chain. When the flexibility of the rubber molecular chain is low, the resilience of the resulting modified rubber elastomer will deteriorate; 3) At the same time, the introduction of too many polar functional groups reduces the breakdown strength of the rubber material, making it unsuitable for use in high electric field environments. Within a reasonable range, elastic properties can be simultaneously achieved with high dielectric constant and high breakdown strength.

[0018] Optionally, the halogenating agent is one or more of N-chlorosuccinimide, sulfonyl chloride, trichloroisocyanuric acid and imidazole chloride ionic liquid.

[0019] It should be noted that, in addition to the halogenating agents listed above, other halogenating agents that can react with double bonds and increase polar groups can achieve the same technical effect of the present application scheme, and by increasing polar groups, a butadiene-butadiene rubber dielectric elastomer with a high dielectric constant can be obtained.

[0020] Optionally, the 1,4-butadiene includes cis-1,4-butadiene and trans-1,4-butadiene, and the 1,4-isoprene includes cis-1,4-isoprene and trans-1,4-isoprene;

[0021] The sum of the amounts of the cis-1,4-butadiene and cis-1,4-isoprene substances accounts for 50-80% of the total amount of the 1,4-butadiene and 1,4-isoprene substances.

[0022] The above content represents the proportion of cis structures in the main chain. A higher content indicates a more flexible main chain. Conversely, a higher trans structure content indicates less flexibility. A flexible main chain is beneficial for rebound performance but detrimental to tensile strength. Products within the above range can achieve a balance between elasticity and tensile strength.

[0023] Optionally, the molecular weight of the butadiene-pentadiene rubber is 50~100w.

[0024] If the molecular weight of the butadiene-vinyl rubber used is too low, the comprehensive mechanical properties of the product will be reduced. If the molecular weight of the butadiene-vinyl rubber is too high, problems such as extrusion deformation and stress concentration will easily occur in subsequent processing techniques such as extrusion and molding, resulting in poor processing performance.

[0025] Optionally, the molecular weight distribution of the butadiene-pentadiene rubber is 1.0-3.0.

[0026] The molecular weight distribution represents the uniformity of the molecular weight distribution of the butadiene-vinyl rubber (BPV) in the dielectric elastomer. Lower molecular weight distribution values ​​indicate a more uniform molecular weight distribution. When used in dielectric elastomers, this can reduce hysteresis and thus improve rebound performance, but at the expense of slightly poorer processing performance. Higher molecular weight distribution values ​​indicate an uneven molecular weight distribution, which is detrimental to rebound performance but beneficial to processing performance. However, the butadiene-vinyl rubber (BPV) within the above range in the present application can achieve both processing and rebound performance.

[0027] Optionally, the mass ratio of the halogenated reagent to the butadiene-vinyl rubber is (10-50):100. The above ratio affects the degree of modification of the polar group. Within the above range, elastic properties, high dielectric constant and high breakdown strength properties can be taken into account at the same time.

[0028] Optionally, the reaction temperature of the chemical modification reaction is 15-70° C., and the reaction time is 0.5-24 h.

[0029] Those skilled in the art can set and adjust this according to the situation. For example, when the temperature is higher, the reaction is faster, so the reaction time can be controlled to be shorter, and vice versa.

[0030] Optionally, the reaction temperature of the chemical modification reaction is 30-60° C., and the reaction time is 1-8 hours.

[0031] The reaction rate under the above conditions is easy to control and the production efficiency is also higher.

[0032] Optionally, stirring is performed during the chemical modification reaction, and the stirring speed is 50-1000 rpm.

[0033] It should be noted that those skilled in the art can make selections and adjustments according to circumstances. For example, by adding stirring operations, the reaction time can be shortened.

[0034] Optionally, the stirring speed is 200~700rpm.

[0035] Optionally, the organic solvent is one or more of toluene, dichloromethane, tetrahydrofuran, petroleum ether, and xylene.

[0036] It should be noted that, in addition to the organic solvents listed above, other solvents that can dissolve the reactants and provide a reaction environment can achieve the same effect, and those skilled in the art can select them as needed.

[0037] Optionally, the organic solvent is one or both of dichloromethane and tetrahydrofuran.

[0038] Optionally, the process of separating the polar butadiene-pentadiene rubber from the butadiene-pentadiene rubber solution after the reaction comprises the following steps:

[0039] S1. Adding a precipitant to precipitate the polar butadiene-pentadiene rubber;

[0040] S2, deionized water cleaning;

[0041] S3. After drying, polar butadiene-pentadiene rubber is obtained.

[0042] Optionally, the precipitant is one or more of methanol, ethanol, and acetone. It should be noted that, in addition to the precipitants listed above, those skilled in the art may also select other suitable precipitants.

[0043] Optionally, the vulcanizing agent used in the vulcanization of the polar butadiene-pentadiene rubber is one or more of sulfur, dibenzoyl peroxide, and dicumyl peroxide.

[0044] Optionally, the vulcanization accelerator used in the vulcanization of the polar butadiene-pentadiene rubber is one or more of CZ, NS, and TMTD.

[0045] Optionally, the mass ratio of polar butadiene-vinyl rubber, vulcanizing agent and vulcanization accelerator in the polar butadiene-vinyl rubber vulcanization is 100: (0.3~5): (0.3~5).

[0046] Optionally, the mass ratio of polar butadiene-vinyl rubber, vulcanizing agent and vulcanization accelerator in the polar butadiene-vinyl rubber vulcanization is 100:(0.5~3):(0.5~3).

[0047] During the vulcanization process, it is necessary to pay attention to controlling the amount of sulfur used as the vulcanizing agent. If the amount of vulcanizing agent is too low, the mechanical properties will be poor; if the amount is too high, the tensile modulus will be high, requiring a higher driving voltage, which may cause breakdown. Therefore, the amount of sulfur needs to be controlled within an appropriate range.

[0048] Optionally, the polar butadiene-pentadiene rubber is vulcanized at a vulcanization temperature of 130-170° C. and a vulcanization time of 5-120 min.

[0049] Optionally, the polar butadiene-pentadiene rubber is vulcanized at a vulcanization temperature of 140-160° C. and a vulcanization time of 10-30 minutes.

[0050] The preparation of the new dielectric elastomer material in the present application is based on chemical modification of butadiene-pentadiene rubber to increase its polarity. This method is simple and fast to operate, has a high yield and a low overall production cost, and is extremely suitable for industrial production.

[0051] The present application provides a dielectric elastomer with a high dielectric constant, wherein the dielectric elastomer has the following structure:

[0052]

[0053] And satisfy 0.2≤(a+d) / (a+b+c+d+e+f)≤0.6;

[0054] R is one or more of -Cl, -SO3H, -Br, and -I.

[0055] It should be noted that the sum of the amounts of 1,2-butadiene and 3,4-isoprene in the butadiene-vinyl rubber used accounts for more than 40% of the total amount of the four structural unit substances. The polar group partially modifies the side double bond, so the proportion of the modified side R group becomes smaller.

[0056] In addition, the above structural formula only reflects the structure modified by the polar group, and also contains side double bonds that are not modified by the polar group. Those skilled in the art can clearly understand the structure of the dielectric elastomer with a high dielectric constant in this application based on the above structural formula and reaction conditions and process.

[0057] The present application provides the dielectric elastomer prepared by the above-mentioned preparation method of the dielectric elastomer with a high dielectric constant or the application of the above-mentioned dielectric elastomer with a high dielectric constant in the fields of wearable electronics, flexible sensors, electronic skin, artificial muscles and soft robots.

[0058] The beneficial effects of this application include but are not limited to:

[0059] 1. The dielectric elastomer with a high dielectric constant, its preparation method, and its application disclosed herein address the problems of existing dielectric elastomer rubber materials such as chloroprene rubber and nitrile rubber. By providing a new dielectric elastomer material with a high dielectric constant, the material not only exhibits excellent rebound properties but also exhibits a high dielectric constant due to the introduction of high-dipole-moment polar groups into its chain structure through chemical modification. Compared to polar nitrile rubber, its dielectric constant is increased by approximately 41%.

[0060] 2. The dielectric elastomer with a high dielectric constant, its preparation method, and its application disclosed herein, based on the chemical modification of butadiene-vinyl butadiene rubber, yields a new dielectric elastomer material with excellent rebound, mechanical, and electrical properties. Its excellent rebound, mechanical properties, and high dielectric constant enable it to achieve improved rebound performance at a lower driving voltage, making it a more ideal dielectric elastomer material compared to existing chloroprene rubber and nitrile rubber.

[0061] 3. According to the dielectric elastomer with a high dielectric constant disclosed herein, its preparation method, and application, the dielectric constant of the butadiene-vinyl rubber dielectric elastomer can be adjusted by adjusting the number of introduced polar groups, and the mechanical properties of the butadiene-vinyl rubber dielectric elastomer can be adjusted by adjusting the amount of vulcanizing agent added, thereby achieving control over the electrical and mechanical properties of the butadiene-vinyl rubber dielectric elastomer. This expands the applicable fields of the prepared butadiene-vinyl rubber dielectric elastomer, which is of great significance for its application in flexible actuators, soft robotics, and other fields.

[0062] 4. According to the dielectric elastomer with a high dielectric constant, its preparation method, and use disclosed herein, the polarity of the butadiene-vinyl rubber is altered by adding a halogenating agent during chemical modification, thereby not only obtaining a butadiene-vinyl rubber with a higher dielectric constant, butadiene-vinyl rubber also exhibits a higher dielectric constant as the mass fraction of the halogenating agent, reaction temperature, and reaction time increase (within a certain range). Furthermore, as the mass fraction of the halogenating agent, reaction temperature, and reaction time increase, more polar functional groups, such as chlorine atoms or ester groups with sulfur atoms, are introduced into the butadiene-vinyl rubber, resulting in an even higher dielectric constant. Furthermore, because more polar groups are grafted onto pendant double bonds, damage to the flexibility of the rubber backbone is avoided.

[0063] 5. According to the dielectric elastomer with a high dielectric constant, its preparation method, and application disclosed herein, the following effects are achieved by introducing polar functional groups: 1) the more polar functional groups introduced, the higher the dielectric constant of the elastomer; 2) however, the introduced polar functional groups reduce the flexibility of the original molecular chain. When the flexibility of the rubber molecular chain is low, the resilience of the resulting modified rubber elastomer will deteriorate; 3) the introduction of too many polar functional groups reduces the breakdown strength of the rubber material, making it unsuitable for use in high electric field environments. Within a reasonable range, elastic properties, high dielectric constant, and high breakdown strength can be simultaneously achieved.

[0064] 6. According to the dielectric elastomer with a high dielectric constant, its preparation method, and application, the preparation of the new dielectric elastomer material in this application is based on chemically modifying butadiene-vinyl rubber to increase its polarity. This method is simple and quick to operate, has a high yield, and has a low overall production cost, making it highly suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0065] The drawings described herein are used to provide a further understanding of the present application and constitute a part of the present application. The illustrative embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:

[0066] Figure 1 This is the reaction principle diagram of the present application scheme;

[0067] Figure 2 This is a diagram of the dielectric constant test results involved in this application. DETAILED DESCRIPTION

[0068] The present application is described in detail below with reference to examples, but the present application is not limited to these examples. Unless otherwise specified, the raw materials and reagents in the examples of the present application were purchased from commercial sources. For example, the nitrile rubber used in the comparative example tests was purchased from NBR 2850 Japan Zeon Co., Ltd. Unless otherwise specified, the butadiene-vinyl rubber used in the present application was prepared by coordination polymerization using butadiene and isoprene as raw materials using an iron-based catalyst.

[0069] In order to solve the problem that the current non-polar rubber has a low dielectric constant, which limits its application in dielectric elastomer actuators, the present application scheme chemically modifies the butadiene-pentadiene rubber matrix with a high double bond side group content, so that more polar groups are grafted onto the side groups of the molecular chain, thereby greatly improving the dielectric constant while reducing the impact on the flexibility of the molecular main chain. A dielectric elastomer rubber material with both high dielectric constant and high resilience is prepared. The reaction process is as follows: Figure 1 shown.

[0070] The present application is described below through specific embodiments.

[0071] Example 1

[0072] (1) 50 g of raw butadiene-vinyl rubber (the sum of the amounts of 1,2-butadiene and 3,4-isoprene substances accounts for 62% of the total amount of the four structural unit substances, the sum of the amounts of cis-1,4-butadiene and cis-1,4-isoprene substances accounts for 73% of the total amount of 1,4-butadiene and 1,4-isoprene substances, the molecular weight of butadiene-vinyl rubber is 72w, and the molecular weight distribution is 2.1) is cut into small particles and fully dissolved in 1000 mL of tetrahydrofuran until the solution becomes uniform. The concentration of the butadiene-vinyl rubber solution is 5 g / 100 ml;

[0073] (2) At 25°C, N-chlorosuccinimide was added to the N-butyl rubber solution at a weight ratio of 1:6. The mixture was stirred for 2 h at a stirring speed of 600 r / min.

[0074] (3) adding methanol as a precipitant to precipitate the polar butadiene-pentadiene rubber, and then washing and drying the polar butadiene-pentadiene rubber several times to obtain the polar butadiene-pentadiene rubber;

[0075] (4) Add polar butyl rubber, vulcanizing agent, and vulcanization accelerator into an internal mixer at a mass ratio of 100:2:0.8 and mix at 90°C for 4 minutes;

[0076] (5) The uniformly mixed rubber material is placed in a mold and vulcanized at 150°C for 20 minutes to obtain a butylene-pentene rubber dielectric elastomer.

[0077] Example 2

[0078] (1) 50 g of raw butadiene-vinyl rubber (the sum of the amounts of 1,2-butadiene and 3,4-isoprene substances accounts for 42% of the total amount of the four structural unit substances, the sum of the amounts of cis-1,4-butadiene and cis-1,4-isoprene substances accounts for 52% of the total amount of 1,4-butadiene and 1,4-isoprene substances, the molecular weight of butadiene-vinyl rubber is 77w, and the molecular weight distribution is 1.2) is cut into small particles and fully dissolved in 1000 mL of tetrahydrofuran until the solution becomes uniform. The concentration of the butadiene-vinyl rubber solution is 5 g / 100 ml;

[0079] (2) Add sulfonyl chloride to the butyl-pentadiene rubber solution at 15°C, with the weight ratio of sulfonyl chloride to butyl-pentadiene rubber being 1:6, and react for 24 hours;

[0080] (3) adding ethanol as a precipitant to precipitate the polar butadiene-vinyl rubber, washing and drying the precipitated polar butadiene-vinyl rubber several times to obtain the polar butadiene-vinyl rubber;

[0081] (4) Add polar butyl rubber, vulcanizing agent, and vulcanization accelerator into an internal mixer at a mass ratio of 100:2:0.8 and mix at 90°C for 4 minutes;

[0082] (5) The uniformly mixed rubber material is placed in a mold and vulcanized at 150°C for 20 minutes to obtain a butylene-pentene rubber dielectric elastomer.

[0083] Example 3

[0084] (1) 50 g of raw butadiene-vinyl rubber (the sum of the amounts of 1,2-butadiene and 3,4-isoprene substances accounts for 80% of the total amount of the four structural unit substances, the sum of the amounts of cis-1,4-butadiene and cis-1,4-isoprene substances accounts for 79% of the total amount of 1,4-butadiene and 1,4-isoprene substances, the molecular weight of butadiene-vinyl rubber is 64w, and the molecular weight distribution is 2.9) is cut into small particles and fully dissolved in 1000 mL of tetrahydrofuran until the solution becomes uniform. The concentration of the butadiene-vinyl rubber solution is 5 g / 100 ml;

[0085] (2) Add trichloroisocyanuric acid to the butylene-butadiene rubber solution at 70°C. The weight ratio of trichloroisocyanuric acid to butylene-butadiene rubber is 1:6. Stir continuously for 0.5 h at a stirring speed of 200 r / min.

[0086] (3) adding acetone as a precipitant to precipitate the polar butadiene-pentadiene rubber, washing and drying the precipitated polar butadiene-pentadiene rubber several times to obtain the polar butadiene-pentadiene rubber;

[0087] (4) Add polar butyl rubber, vulcanizing agent, and vulcanization accelerator into an internal mixer at a mass ratio of 100:2:0.8 and mix at 90°C for 4 minutes;

[0088] (5) The uniformly mixed rubber material is placed in a mold and vulcanized at 150°C for 20 minutes to obtain a butylene-pentene rubber dielectric elastomer.

[0089] Example 4

[0090] In this embodiment, the weight ratio of the added N-chlorosuccinimide to the added butadiene-vinyl rubber is 1:1, and the other conditions are the same as those in Example 1.

[0091] Example 5

[0092] In this embodiment, the weight ratio of the added N-chlorosuccinimide to the added butadiene-vinyl rubber is 1:15, and the other conditions are the same as those in Example 1.

[0093] Example 6

[0094] The sum of the amounts of 1,2-butadiene and 3,4-isoprene in the butadiene-vinyl rubber used in this embodiment accounts for 41% of the total amount of the four structural unit substances, and the other conditions are the same as those in Example 1.

[0095] Example 7

[0096] The sum of the amounts of 1,2-butadiene and 3,4-isoprene in the butadiene-vinyl rubber used in this embodiment accounts for 30% of the total amount of the four structural unit substances, and the other conditions are the same as those in Example 1.

[0097] Example 8

[0098] The molecular weight of the butadiene-vinyl rubber used in this embodiment is 30w, and the other conditions are the same as those in Example 1.

[0099] Example 9

[0100] The molecular weight distribution of the butadiene-vinyl butadiene rubber used in this embodiment is 4.3, and the other conditions are the same as those in Example 1.

[0101] Comparative Example 1

[0102] The difference between Comparative Example 1 and Example 1 is that the butadiene-pentadiene rubber is replaced by styrene-butadiene rubber, and the other conditions are the same as those of Example 1.

[0103] Comparative Example 2

[0104] The nitrile rubber purchased for testing its mechanical properties, dielectric constant and breakdown voltage was NBR 2850 from Japan Zeon Co., Ltd.

[0105] Test Method

[0106] The dielectric elastomers obtained in the examples and comparative examples were subjected to the following performance tests.

[0107] Mechanical property measurement: According to the national standard GB / T 589-2008, the dielectric elastomer sample is a 100 mm × 4 mm × 1 mm specimen.

[0108] Dielectric constant determination: The dielectric constant is tested at room temperature using an impedance meter at a frequency of 100 to 10 6 The dielectric elastomer sample is a disc with a diameter of 2 cm and a thickness of 1 mm.

[0109] Breakdown Strength Measurement: Copper electrodes are deposited on the upper and lower surfaces of the dielectric elastomer material. A DC high-voltage power supply is then connected to the positive and negative electrodes of the electrodes and a voltage is applied to the material to measure the breakdown strength.

[0110] The test results are shown in Table 1 below, where the dielectric constant test results are as follows: Figure 2 shown.

[0111] Table 1 Test results of dielectric elastomer properties of examples and comparative examples

[0112]

[0113] According to the results in Table 1, compared with Examples 1 to 3: Example 4 increases the amount of halogenated reagent, resulting in a significant increase in the dielectric constant, but a significant decrease in the breakdown strength; Example 5 reduces the amount of halogenated reagent, the dielectric constant increases slightly, but the breakdown strength remains at a high level; the double bond side group content of the butadiene-pentadiene rubber used in Example 6 is low, so the dielectric constant increases relatively little, because part of the main chain double bonds react with the halogenated reagent, thereby increasing the initial modulus and decreasing the breakdown strength; the double bond side group content of the butadiene-pentadiene rubber used in Example 7 is further reduced, resulting in the main chain double bonds being reacted with the halogenated reagent, so the dielectric constant and the breakdown strength are significantly decreased. The breakdown strength decreased and the tensile properties were also affected; Example 8 used butadiene-vinyl rubber with a lower molecular weight, which resulted in a decrease in the mechanical properties of the material; Example 9 used butadiene-vinyl rubber with a higher molecular weight distribution, and the mechanical properties of the material also decreased; Comparative Example 1 used styrene-butadiene rubber for modification. Due to the low content of side double bonds and the large steric hindrance of the benzene ring, the dielectric constant of the modified styrene-butadiene rubber was low and the initial modulus was high, making it unsuitable for use as a dielectric elastomer material; Comparative Example 2 tested commercial nitrile rubber. Although the dielectric constant was high, the breakdown strength was too low, and it was also unsuitable for direct use as a dielectric elastomer material.

[0114] The foregoing is merely an embodiment of the present application, and the scope of protection of the present application is not limited by these specific embodiments, but is determined by the claims of the present application. For those skilled in the art, the present application may have various modifications and variations. Any modifications, equivalent substitutions, improvements, etc. made within the technical ideas and principles of the present application should be included in the scope of protection of the present application.

Claims

1. A method for preparing a dielectric elastomer with a high dielectric constant, characterized in that: The preparation method comprises the following steps: 1) dissolving butadiene-pentadiene rubber in an organic solvent to obtain butadiene-pentadiene rubber solution; 2) Adding a halogenating agent to the butylene-pentadiene rubber solution to carry out a chemical modification reaction; 3) Separating and obtaining polar butadiene-vinyl rubber from the butadiene-vinyl rubber solution after the reaction; 4) vulcanizing the polar butadiene-pentadiene rubber to obtain the dielectric elastomer having a high dielectric constant; The butadiene-vinyl rubber comprises four structural units, namely 1,2-butadiene, 1,4-butadiene, 3,4-isoprene and 1,4-isoprene; the sum of the amounts of the 1,2-butadiene and 3,4-isoprene substances accounts for more than 40% of the total amount of the four structural units; the 1,4-butadiene comprises cis-1,4-butadiene and trans-1,4-butadiene, and the 1,4-isoprene comprises cis-1,4-isoprene and trans-1,4-isoprene; the sum of the amounts of the cis-1,4-butadiene and cis-1,4-isoprene substances accounts for 50-80% of the total amount of the 1,4-butadiene and 1,4-isoprene substances; The molecular weight of the butadiene-vinyl rubber is 50-100w, and the molecular weight distribution of the butadiene-vinyl rubber is 1.0-3.0; the halogenation agent is one or more of N-chlorosuccinimide, sulfonyl chloride, trichloroisocyanuric acid and chloride imidazole ionic liquid.

2. The method for preparing a dielectric elastomer with a high dielectric constant according to claim 1, characterized in that: The mass ratio of the halogenating agent to the butadiene-pentadiene rubber is (10-50):

100.

3. The method for preparing a dielectric elastomer with a high dielectric constant according to claim 1, wherein: The reaction temperature of the chemical modification reaction is 15-70° C., and the reaction time is 0.5-24 h.

4. A dielectric elastomer with a high dielectric constant, characterized in that The dielectric elastomer has the following structure: And satisfy 0.2≤(a+d) / (a+b+c+d+e+f)≤0.6; R is one or more of -Cl, -SO3H, -Br, and -I.

5. Application of the dielectric elastomer prepared by the method for preparing a dielectric elastomer with a high dielectric constant according to any one of claims 1 to 3 or the dielectric elastomer with a high dielectric constant according to claim 4 in the fields of wearable electronics, flexible sensors, electronic skin, artificial muscles and soft robots.

Citation Information

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